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Sample records for ketone body flux

  1. Perinatal changes in myocardial supply and flux of fatty acids, carbohydrates, and ketone bodies in lambs

    NARCIS (Netherlands)

    Bartelds, B; Gratama, JWC; Knoester, H; Takens, J; Smid, GB; Aarnoudse, JG; Heymans, HSA; Kuipers, JRG

    No information is available on perinatal changes in myocardial metabolism in vivo. We measured myocardial supply and flux of fatty acids, carbohydrates, and ketone bodies in chronically instrumented fetal, newborn (1-4 days), and juvenile (7 wk) lambs, by measuring aorta-coronary sinus concentration

  2. Ketone bodies in epilepsy.

    Science.gov (United States)

    McNally, Melanie A; Hartman, Adam L

    2012-04-01

    Seizures that are resistant to standard medications remain a major clinical problem. One underutilized option for patients with medication-resistant seizures is the high-fat, low-carbohydrate ketogenic diet. The diet received its name based on the observation that patients consuming this diet produce ketone bodies (e.g., acetoacetate, β-hydroxybutyrate, and acetone). Although the exact mechanisms of the diet are unknown, ketone bodies have been hypothesized to contribute to the anticonvulsant and antiepileptic effects. In this review, anticonvulsant properties of ketone bodies and the ketogenic diet are discussed (including GABAergic and glutamatergic effects). Because of the importance of ketone body metabolism in the early stages of life, the effects of ketone bodies on developing neurons in vitro also are discussed. Understanding how ketone bodies exert their effects will help optimize their use in treating epilepsy and other neurological disorders. © 2012 The Authors. Journal of Neurochemistry © 2012 International Society for Neurochemistry.

  3. The inverse problem of brain energetics: ketone bodies as alternative substrates

    Energy Technology Data Exchange (ETDEWEB)

    Calvetti, D; Occhipinti, R [Case Western Reserve University, Department of Mathematics, 10900 Euclid Avenue, Cleveland, OH 44106 (United States); Somersalo, E [Helsinki University of Technology, Institute of Mathematics, P. O. Box 1100, FIN-02015 HUT (Finland)], E-mail: daniela.calvetti@case.edu, E-mail: rossana.occhipinti@case.edu, E-mail: erkki.somersalo@tkk.fi

    2008-07-15

    Little is known about brain energy metabolism under ketosis, although there is evidence that ketone bodies have a neuroprotective role in several neurological disorders. We investigate the inverse problem of estimating reaction fluxes and transport rates in the different cellular compartments of the brain, when the data amounts to a few measured arterial venous concentration differences. By using a recently developed methodology to perform Bayesian Flux Balance Analysis and a new five compartment model of the astrocyte-glutamatergic neuron cellular complex, we are able to identify the preferred biochemical pathways during shortage of glucose and in the presence of ketone bodies in the arterial blood. The analysis is performed in a minimally biased way, therefore revealing the potential of this methodology for hypothesis testing.

  4. The inverse problem of brain energetics: ketone bodies as alternative substrates

    International Nuclear Information System (INIS)

    Calvetti, D; Occhipinti, R; Somersalo, E

    2008-01-01

    Little is known about brain energy metabolism under ketosis, although there is evidence that ketone bodies have a neuroprotective role in several neurological disorders. We investigate the inverse problem of estimating reaction fluxes and transport rates in the different cellular compartments of the brain, when the data amounts to a few measured arterial venous concentration differences. By using a recently developed methodology to perform Bayesian Flux Balance Analysis and a new five compartment model of the astrocyte-glutamatergic neuron cellular complex, we are able to identify the preferred biochemical pathways during shortage of glucose and in the presence of ketone bodies in the arterial blood. The analysis is performed in a minimally biased way, therefore revealing the potential of this methodology for hypothesis testing

  5. The inverse problem of brain energetics: ketone bodies as alternative substrates

    Science.gov (United States)

    Calvetti, D.; Occhipinti, R.; Somersalo, E.

    2008-07-01

    Little is known about brain energy metabolism under ketosis, although there is evidence that ketone bodies have a neuroprotective role in several neurological disorders. We investigate the inverse problem of estimating reaction fluxes and transport rates in the different cellular compartments of the brain, when the data amounts to a few measured arterial venous concentration differences. By using a recently developed methodology to perform Bayesian Flux Balance Analysis and a new five compartment model of the astrocyte-glutamatergic neuron cellular complex, we are able to identify the preferred biochemical pathways during shortage of glucose and in the presence of ketone bodies in the arterial blood. The analysis is performed in a minimally biased way, therefore revealing the potential of this methodology for hypothesis testing.

  6. Dual-isotope technique for determination of in vivo ketone body kinetics

    International Nuclear Information System (INIS)

    Miles, J.M.; Schwenk, W.F.; McClean, K.L.; Haymond, M.W.

    1986-01-01

    Total ketone body specific activity has been widely used in studies of ketone body metabolism to circumvent so-called isotope disequilibrium between the two major ketone body pools, acetoacetate and beta-hydroxybutyrate. Recently, this approach has been criticized on theoretical grounds. In the present studies, [13C]acetoacetate and beta-[14C]hydroxybutyrate were simultaneously infused in nine mongrel dogs before and during an infusion of either unlabeled sodium acetoacetate or unlabeled sodium beta-hydroxybutyrate. Ketone body turnover was determined using total ketone body specific activity, total ketone body moles % enrichment, and an open two-pool model, both before and during the exogenous infusion of unlabeled ketone bodies. Basal ketone body turnover rates were significantly higher using [13C]acetoacetate than with either beta-[14C]hydroxybutyrate alone or the dual-isotope model (3.6 +/- 0.5 vs. 2.2 +/- 0.2 and 2.7 +/- 0.2 mumol X kg-1 X min-1, respectively, P less than 0.05). During exogenous infusion of unlabeled sodium acetoacetate, the dual-isotope model provided the best estimate of ketone body inflow, whereas 14C specific activity underestimated the known rate of acetoacetate infusion by 55% (P less than 0.02). During sodium beta-hydroxybutyrate infusion, [13C]-acetoacetate overestimated ketone body inflow by 55% (P = NS), while better results were obtained with 14C beta-hydroxybutyrate alone and the two-pool model. Ketone body interconversion as estimated by the dual-isotope technique increased markedly during exogenous ketone body infusion. In conclusion, significant errors in estimation of ketone body inflow were made using single-isotope techniques, whereas a dual-isotope model provided reasonably accurate estimates of ketone body inflow during infusion of exogenous acetoacetate and beta-hydroxybutyrate

  7. Is there an astrocyte-neuron ketone body shuttle?

    Science.gov (United States)

    Guzmán, M; Blázquez, C

    2001-01-01

    Ketone bodies can replace glucose as the major source of brain energy when glucose becomes scarce. Although it is generally assumed that the liver supplies extrahepatic tissues with ketone bodies, recent evidence shows that astrocytes are also ketogenic cells. Moreover, the partitioning of fatty acids between ketogenesis and ceramide synthesis de novo might control the survival/death decision of neural cells. These findings support the notion that astrocytes might supply neurons with ketone bodies in situ, and raise the possibility that astrocyte ketogenesis is a cytoprotective pathway.

  8. Ketone Bodies Mediate Antiseizure Effects

    Directory of Open Access Journals (Sweden)

    Jena M. Krueger

    2015-10-01

    Full Text Available Investigators from The Barrow Neurological Institute, Creighton University, University of Kentucky and the University of Calgary Faculty of Medicine investigated the effect of ketone bodies and the ketogenic diet on epileptic Kcna1-null mice.

  9. Metabolism of ketone bodies during exercise and training: physiological basis for exogenous supplementation

    Science.gov (United States)

    Evans, Mark; Cogan, Karl E.

    2016-01-01

    Abstract Optimising training and performance through nutrition strategies is central to supporting elite sportspeople, much of which has focused on manipulating the relative intake of carbohydrate and fat and their contributions as fuels for energy provision. The ketone bodies, namely acetoacetate, acetone and β‐hydroxybutyrate (βHB), are produced in the liver during conditions of reduced carbohydrate availability and serve as an alternative fuel source for peripheral tissues including brain, heart and skeletal muscle. Ketone bodies are oxidised as a fuel source during exercise, are markedly elevated during the post‐exercise recovery period, and the ability to utilise ketone bodies is higher in exercise‐trained skeletal muscle. The metabolic actions of ketone bodies can alter fuel selection through attenuating glucose utilisation in peripheral tissues, anti‐lipolytic effects on adipose tissue, and attenuation of proteolysis in skeletal muscle. Moreover, ketone bodies can act as signalling metabolites, with βHB acting as an inhibitor of histone deacetylases, an important regulator of the adaptive response to exercise in skeletal muscle. Recent development of ketone esters facilitates acute ingestion of βHB that results in nutritional ketosis without necessitating restrictive dietary practices. Initial reports suggest this strategy alters the metabolic response to exercise and improves exercise performance, while other lines of evidence suggest roles in recovery from exercise. The present review focuses on the physiology of ketone bodies during and after exercise and in response to training, with specific interest in exploring the physiological basis for exogenous ketone supplementation and potential benefits for performance and recovery in athletes. PMID:27861911

  10. Metabolism of ketone bodies during exercise and training: physiological basis for exogenous supplementation.

    Science.gov (United States)

    Evans, Mark; Cogan, Karl E; Egan, Brendan

    2017-05-01

    Optimising training and performance through nutrition strategies is central to supporting elite sportspeople, much of which has focused on manipulating the relative intake of carbohydrate and fat and their contributions as fuels for energy provision. The ketone bodies, namely acetoacetate, acetone and β-hydroxybutyrate (βHB), are produced in the liver during conditions of reduced carbohydrate availability and serve as an alternative fuel source for peripheral tissues including brain, heart and skeletal muscle. Ketone bodies are oxidised as a fuel source during exercise, are markedly elevated during the post-exercise recovery period, and the ability to utilise ketone bodies is higher in exercise-trained skeletal muscle. The metabolic actions of ketone bodies can alter fuel selection through attenuating glucose utilisation in peripheral tissues, anti-lipolytic effects on adipose tissue, and attenuation of proteolysis in skeletal muscle. Moreover, ketone bodies can act as signalling metabolites, with βHB acting as an inhibitor of histone deacetylases, an important regulator of the adaptive response to exercise in skeletal muscle. Recent development of ketone esters facilitates acute ingestion of βHB that results in nutritional ketosis without necessitating restrictive dietary practices. Initial reports suggest this strategy alters the metabolic response to exercise and improves exercise performance, while other lines of evidence suggest roles in recovery from exercise. The present review focuses on the physiology of ketone bodies during and after exercise and in response to training, with specific interest in exploring the physiological basis for exogenous ketone supplementation and potential benefits for performance and recovery in athletes. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

  11. Validation of a tracer technique to determine nonsteady-state ketone body turnover rates in man

    International Nuclear Information System (INIS)

    Keller, U.; Sonnenberg, G.E.; Stauffacher, W.

    1981-01-01

    The features of a single-compartment model of total ketone bodies were evaluated using primed constant infusions of [3-14C]acetoacetate (AcAc) and of D-[3-14C]beta-hydroxybutyrate (beta OHB) in 12 postabsorptive subjects. The volume of distribution (VD) of AcAc was 0.18 +- 0.01 liter/kg (n = 9), and that of beta OHB was similar, 0.18 +- 0.02 liter/kg (n = 3). The production rate of total ketone bodies was calculated using the combined specific activity of AcAc and of beta OHB. The mean basal total ketone body production rates were similar using either [14C]AcAc (6.5 mumol . kg-1 . min-1) or [14C]beta OHB (6.8 mumol . kg-1 . min-1). To determine the pool fraction that was rapidly mixed during nonsteady state of ketone body inflow, unlabeled AcAc was infused with stepwise increasing and decreasing rates between 5 and 25 mumol . kg-1 . m-1 to mimic nonsteady-state ketone body production rates. The functional pool fraction P was determined as the pool fraction that provided the best match between tracer-determined rates of ketone production and rates of AcAc infusion. P of total ketone bodies was almost equal to 1 using either [14C]AcAc (1.05 +- 0.16) or [14C]beta OHB (1.00 +- 0.06), suggesting rapid mixing of ketone bodies throughout the entire pool. The described pool model may be used to determine total ketone body kinetics during acute perturbations of the steady state

  12. Ketones blood test

    Science.gov (United States)

    Acetone bodies; Ketones - serum; Nitroprusside test; Ketone bodies - serum; Ketones - blood; Ketoacidosis - ketones blood test ... fat cells break down in the blood. This test is used to diagnose ketoacidosis . This is a ...

  13. Human ketone body production and utilization studied using tracer techniques: Regulation by free fatty acids, insulin, catecholamines, and thyroid hormones

    Energy Technology Data Exchange (ETDEWEB)

    Keller, U.; Lustenberger, M.; Mueller-Brand, J.G.; Gerber, P.P.; Stauffacher, W.

    1989-05-01

    Ketone body concentrations fluctuate markedly during physiological and pathological conditions. Tracer techniques have been developed in recent years to study production, utilization, and the metabolic clearance rate of ketone bodies. This review describes data on the roles of insulin, catecholamines, and thyroid hormones in the regulation of ketone body kinetics. The data indicate that insulin lowers ketone body concentrations by three independent mechanisms: first, it inhibits lipolysis, and thus lowers free fatty acid availability for ketogenesis; second, it restrains ketone body production within the liver; third, it enhances peripheral ketone body utilization. To assess these effects in humans in vivo, experimental models were developed to study insulin effects with controlled concentrations of free fatty acids, insulin, glucagon, and ketone bodies. Presently available data also support an important role of catecholamines in increasing ketone body concentrations. Evidence was presented that norepinephrine increases ketogenesis not only by stimulating lipolysis, and thus releasing free fatty acids, but also by increasing intrahepatic ketogenesis. Thyroid hormone availability was associated with lipolysis and ketogenesis. Ketone body concentrations after an overnight fast were only modestly elevated in hyperthyroidism resulting from increased peripheral ketone body clearance. There was a significant correlation between serum triiodothyronine levels and the ketone body metabolic clearance rate. Thus, ketone body homeostasis in human subjects resulted from the interaction of hormones such as insulin, catecholamines, and thyroid hormones regulating lipolysis, intrahepatic ketogenesis, and peripheral ketone body utilization. 58 references.

  14. Human ketone body production and utilization studied using tracer techniques: Regulation by free fatty acids, insulin, catecholamines, and thyroid hormones

    International Nuclear Information System (INIS)

    Keller, U.; Lustenberger, M.; Mueller-Brand, J.G.; Gerber, P.P.; Stauffacher, W.

    1989-01-01

    Ketone body concentrations fluctuate markedly during physiological and pathological conditions. Tracer techniques have been developed in recent years to study production, utilization, and the metabolic clearance rate of ketone bodies. This review describes data on the roles of insulin, catecholamines, and thyroid hormones in the regulation of ketone body kinetics. The data indicate that insulin lowers ketone body concentrations by three independent mechanisms: first, it inhibits lipolysis, and thus lowers free fatty acid availability for ketogenesis; second, it restrains ketone body production within the liver; third, it enhances peripheral ketone body utilization. To assess these effects in humans in vivo, experimental models were developed to study insulin effects with controlled concentrations of free fatty acids, insulin, glucagon, and ketone bodies. Presently available data also support an important role of catecholamines in increasing ketone body concentrations. Evidence was presented that norepinephrine increases ketogenesis not only by stimulating lipolysis, and thus releasing free fatty acids, but also by increasing intrahepatic ketogenesis. Thyroid hormone availability was associated with lipolysis and ketogenesis. Ketone body concentrations after an overnight fast were only modestly elevated in hyperthyroidism resulting from increased peripheral ketone body clearance. There was a significant correlation between serum triiodothyronine levels and the ketone body metabolic clearance rate. Thus, ketone body homeostasis in human subjects resulted from the interaction of hormones such as insulin, catecholamines, and thyroid hormones regulating lipolysis, intrahepatic ketogenesis, and peripheral ketone body utilization. 58 references

  15. Antioxidant capacity contributes to protection of ketone bodies against oxidative damage induced during hypoglycemic conditions.

    Science.gov (United States)

    Haces, María L; Hernández-Fonseca, Karla; Medina-Campos, Omar N; Montiel, Teresa; Pedraza-Chaverri, José; Massieu, Lourdes

    2008-05-01

    Ketone bodies play a key role in mammalian energy metabolism during the suckling period. Normally ketone bodies' blood concentration during adulthood is very low, although it can rise during starvation, an exogenous infusion or a ketogenic diet. Whenever ketone bodies' levels increase, their oxidation in the brain rises. For this reason they have been used as protective molecules against refractory epilepsy and in experimental models of ischemia and excitotoxicity. The mechanisms underlying the protective effect of these compounds are not completely understood. Here, we studied a possible antioxidant capacity of ketone bodies and whether it contributes to the protection against oxidative damage induced during hypoglycemia. We report for the first time the scavenging capacity of the ketone bodies, acetoacetate (AcAc) and both the physiological and non-physiological isomers of beta-hydroxybutyrate (D- and L-BHB, respectively), for diverse reactive oxygen species (ROS). Hydroxyl radicals (.OH) were effectively scavenged by D- and L-BHB. In addition, the three ketone bodies were able to reduce cell death and ROS production induced by the glycolysis inhibitor, iodoacetate (IOA), while only D-BHB and AcAc prevented neuronal ATP decline. Finally, in an in vivo model of insulin-induced hypoglycemia, the administration of D- or L-BHB, but not of AcAc, was able to prevent the hypoglycemia-induced increase in lipid peroxidation in the rat hippocampus. Our data suggest that the antioxidant capacity contributes to protection of ketone bodies against oxidative damage in in vitro and in vivo models associated with free radical production and energy impairment.

  16. Improved cerebral energetics and ketone body metabolism in db/db mice

    DEFF Research Database (Denmark)

    Andersen, Jens V; Christensen, Sofie K; Nissen, Jakob D

    2017-01-01

    It is becoming evident that type 2 diabetes mellitus is affecting brain energy metabolism. The importance of alternative substrates for the brain in type 2 diabetes mellitus is poorly understood. The aim of this study was to investigate whether ketone bodies are relevant candidates to compensate...... metabolism in type 2 diabetes mellitus. The increased hippocampal ketone body utilization and improved mitochondrial function in db/db mice, may act as adaptive mechanisms in order to maintain cerebral energetics during hampered glucose metabolism....

  17. Ketones urine test

    Science.gov (United States)

    Ketone bodies - urine; Urine ketones; Ketoacidosis - urine ketones test; Diabetic ketoacidosis - urine ketones test ... Urine ketones are usually measured as a "spot test." This is available in a test kit that ...

  18. Successful adaptation to ketosis by mice with tissue-specific deficiency of ketone body oxidation.

    Science.gov (United States)

    Cotter, David G; Schugar, Rebecca C; Wentz, Anna E; d'Avignon, D André; Crawford, Peter A

    2013-02-15

    During states of low carbohydrate intake, mammalian ketone body metabolism transfers energy substrates originally derived from fatty acyl chains within the liver to extrahepatic organs. We previously demonstrated that the mitochondrial enzyme coenzyme A (CoA) transferase [succinyl-CoA:3-oxoacid CoA transferase (SCOT), encoded by nuclear Oxct1] is required for oxidation of ketone bodies and that germline SCOT-knockout (KO) mice die within 48 h of birth because of hyperketonemic hypoglycemia. Here, we use novel transgenic and tissue-specific SCOT-KO mice to demonstrate that ketone bodies do not serve an obligate energetic role within highly ketolytic tissues during the ketogenic neonatal period or during starvation in the adult. Although transgene-mediated restoration of myocardial CoA transferase in germline SCOT-KO mice is insufficient to prevent lethal hyperketonemic hypoglycemia in the neonatal period, mice lacking CoA transferase selectively within neurons, cardiomyocytes, or skeletal myocytes are all viable as neonates. Like germline SCOT-KO neonatal mice, neonatal mice with neuronal CoA transferase deficiency exhibit increased cerebral glycolysis and glucose oxidation, and, while these neonatal mice exhibit modest hyperketonemia, they do not develop hypoglycemia. As adults, tissue-specific SCOT-KO mice tolerate starvation, exhibiting only modestly increased hyperketonemia. Finally, metabolic analysis of adult germline Oxct1(+/-) mice demonstrates that global diminution of ketone body oxidation yields hyperketonemia, but hypoglycemia emerges only during a protracted state of low carbohydrate intake. Together, these data suggest that, at the tissue level, ketone bodies are not a required energy substrate in the newborn period or during starvation, but rather that integrated ketone body metabolism mediates adaptation to ketogenic nutrient states.

  19. The contribution of ketone bodies to basal and activity-dependent neuronal oxidation in vivo.

    Science.gov (United States)

    Chowdhury, Golam M I; Jiang, Lihong; Rothman, Douglas L; Behar, Kevin L

    2014-07-01

    The capacity of ketone bodies to replace glucose in support of neuronal function is unresolved. Here, we determined the contributions of glucose and ketone bodies to neocortical oxidative metabolism over a large range of brain activity in rats fasted 36 hours and infused intravenously with [2,4-(13)C₂]-D-β-hydroxybutyrate (BHB). Three animal groups and conditions were studied: awake ex vivo, pentobarbital-induced isoelectricity ex vivo, and halothane-anesthetized in vivo, the latter data reanalyzed from a recent study. Rates of neuronal acetyl-CoA oxidation from ketone bodies (V(acCoA-kbN)) and pyruvate (V(pdhN)), and the glutamate-glutamine cycle (V(cyc)) were determined by metabolic modeling of (13)C label trapped in major brain amino acid pools. V(acCoA-kbN) increased gradually with increasing activity, as compared with the steeper change in tricarboxylic acid (TCA) cycle rate (V(tcaN)), supporting a decreasing percentage of neuronal ketone oxidation: ∼100% (isoelectricity), 56% (halothane anesthesia), 36% (awake) with the BHB plasma levels achieved in our experiments (6 to 13 mM). In awake animals ketone oxidation reached saturation for blood levels >17 mM, accounting for 62% of neuronal substrate oxidation, the remainder (38%) provided by glucose. We conclude that ketone bodies present at sufficient concentration to saturate metabolism provides full support of basal (housekeeping) energy needs and up to approximately half of the activity-dependent oxidative needs of neurons.

  20. Ketone bodies effectively compete with glucose for neuronal acetyl-CoA generation in rat hippocampal slices.

    Science.gov (United States)

    Valente-Silva, Paula; Lemos, Cristina; Köfalvi, Attila; Cunha, Rodrigo A; Jones, John G

    2015-09-01

    Ketone bodies can be used for cerebral energy generation in situ, when their availability is increased as during fasting or ingestion of a ketogenic diet. However, it is not known how effectively ketone bodies compete with glucose, lactate, and pyruvate for energy generation in the brain parenchyma. Hence, the contributions of exogenous 5.0 mM [1-(13)C]glucose and 1.0 mM [2-(13)C]lactate + 0.1 mM pyruvate (combined [2-(13)C]lactate + [2-(13)C]pyruvate) to acetyl-CoA production were measured both without and with 5.0 mM [U-(13)C]3-hydroxybutyrate in superfused rat hippocampal slices by (13)C NMR non-steady-state isotopomer analysis of tissue glutamate and GABA. Without [U-(13)C]3-hydroxybutyrate, glucose, combined lactate + pyruvate, and unlabeled endogenous sources contributed (mean ± SEM) 70 ± 7%, 10 ± 2%, and 20 ± 8% of acetyl-CoA, respectively. With [U-(13)C]3-hydroxybutyrate, glucose contributions significantly fell from 70 ± 7% to 21 ± 3% (p neurons. The appearance of superfusate lactate derived from glycolysis of [1-(13)C]glucose did not decrease significantly in the presence of 3-hydroxybutyrate, hence total glycolytic flux (Krebs cycle inflow + exogenous lactate formation) was attenuated by 3-hydroxybutyrate. This indicates that, under these conditions, 3-hydroxybutyrate inhibited glycolytic flux upstream of pyruvate kinase. Copyright © 2015 John Wiley & Sons, Ltd.

  1. A ketogenic diet increases transport and oxidation of ketone bodies in RG2 and 9L gliomas without affecting tumor growth.

    Science.gov (United States)

    De Feyter, Henk M; Behar, Kevin L; Rao, Jyotsna U; Madden-Hennessey, Kirby; Ip, Kevan L; Hyder, Fahmeed; Drewes, Lester R; Geschwind, Jean-François; de Graaf, Robin A; Rothman, Douglas L

    2016-08-01

    The dependence of tumor cells, particularly those originating in the brain, on glucose is the target of the ketogenic diet, which creates a plasma nutrient profile similar to fasting: increased levels of ketone bodies and reduced plasma glucose concentrations. The use of ketogenic diets has been of particular interest for therapy in brain tumors, which reportedly lack the ability to oxidize ketone bodies and therefore would be starved during ketosis. Because studies assessing the tumors' ability to oxidize ketone bodies are lacking, we investigated in vivo the extent of ketone body oxidation in 2 rodent glioma models. Ketone body oxidation was studied using (13)C MR spectroscopy in combination with infusion of a (13)C-labeled ketone body (beta-hydroxybutyrate) in RG2 and 9L glioma models. The level of ketone body oxidation was compared with nontumorous cortical brain tissue. The level of (13)C-beta-hydroxybutyrate oxidation in 2 rat glioma models was similar to that of contralateral brain. In addition, when glioma-bearing animals were fed a ketogenic diet, the ketone body monocarboxylate transporter was upregulated, facilitating uptake and oxidation of ketone bodies in the gliomas. These results demonstrate that rat gliomas can oxidize ketone bodies and indicate upregulation of ketone body transport when fed a ketogenic diet. Our findings contradict the hypothesis that brain tumors are metabolically inflexible and show the need for additional research on the use of ketogenic diets as therapy targeting brain tumor metabolism. © The Author(s) 2016. Published by Oxford University Press on behalf of the Society for Neuro-Oncology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  2. Lauric Acid Stimulates Ketone Body Production in the KT-5 Astrocyte Cell Line.

    Science.gov (United States)

    Nonaka, Yudai; Takagi, Tetsuo; Inai, Makoto; Nishimura, Shuhei; Urashima, Shogo; Honda, Kazumitsu; Aoyama, Toshiaki; Terada, Shin

    2016-08-01

    Coconut oil has recently attracted considerable attention as a potential Alzheimer's disease therapy because it contains large amounts of medium-chain fatty acids (MCFAs) and its consumption is thought to stimulate hepatic ketogenesis, supplying an alternative energy source for brains with impaired glucose metabolism. In this study, we first reevaluated the responses of plasma ketone bodies to oral administration of coconut oil to rats. We found that the coconut oil-induced increase in plasma ketone body concentration was negligible and did not significantly differ from that observed after high-oleic sunflower oil administration. In contrast, the administration of coconut oil substantially increased the plasma free fatty acid concentration and lauric acid content, which is the major MCFA in coconut oil. Next, to elucidate whether lauric acid can activate ketogenesis in astrocytes with the capacity to generate ketone bodies from fatty acids, we treated the KT-5 astrocyte cell line with 50 and 100 μM lauric acid for 4 h. The lauric acid treatments increased the total ketone body concentration in the cell culture supernatant to a greater extent than oleic acid, suggesting that lauric acid can directly and potently activate ketogenesis in KT-5 astrocytes. These results suggest that coconut oil intake may improve brain health by directly activating ketogenesis in astrocytes and thereby by providing fuel to neighboring neurons.

  3. Effects of ketone bodies in Alzheimer's disease in relation to neural hypometabolism, β-amyloid toxicity, and astrocyte function

    DEFF Research Database (Denmark)

    Hertz, Leif; Chen, Ye; Waagepetersen, Helle S

    2015-01-01

    Diet supplementation with ketone bodies (acetoacetate and β-hydroxybuturate) or medium-length fatty acids generating ketone bodies has consistently been found to cause modest improvement of mental function in Alzheimer's patients. It was suggested that the therapeutic effect might be more...

  4. Fenofibrate induces ketone body production in melanoma and glioblastoma cells

    Directory of Open Access Journals (Sweden)

    Maja M Grabacka

    2016-02-01

    Full Text Available Ketone bodies (beta-hydroxybutyrate, bHB, acetoacetate are mainly produced in the liver during prolonged fasting or starvation. bHB is a very efficient energy substrate for sustaining ATP production in peripheral tissues; importantly its consumption is preferred over glucose. However, the majority of malignant cells, particularly cancer cells of neuroectodermal origin such as glioblastoma, are not able to use ketone bodies as a source of energy. Here, we report a novel observation that fenofibrate, a synthetic peroxisome proliferator-activated receptor alpha (PPARa agonist, induces bHB production in melanoma and glioblastoma cells, as well as in neurospheres composed of nontransformed cells. Unexpectedly, this effect is not dependent on PPARa activity or its expression level. The fenofibrate-induced ketogenesis is accompanied by growth arrest and down-regulation of transketolase, but the NADP/NADPH and GSH/GSSG ratios remain unaffected. Our results reveal a new, intriguing aspect of cancer cell biology and highlight the benefits of fenofibrate as a supplement to both canonical and dietary (ketogenic therapeutic approaches against glioblastoma.

  5. The Ketone Body, β-Hydroxybutyrate Stimulates the Autophagic Flux and Prevents Neuronal Death Induced by Glucose Deprivation in Cortical Cultured Neurons.

    Science.gov (United States)

    Camberos-Luna, Lucy; Gerónimo-Olvera, Cristian; Montiel, Teresa; Rincon-Heredia, Ruth; Massieu, Lourdes

    2016-03-01

    Glucose is the major energy substrate in brain, however, during ketogenesis induced by starvation or prolonged hypoglycemia, the ketone bodies (KB), acetoacetate and β-hydroxybutyrate (BHB) can substitute for glucose. KB improve neuronal survival in diverse injury models, but the mechanisms by which KB prevent neuronal damage are still not well understood. In the present study we have investigated whether protection by the D isomer of BHB (D-BHB) against neuronal death induced by glucose deprivation (GD), is related to autophagy. Autophagy is a lysosomal-dependent degradation process activated during nutritional stress, which leads to the digestion of damaged proteins and organelles providing energy for cell survival. Results show that autophagy is activated in cortical cultured neurons during GD, as indicated by the increase in the levels of the lipidated form of the microtubule associated protein light chain 3 (LC3-II), and the number of autophagic vesicles. At early phases of glucose reintroduction (GR), the levels of p62 declined suggesting that the degradation of the autophagolysosomal content takes place at this time. In cultures exposed to GD and GR in the presence of D-BHB, the levels of LC3-II and p62 rapidly declined and remained low during GR, suggesting that the KB stimulates the autophagic flux preventing autophagosome accumulation and improving neuronal survival.

  6. Study of ketone body kinetics in children by a combined perfusion of 13C and 2H3 tracers

    International Nuclear Information System (INIS)

    Bougneres, P.F.; Ferre, P.

    1987-01-01

    Ketone body kinetics were quantified in six children (3-5 yr old), who were fasted for 13-22 h, by a combined perfusion of [3- 13 C]acetoacetate ([ 13 C]AcAc) and D-(-)-beta-[4,4,4- 2 H3]hydroxybutyrate (beta-[ 2 H3]OHB) and gas chromatography-mass spectrometry analysis. Results were analyzed according to the single-pool (combined enrichments) or the two-accessible pools models. After 20-22 h of fasting, ketone body turnover rate was 30-50 mumol.kg-1.min-1, a rate achieved after several days of fasting in adults. At low ketosis, acetoacetate was the ketone body preferentially synthesized de novo and utilized irreversibly. When ketosis increased, acetoacetate irreversible disposal was not enhanced, since it was largely converted into beta-OHB, whereas beta-OHB irreversible disposal was very much increased. The single-pool and two-pool models gave similar ketone body turnover rates when [ 13 C]AcAc was the tracer, whereas the use of beta-[ 2 H3]OHB gave some more divergent results, especially at low ketosis. These studies demonstrate that ketogenesis is very active in short-term fasted children and that the use of a combined infusion of [ 13 C]AcAc and beta-[ 2 H3]OHB is a convenient way to give insight into individual ketone body kinetics

  7. Enhancement of L-3-hydroxybutyryl-CoA dehydrogenase activity and circulating ketone body levels by pantethine. Relevance to dopaminergic injury.

    Science.gov (United States)

    Cornille, Emilie; Abou-Hamdan, Mhamad; Khrestchatisky, Michel; Nieoullon, André; de Reggi, Max; Gharib, Bouchra

    2010-04-23

    The administration of the ketone bodies hydroxybutyrate and acetoacetate is known to exert a protective effect against metabolic disorders associated with cerebral pathologies. This suggests that the enhancement of their endogenous production might be a rational therapeutic approach. Ketone bodies are generated by fatty acid beta-oxidation, a process involving a mitochondrial oxido-reductase superfamily, with fatty acid-CoA thioesters as substrates. In this report, emphasis is on the penultimate step of the process, i.e. L-3-hydroxybutyryl-CoA dehydrogenase activity. We determined changes in enzyme activity and in circulating ketone body levels in the MPTP mouse model of Parkinson's disease. Since the active moiety of CoA is pantetheine, mice were treated with pantethine, its naturally-occurring form. Pantethine has the advantage of being known as an anti-inflammatory and hypolipidemic agent with very few side effects. We found that dehydrogenase activity and circulating ketone body levels were drastically reduced by the neurotoxin MPTP, whereas treatment with pantethine overcame these adverse effects. Pantethine prevented dopaminergic neuron loss and motility disorders. In vivo and in vitro experiments showed that the protection was associated with enhancement of glutathione (GSH) production as well as restoration of respiratory chain complex I activity and mitochondrial ATP levels. Remarkably, pantethine treatment boosted the circulating ketone body levels in MPTP-intoxicated mice, but not in normal animals. These finding demonstrate the feasibility of the enhancement of endogenous ketone body production and provide a promising therapeutic approach to Parkinson's disease as well as, conceivably, to other neurodegenerative disorders.

  8. Enhancement of L-3-hydroxybutyryl-CoA dehydrogenase activity and circulating ketone body levels by pantethine. Relevance to dopaminergic injury

    Directory of Open Access Journals (Sweden)

    de Reggi Max

    2010-04-01

    Full Text Available Abstract Background The administration of the ketone bodies hydroxybutyrate and acetoacetate is known to exert a protective effect against metabolic disorders associated with cerebral pathologies. This suggests that the enhancement of their endogenous production might be a rational therapeutic approach. Ketone bodies are generated by fatty acid beta-oxidation, a process involving a mitochondrial oxido-reductase superfamily, with fatty acid-CoA thioesters as substrates. In this report, emphasis is on the penultimate step of the process, i.e. L-3-hydroxybutyryl-CoA dehydrogenase activity. We determined changes in enzyme activity and in circulating ketone body levels in the MPTP mouse model of Parkinson's disease. Since the active moiety of CoA is pantetheine, mice were treated with pantethine, its naturally-occurring form. Pantethine has the advantage of being known as an anti-inflammatory and hypolipidemic agent with very few side effects. Results We found that dehydrogenase activity and circulating ketone body levels were drastically reduced by the neurotoxin MPTP, whereas treatment with pantethine overcame these adverse effects. Pantethine prevented dopaminergic neuron loss and motility disorders. In vivo and in vitro experiments showed that the protection was associated with enhancement of glutathione (GSH production as well as restoration of respiratory chain complex I activity and mitochondrial ATP levels. Remarkably, pantethine treatment boosted the circulating ketone body levels in MPTP-intoxicated mice, but not in normal animals. Conclusions These finding demonstrate the feasibility of the enhancement of endogenous ketone body production and provide a promising therapeutic approach to Parkinson's disease as well as, conceivably, to other neurodegenerative disorders.

  9. The depolarizing action of GABA in cultured hippocampal neurons is not due to the absence of ketone bodies.

    Science.gov (United States)

    Waddell, Jaylyn; Kim, Jimok; Alger, Bradley E; McCarthy, Margaret M

    2011-01-01

    Two recent reports propose that the depolarizing action of GABA in the immature brain is an artifact of in vitro preparations in which glucose is the only energy source. The authors argue that this does not mimic the physiological environment because the suckling rats use ketone bodies and pyruvate as major sources of metabolic energy. Here, we show that availability of physiologically relevant levels of ketone bodies has no impact on the excitatory action of GABA in immature cultured hippocampal neurons. Addition of β-hydroxybutyrate (BHB), the primary ketone body in the neonate rat, affected neither intracellular calcium elevation nor membrane depolarizations induced by the GABA-A receptor agonist muscimol, when assessed with calcium imaging or perforated patch-clamp recording, respectively. These results confirm that the addition of ketone bodies to the extracellular environment to mimic conditions in the neonatal brain does not reverse the chloride gradient and therefore render GABA hyperpolarizing. Our data are consistent with the existence of a genuine "developmental switch" mechanism in which GABA goes from having a predominantly excitatory role in immature cells to a predominantly inhibitory one in adults.

  10. Regulation of hypothalamic neuronal sensing and food intake by ketone bodies and fatty acids.

    Science.gov (United States)

    Le Foll, Christelle; Dunn-Meynell, Ambrose A; Miziorko, Henri M; Levin, Barry E

    2014-04-01

    Metabolic sensing neurons in the ventromedial hypothalamus (VMH) alter their activity when ambient levels of metabolic substrates, such as glucose and fatty acids (FA), change. To assess the relationship between a high-fat diet (HFD; 60%) intake on feeding and serum and VMH FA levels, rats were trained to eat a low-fat diet (LFD; 13.5%) or an HFD in 3 h/day and were monitored with VMH FA microdialysis. Despite having higher serum levels, HFD rats had lower VMH FA levels but ate less from 3 to 6 h of refeeding than did LFD rats. However, VMH β-hydroxybutyrate (β-OHB) and VMH-to-serum β-OHB ratio levels were higher in HFD rats during the first 1 h of refeeding, suggesting that VMH astrocyte ketone production mediated their reduced intake. In fact, using calcium imaging in dissociated VMH neurons showed that ketone bodies overrode normal FA sensing, primarily by exciting neurons that were activated or inhibited by oleic acid. Importantly, bilateral inhibition of VMH ketone production with a 3-hydroxy-3-methylglutaryl-CoA synthase inhibitor reversed the 3- to 6-h HFD-induced inhibition of intake but had no effect in LFD-fed rats. These data suggest that a restricted HFD intake regimen inhibits caloric intake as a consequence of FA-induced VMH ketone body production by astrocytes.

  11. The AMP-activated protein kinase is involved in the regulation of ketone body production by astrocytes.

    Science.gov (United States)

    Blázquez, C; Woods, A; de Ceballos, M L; Carling, D; Guzmán, M

    1999-10-01

    The possible role of the AMP-activated protein kinase (AMPK), a highly conserved stress-activated kinase, in the regulation of ketone body production by astrocytes was studied. AMPK activity in rat cortical astrocytes was three times higher than in rat cortical neurons. AMPK in astrocytes was shown to be functionally active. Thus, incubation of astrocytes with 5-aminoimidazole-4-carboxamide ribonucleoside (AICAR), a cell-permeable activator of AMPK, stimulated both ketogenesis from palmitate and carnitine palmitoyltransferase I. This was concomitant to a decrease of intracellular malonyl-CoA levels and an inhibition of acetyl-CoA carboxylase/fatty acid synthesis and 3-hydroxy-3-methylglutaryl-CoA reductase/cholesterol synthesis. Moreover, in microdialysis experiments AICAR was shown to stimulate brain ketogenesis markedly. The effect of chemical hypoxia on AMPK and the ketogenic pathway was studied subsequently. Incubation of astrocytes with azide led to a remarkable drop of fatty acid beta-oxidation. However, activation of AMPK during hypoxia compensated the depression of beta-oxidation, thereby sustaining ketone body production. This effect seemed to rely on the cascade hypoxia --> increase of the AMP/ATP ratio --> AMPK stimulation --> acetyl-CoA carboxylase inhibition --> decrease of malonyl-CoA concentration --> carnitine palmitoyltransferase I deinhibition --> enhanced ketogenesis. Furthermore, incubation of neurons with azide blunted lactate oxidation, but not 3-hydroxybutyrate oxidation. Results show that (a) AMPK plays an active role in the regulation of ketone body production by astrocytes, and (b) ketone bodies produced by astrocytes during hypoxia might be a substrate for neuronal oxidative metabolism.

  12. Comparison of palmitic acid kinetics during glucose or ketone body infusions

    Energy Technology Data Exchange (ETDEWEB)

    Birkhahn, R.H.; Block, D.J.; Birkhahn, G.C.; Thomford, N.R.

    1986-03-05

    Ketone body interactions can be observed for extended ketosis by infusion by monoacetoacetin (the monoglyceride of acetoacetic acid). Palmitic acid kinetics were compared on the 5th day of glucose or ketone body-glucose infusions. 20 rats were fed complete diets intravenously at the rate of 50 ml/day. All diets contained vitamins, trace minerals, electrolytes, amino acids and 1 kcal/ml of non-protein energy. Rats were divided by energy source: Group A (n = 10) received energy from glucose and Group B (n = 10) from 72% monoacetoacetin plus 28% glucose. Diets were given at 1/2 and 3/4 rats on days 1 and 2, respectively and at full rate for days 3-5. Urinary nitrogen losses, body weight and dietary intake were measured daily. Palmitate kinetics was measured on day 5 using a continuous infusion of (1-/sup 14/C) palmitate and measuring C-14 in breath and plasma and plasma palmitate by GC. The two groups had similar body weight changes and urinary nitrogen losses over the 3 days of full intake Group A had lower plasma palmitate (88 +/- 7 vs 105 +/- 6 micromol/l) but similar turnover (17.1 +/- 2.4 vs 15.0 +/- 1.9 mmol/hr) and oxidation 2.3 +/- 0.3 vs 2.2 +/- 0.05 mmol/hr) compared to Group B. These data show that feeding monoacetoacetin intravenously does not stimulate fatty acid metabolism in the well nourished rat.

  13. Comparison of palmitic acid kinetics during glucose or ketone body infusions

    International Nuclear Information System (INIS)

    Birkhahn, R.H.; Block, D.J.; Birkhahn, G.C.; Thomford, N.R.

    1986-01-01

    Ketone body interactions can be observed for extended ketosis by infusion by monoacetoacetin (the monoglyceride of acetoacetic acid). Palmitic acid kinetics were compared on the 5th day of glucose or ketone body-glucose infusions. 20 rats were fed complete diets intravenously at the rate of 50 ml/day. All diets contained vitamins, trace minerals, electrolytes, amino acids and 1 kcal/ml of non-protein energy. Rats were divided by energy source: Group A (n = 10) received energy from glucose and Group B (n = 10) from 72% monoacetoacetin plus 28% glucose. Diets were given at 1/2 and 3/4 rats on days 1 and 2, respectively and at full rate for days 3-5. Urinary nitrogen losses, body weight and dietary intake were measured daily. Palmitate kinetics was measured on day 5 using a continuous infusion of [1- 14 C] palmitate and measuring C-14 in breath and plasma and plasma palmitate by GC. The two groups had similar body weight changes and urinary nitrogen losses over the 3 days of full intake Group A had lower plasma palmitate (88 +/- 7 vs 105 +/- 6 micromol/l) but similar turnover (17.1 +/- 2.4 vs 15.0 +/- 1.9 mmol/hr) and oxidation 2.3 +/- 0.3 vs 2.2 +/- 0.05 mmol/hr) compared to Group B. These data show that feeding monoacetoacetin intravenously does not stimulate fatty acid metabolism in the well nourished rat

  14. Study of ketone body kinetics in children by a combined perfusion of /sup 13/C and /sup 2/H3 tracers

    Energy Technology Data Exchange (ETDEWEB)

    Bougneres, P.F.; Ferre, P.

    1987-11-01

    Ketone body kinetics were quantified in six children (3-5 yr old), who were fasted for 13-22 h, by a combined perfusion of (3-/sup 13/C)acetoacetate ((/sup 13/C)AcAc) and D-(-)-beta-(4,4,4-/sup 2/H3)hydroxybutyrate (beta-(/sup 2/H3)OHB) and gas chromatography-mass spectrometry analysis. Results were analyzed according to the single-pool (combined enrichments) or the two-accessible pools models. After 20-22 h of fasting, ketone body turnover rate was 30-50 mumol.kg-1.min-1, a rate achieved after several days of fasting in adults. At low ketosis, acetoacetate was the ketone body preferentially synthesized de novo and utilized irreversibly. When ketosis increased, acetoacetate irreversible disposal was not enhanced, since it was largely converted into beta-OHB, whereas beta-OHB irreversible disposal was very much increased. The single-pool and two-pool models gave similar ketone body turnover rates when (/sup 13/C)AcAc was the tracer, whereas the use of beta-(/sup 2/H3)OHB gave some more divergent results, especially at low ketosis. These studies demonstrate that ketogenesis is very active in short-term fasted children and that the use of a combined infusion of (/sup 13/C)AcAc and beta-(/sup 2/H3)OHB is a convenient way to give insight into individual ketone body kinetics.

  15. Ketone body metabolism in normal and diabetic human skeletal muscle

    International Nuclear Information System (INIS)

    Nosadini, R.; Avogaro, A.; Sacca, L.

    1985-01-01

    Although the liver is considered the major source of ketone bodies (KB) in humans, these compounds may also be formed by nonhepatic tissues. To study this aspect further, 3-[ 14 C]hydroxybutyrate (BOH) or [3- 14 C]acetoacetate (AcAc) were constantly infused after a priming dose and contemporaneous arterial and venous samples were taken at splanchnic, heart, kidney, and leg sites in eight normal subjects (N) undergoing diagnostic catheterization and at the forearm site in five normal and six ketotic diabetic (D) subjects. After 70 min of infusion, tracer and tracee levels of AcAc and BOH reached a steady state in the artery and vein in both normal and diabetic subjects. The venous-arterial (V-A) difference at the forearm step for cold KB was negligible both in normal and diabetic subjects, whereas for labeled KB it was approximately 10-fold higher in diabetic subjects (V-A AcAc, -31 +/- 7 and -270 +/- 34 dpm/ml in N and D, respectively; V-A BOH, -38 +/- 6 and -344 +/- 126 dpm/ml in N and D, respectively). The authors assumed that the V-A difference in tracer concentration was consistent with dilution of the tracer by newly synthesized tracee inside the muscle and calculated that the forearm muscle produces KB at a rate of 16.2 +/- 3.3 mumol/min in D and 0.9 +/- 0.9 mumol/min in N. These findings can be accounted for by the hypothesis that the disappearance flux of KB from circulation was replaced by an equivalent flux of KB entering the vein at the muscle step in D but not in N. Moreover, in N KB were not only produced but also utilized by the splanchnic area (39 +/- 9 mumol/min)

  16. The rate of cerebral utilization of glucose, ketone bodies, and oxygen: a comparative in vivo study of infant and adult rats.

    Science.gov (United States)

    Dahlquist, G; Persson, B

    1976-11-01

    Cerebral blood flow (CBF) was measured by means of Celabeled microspheres in infant (20-day-old) and adult (3-month-old) rats, anesthetised with Na-5-ethyl-5-(1-methylpropyl)2-thiobarbituric acid. Cerebral arteriovenous differences of acetoacetate, D-beta-hydroxybutyrate, glucose, lactate, and oxygen and brain DNA content were determined in other groups of similarly treated infant and adult animals fed or starved for 48 or 72 hr. The mean CBF values of 0.48+/-0.04 and 0.62+/-0.07 ml/(g X min), +/- SEM, in infant and adult animals, respectively, were not significantly different. CBF was unaffected by starvation. At any given arterial concentration the cerebral arteriovenous difference of acetoacetate was significantly higher in infant than adult rats. The same was true for D-beta-hydroxybutyrate at arterial concentrations above 1 mmol/liter. There was an approximately linear relationship between arterial concentration of acetoacetate and its cerebral arteriovenous difference in both infant and adult rats. A similar relationship was found for D-beta-hydroxybutyrate only in infant animals. In the fed state, the cerebral uptake of glucose and ketone bodies (micromoles per (mg DNA X min)) was not different in infant and adult rats. During starvation, cerebral uptake of ketone bodies expressed as micromoles per (mg DNA X min) was higher in infant than adult rats, indicating a higher rate of utilization of ketone bodies per cell in these animals. For glucose, no such difference was found in either fed or starved groups (Table 3). The average percentage of the total cerebral uptake of substrates (micromoles per min) accounted for by ketone bodies increased in both infant and adult rats during starvation. This percentage value was clearly higher in infant than adult rats during starvation. After 72 hr of starvation the values were 38.8% and 15.2% in infant and adult rats, respectively (Fig. 3). Calculated cerebral metabolic rate for oxygen (CMRO2), assuming complete

  17. Caloric restriction increases ketone bodies metabolism and preserves blood flow in aging brain.

    Science.gov (United States)

    Lin, Ai-Ling; Zhang, Wei; Gao, Xiaoli; Watts, Lora

    2015-07-01

    Caloric restriction (CR) has been shown to increase the life span and health span of a broad range of species. However, CR effects on in vivo brain functions are far from explored. In this study, we used multimetric neuroimaging methods to characterize the CR-induced changes of brain metabolic and vascular functions in aging rats. We found that old rats (24 months of age) with CR diet had reduced glucose uptake and lactate concentration, but increased ketone bodies level, compared with the age-matched and young (5 months of age) controls. The shifted metabolism was associated with preserved vascular function: old CR rats also had maintained cerebral blood flow relative to the age-matched controls. When investigating the metabolites in mitochondrial tricarboxylic acid cycle, we found that citrate and α-ketoglutarate were preserved in the old CR rats. We suggest that CR is neuroprotective; ketone bodies, cerebral blood flow, and α-ketoglutarate may play important roles in preserving brain physiology in aging. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  18. Determination of ketone bodies in blood by headspace gas chromatography-mass spectrometry

    DEFF Research Database (Denmark)

    Holm, Karen Marie Dollerup; Linnet, Kristian; Rasmussen, Brian Schou

    2010-01-01

    A gas chromatography-mass spectrometry (GC-MS) method for determination of ketone bodies (ß-hydroxybutyrate, acetone, and acetoacetate) in blood is presented. The method is based on enzymatic oxidation of D-ß-hydroxybutyrate to acetoacetate, followed by decarboxylation to acetone, which...... was quantified by the use of headspace GC-MS using acetone-(13)C(3) as an internal standard. The developed method was found to have intra- and total interday relative standard deviations

  19. Inborn Errors of Metabolism with Acidosis: Organic Acidemias and Defects of Pyruvate and Ketone Body Metabolism.

    Science.gov (United States)

    Schillaci, Lori-Anne P; DeBrosse, Suzanne D; McCandless, Shawn E

    2018-04-01

    When a child presents with high-anion gap metabolic acidosis, the pediatrician can proceed with confidence by recalling some basic principles. Defects of organic acid, pyruvate, and ketone body metabolism that present with acute acidosis are reviewed. Flowcharts for identifying the underlying cause and initiating life-saving therapy are provided. By evaluating electrolytes, blood sugar, lactate, ammonia, and urine ketones, the provider can determine the likelihood of an inborn error of metabolism. Freezing serum, plasma, and urine samples during the acute presentation for definitive diagnostic testing at the provider's convenience aids in the differential diagnosis. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Fast quantification of short chain fatty acids and ketone bodies by liquid chromatography-tandem mass spectrometry after facile derivatization coupled with liquid-liquid extraction.

    Science.gov (United States)

    Zeng, Mingfei; Cao, Huachuan

    2018-04-15

    Short chain fatty acids (SCFA) and ketone bodies recently emerged as important physiological relevant metabolites because of their association with microbiota, immunology, obesity and other metabolic states. They were commonly analyzed by GC-MS with long run time and laborious sample preparation. In this study we developed a novel LC-MS/MS method using fast derivatization coupled with liquid-liquid extraction to detect SCFA and ketone bodies in plasma and feces. Several different derivatization reagents were evaluated to compare the efficiency, the sensitivity and chromatographic separation of structural isomers. O‑benzylhydroxylamine was selected for its superior overall performance in reaction time and isomeric separation that allowed the measurement of each SCFAs and ketone bodies free from interferences. The derivatization procedure is facile and reproducible in aqueous-organic medium, which abolished the evaporation procedure hampering the analysis of volatile short chain acids. Enhancement in sensitivity remarkably improved the detection limit of SCFA and ketone bodies to sub-fmol level. This novel method was applied to quantify these metabolites in fecal and plasma samples from lean and DIO mouse. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Cerebral ketone body metabolism.

    Science.gov (United States)

    Morris, A A M

    2005-01-01

    Ketone bodies (KBs) are an important source of energy for the brain. During the neonatal period, they are also precursors for the synthesis of lipids (especially cholesterol) and amino acids. The rate of cerebral KB metabolism depends primarily on the concentration in blood; high concentrations occur during fasting and on a high-fat diet. Cerebral KB metabolism is also regulated by the permeability of the blood-brain barrier (BBB), which depends on the abundance of monocarboxylic acid transporters (MCT1). The BBB's permeability to KBs increases with fasting in humans. In rats, permeability increases during the suckling period, but human neonates have not been studied. Monocarboxylic acid transporters are also present in the plasma membranes of neurons and glia but their role in regulating KB metabolism is uncertain. Finally, the rate of cerebral KB metabolism depends on the activities of the relevant enzymes in brain. The activities vary with age in rats, but reliable results are not available for humans. Cerebral KB metabolism in humans differs from that in the rat in several respects. During fasting, for example, KBs supply more of the brain's energy in humans than in the rat. Conversely, KBs are probably used more extensively in the brain of suckling rats than in human neonates. These differences complicate the interpretation of rodent studies. Most patients with inborn errors of ketogenesis develop normally, suggesting that the only essential role for KBs is as an alternative fuel during illness or prolonged fasting. On the other hand, in HMG-CoA lyase deficiency, imaging generally shows asymptomatic white-matter abnormalities. The ability of KBs to act as an alternative fuel explains the effectiveness of the ketogenic diet in GLUT1 deficiency, but its effectiveness in epilepsy remains unexplained.

  2. Differential utilization of ketone bodies by neurons and glioma cell lines: a rationale for ketogenic diet as experimental glioma therapy.

    Science.gov (United States)

    Maurer, Gabriele D; Brucker, Daniel P; Bähr, Oliver; Harter, Patrick N; Hattingen, Elke; Walenta, Stefan; Mueller-Klieser, Wolfgang; Steinbach, Joachim P; Rieger, Johannes

    2011-07-26

    Even in the presence of oxygen, malignant cells often highly depend on glycolysis for energy generation, a phenomenon known as the Warburg effect. One strategy targeting this metabolic phenotype is glucose restriction by administration of a high-fat, low-carbohydrate (ketogenic) diet. Under these conditions, ketone bodies are generated serving as an important energy source at least for non-transformed cells. To investigate whether a ketogenic diet might selectively impair energy metabolism in tumor cells, we characterized in vitro effects of the principle ketone body 3-hydroxybutyrate in rat hippocampal neurons and five glioma cell lines. In vivo, a non-calorie-restricted ketogenic diet was examined in an orthotopic xenograft glioma mouse model. The ketone body metabolizing enzymes 3-hydroxybutyrate dehydrogenase 1 and 2 (BDH1 and 2), 3-oxoacid-CoA transferase 1 (OXCT1) and acetyl-CoA acetyltransferase 1 (ACAT1) were expressed at the mRNA and protein level in all glioma cell lines. However, no activation of the hypoxia-inducible factor-1α (HIF-1α) pathway was observed in glioma cells, consistent with the absence of substantial 3-hydroxybutyrate metabolism and subsequent accumulation of succinate. Further, 3-hydroxybutyrate rescued hippocampal neurons from glucose withdrawal-induced cell death but did not protect glioma cell lines. In hypoxia, mRNA expression of OXCT1, ACAT1, BDH1 and 2 was downregulated. In vivo, the ketogenic diet led to a robust increase of blood 3-hydroxybutyrate, but did not alter blood glucose levels or improve survival. In summary, glioma cells are incapable of compensating for glucose restriction by metabolizing ketone bodies in vitro, suggesting a potential disadvantage of tumor cells compared to normal cells under a carbohydrate-restricted ketogenic diet. Further investigations are necessary to identify co-treatment modalities, e.g. glycolysis inhibitors or antiangiogenic agents that efficiently target non-oxidative pathways.

  3. Differential utilization of ketone bodies by neurons and glioma cell lines: a rationale for ketogenic diet as experimental glioma therapy

    International Nuclear Information System (INIS)

    Maurer, Gabriele D; Brucker, Daniel P; Bähr, Oliver; Harter, Patrick N; Hattingen, Elke; Walenta, Stefan; Mueller-Klieser, Wolfgang; Steinbach, Joachim P; Rieger, Johannes

    2011-01-01

    Even in the presence of oxygen, malignant cells often highly depend on glycolysis for energy generation, a phenomenon known as the Warburg effect. One strategy targeting this metabolic phenotype is glucose restriction by administration of a high-fat, low-carbohydrate (ketogenic) diet. Under these conditions, ketone bodies are generated serving as an important energy source at least for non-transformed cells. To investigate whether a ketogenic diet might selectively impair energy metabolism in tumor cells, we characterized in vitro effects of the principle ketone body 3-hydroxybutyrate in rat hippocampal neurons and five glioma cell lines. In vivo, a non-calorie-restricted ketogenic diet was examined in an orthotopic xenograft glioma mouse model. The ketone body metabolizing enzymes 3-hydroxybutyrate dehydrogenase 1 and 2 (BDH1 and 2), 3-oxoacid-CoA transferase 1 (OXCT1) and acetyl-CoA acetyltransferase 1 (ACAT1) were expressed at the mRNA and protein level in all glioma cell lines. However, no activation of the hypoxia-inducible factor-1α (HIF-1α) pathway was observed in glioma cells, consistent with the absence of substantial 3-hydroxybutyrate metabolism and subsequent accumulation of succinate. Further, 3-hydroxybutyrate rescued hippocampal neurons from glucose withdrawal-induced cell death but did not protect glioma cell lines. In hypoxia, mRNA expression of OXCT1, ACAT1, BDH1 and 2 was downregulated. In vivo, the ketogenic diet led to a robust increase of blood 3-hydroxybutyrate, but did not alter blood glucose levels or improve survival. In summary, glioma cells are incapable of compensating for glucose restriction by metabolizing ketone bodies in vitro, suggesting a potential disadvantage of tumor cells compared to normal cells under a carbohydrate-restricted ketogenic diet. Further investigations are necessary to identify co-treatment modalities, e.g. glycolysis inhibitors or antiangiogenic agents that efficiently target non-oxidative pathways

  4. Regulation of Ketone Body Metabolism and the Role of PPARα

    Directory of Open Access Journals (Sweden)

    Maja Grabacka

    2016-12-01

    Full Text Available Ketogenesis and ketolysis are central metabolic processes activated during the response to fasting. Ketogenesis is regulated in multiple stages, and a nuclear receptor peroxisome proliferator activated receptor α (PPARα is one of the key transcription factors taking part in this regulation. PPARα is an important element in the metabolic network, where it participates in signaling driven by the main nutrient sensors, such as AMP-activated protein kinase (AMPK, PPARγ coactivator 1α (PGC-1α, and mammalian (mechanistic target of rapamycin (mTOR and induces hormonal mediators, such as fibroblast growth factor 21 (FGF21. This work describes the regulation of ketogenesis and ketolysis in normal and malignant cells and briefly summarizes the positive effects of ketone bodies in various neuropathologic conditions.

  5. Biomarkers, ketone bodies, and the prevention of Alzheimer's disease.

    Science.gov (United States)

    VanItallie, Theodore B

    2015-03-01

    Sporadic Alzheimer's disease (spAD) has three successive phases: preclinical, mild cognitive impairment, and dementia. Individuals in the preclinical phase are cognitively normal. Diagnosis of preclinical spAD requires evidence of pathologic brain changes provided by established biomarkers. Histopathologic features of spAD include (i) extra-cellular cerebral amyloid plaques and intracellular neurofibrillary tangles that embody hyperphosphorylated tau; and (ii) neuronal and synaptic loss. Amyloid-PET brain scans conducted during spAD's preclinical phase have disclosed abnormal accumulations of amyloid-beta (Aβ) in cognitively normal, high-risk individuals. However, this measure correlates poorly with changes in cognitive status. In contrast, MRI measures of brain atrophy consistently parallel cognitive deterioration. By the time dementia appears, amyloid deposition has already slowed or ceased. When a new treatment offers promise of arresting or delaying progression of preclinical spAD, its effectiveness must be inferred from intervention-correlated changes in biomarkers. Herein, differing tenets of the amyloid cascade hypothesis (ACH) and the mitochondrial cascade hypothesis (MCH) are compared. Adoption of the ACH suggests therapeutic research continue to focus on aspects of the amyloid pathways. Adoption of the MCH suggests research emphasis be placed on restoration and stabilization of mitochondrial function. Ketone ester (KE)-induced elevation of plasma ketone body (KB) levels improves mitochondrial metabolism and prevents or delays progression of AD-like pathologic changes in several AD animal models. Thus, as a first step, it is imperative to determine whether KE-caused hyperketonemia can bring about favorable changes in biomarkers of AD pathology in individuals who are in an early stage of AD's preclinical phase. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. 21 CFR 862.1435 - Ketones (nonquantitative) test system.

    Science.gov (United States)

    2010-04-01

    ...) test system is a device intended to identify ketones in urine and other body fluids. Identification of ketones is used in the diagnosis and treatment of acidosis (a condition characterized by abnormally high...) Classification. Class I (general controls). The device is exempt from the premarket notification procedures in...

  7. Differential utilization of ketone bodies by neurons and glioma cell lines: a rationale for ketogenic diet as experimental glioma therapy

    Directory of Open Access Journals (Sweden)

    Mueller-Klieser Wolfgang

    2011-07-01

    Full Text Available Abstract Background Even in the presence of oxygen, malignant cells often highly depend on glycolysis for energy generation, a phenomenon known as the Warburg effect. One strategy targeting this metabolic phenotype is glucose restriction by administration of a high-fat, low-carbohydrate (ketogenic diet. Under these conditions, ketone bodies are generated serving as an important energy source at least for non-transformed cells. Methods To investigate whether a ketogenic diet might selectively impair energy metabolism in tumor cells, we characterized in vitro effects of the principle ketone body 3-hydroxybutyrate in rat hippocampal neurons and five glioma cell lines. In vivo, a non-calorie-restricted ketogenic diet was examined in an orthotopic xenograft glioma mouse model. Results The ketone body metabolizing enzymes 3-hydroxybutyrate dehydrogenase 1 and 2 (BDH1 and 2, 3-oxoacid-CoA transferase 1 (OXCT1 and acetyl-CoA acetyltransferase 1 (ACAT1 were expressed at the mRNA and protein level in all glioma cell lines. However, no activation of the hypoxia-inducible factor-1α (HIF-1α pathway was observed in glioma cells, consistent with the absence of substantial 3-hydroxybutyrate metabolism and subsequent accumulation of succinate. Further, 3-hydroxybutyrate rescued hippocampal neurons from glucose withdrawal-induced cell death but did not protect glioma cell lines. In hypoxia, mRNA expression of OXCT1, ACAT1, BDH1 and 2 was downregulated. In vivo, the ketogenic diet led to a robust increase of blood 3-hydroxybutyrate, but did not alter blood glucose levels or improve survival. Conclusion In summary, glioma cells are incapable of compensating for glucose restriction by metabolizing ketone bodies in vitro, suggesting a potential disadvantage of tumor cells compared to normal cells under a carbohydrate-restricted ketogenic diet. Further investigations are necessary to identify co-treatment modalities, e.g. glycolysis inhibitors or antiangiogenic

  8. Metabolism of fatty acids and the levels of ketone bodies in the livers of pyridoxine-deficient rats

    International Nuclear Information System (INIS)

    Gomikawa, Shuzo; Okada, Mitsuko

    1978-01-01

    Lipid metabolism was examined in rats fed a high-protein pyridoxine-deficient diet, and their livers were found to contain large amounts of lipids, mainly in the forms of triglycerides and cholesteryl ester. The contents of ketone bodies in the livers of pyridoxine-deficient and the control rats were similar. Their NAD + /NADH ratios, calculated from the amounts of ketone bodies, were also similar in pyridoxine-deficient and control groups when the animals were fed, but the ratio in pyridoxine-deficient rats was lower than that of control rats when the animals were starved. After injection of 14 C-linoleic acid, the amounts of expired 14 CO 2 in pyridoxine-deficient and control rats were similar. The pattern of incorporations of 14 C-linoleic acid into various lipid components of the livers were examined; incorporation into the phospholipid fraction was similar in control and deficient rats, but the incorporation into the triglyceride fraction was slower, and the incorporation into cholesterol was faster in deficient animals than in controls. (auth.)

  9. Ketone-body utilization and lipid synthesis by developing rat brain—a comparison between in vivo and in vitro experiments

    NARCIS (Netherlands)

    Klein, W.; Lopes-Cardozo, M.

    1984-01-01

    The distribution of ketone bodies between oxidation and lipid synthesis was analysed in homogenates of developing rat brain. The capacity for lipid synthesis of homogenized or minced brain preparations was compared with rates of lipid synthesis in vivo, assessed by incorporation of ³H from

  10. Perspectives on the metabolic management of epilepsy through dietary reduction of glucose and elevation of ketone bodies.

    Science.gov (United States)

    Greene, Amanda E; Todorova, Mariana T; Seyfried, Thomas N

    2003-08-01

    Brain cells are metabolically flexible because they can derive energy from both glucose and ketone bodies (acetoacetate and beta-hydroxybutyrate). Metabolic control theory applies principles of bioenergetics and genome flexibility to the management of complex phenotypic traits. Epilepsy is a complex brain disorder involving excessive, synchronous, abnormal electrical firing patterns of neurons. We propose that many epilepsies with varied etiologies may ultimately involve disruptions of brain energy homeostasis and are potentially manageable through principles of metabolic control theory. This control involves moderate shifts in the availability of brain energy metabolites (glucose and ketone bodies) that alter energy metabolism through glycolysis and the tricarboxylic acid cycle, respectively. These shifts produce adjustments in gene-linked metabolic networks that manage or control the seizure disorder despite the continued presence of the inherited or acquired factors responsible for the epilepsy. This hypothesis is supported by information on the management of seizures with diets including fasting, the ketogenic diet and caloric restriction. A better understanding of the compensatory genetic and neurochemical networks of brain energy metabolism may produce novel antiepileptic therapies that are more effective and biologically friendly than those currently available.

  11. Effect of insulin pump and continuous intravenous insulin on ketone body metabolism, blood gas indexes and stress state in patients with diabetic ketoacidosis

    Directory of Open Access Journals (Sweden)

    Hui-Jin Shi

    2017-09-01

    Full Text Available Objective: To study the effect of insulin pump and continuous intravenous insulin on ketone body metabolism, blood gas indexes and stress state in patients with diabetic ketoacidosis. Methods: Patients with diabetic ketoacidosis who were treated in Meizhou Maternal and Child Heath Hospital between May 2014 and March 2017 were selected as the research subjects and randomly divided into the group A who received subcutaneous insulin infusion by insulin pump and the group B who received intravenous small-dose insulin injection by micropump. The indexes of ketone body, blood gas and stress were measured before and after treatment. Results: 12 h and 24 h after treatment, serum β-hydroxybutyrate, MDA, NE, ACTH and Cor contents of both groups of patients were significantly lower than those before treatment while pH, HCO3 - and base excess levels as well as serum SOD, GSH-Px, CAT and TAC contents were significantly higher than those before treatment, and serum β-hydroxybutyrate, MDA, NE, ACTH and Cor contents of group A were significantly lower than those of group B while pH, HCO3 - and base excess levels as well as serum SOD, GSH-Px, CAT and TAC contents were significantly higher than those of group B. Conclusion: Subcutaneous insulin infusion by insulin pump can improve ketone body metabolism, acidosis status and stress state in patients with diabetic ketoacidosis.

  12. Systemic, cerebral and skeletal muscle ketone body and energy metabolism during acute hyper-D-β-hydroxybutyratemia in post-absorptive healthy males

    DEFF Research Database (Denmark)

    Mikkelsen, Kristian H; Seifert, Thomas; Secher, Niels H

    2015-01-01

    CONTEXT: Ketone bodies are substrates during fasting and when on a ketogenic diet not the least for the brain and implicated in the management of epileptic seizures and dementia. Moreover, D-β-hydroxybutyrate (HOB) is suggested to reduce blood glucose and fatty acid levels. OBJECTIVES...

  13. Comparing Finger-stick β-Hydroxybutyrate with Dipstick Urine Tests in the Detection of Ketone Bodies

    Directory of Open Access Journals (Sweden)

    Baris KURU

    2014-06-01

    Full Text Available SUMMARY: Objectives: Blood ketone (beta-hydroxybutyrate measurements are suggested instead of urine ketone (acetoacetate measurements in the diagnosis of diabetic ketoacidosis. Urine ketone examination is difficult and time consuming, and may result in an incorrect interpretation. Studies performed in emergency departments on blood ketones are limited. Our objective is to compare urine ketones and capillary blood ketones in patients whose serum glucose levels were ≥150 mg/dl. Methods: In our cross-sectional prospective study, finger-stick blood beta-hydroxybutyrate, arterial blood gas and urine ketone measurements of patients whose serum glucose levels were 150 mg/dL and higher were performed in the emergency department. Results: A total of 265 patients were included in the study. The mean age of the patients was 62.4±14.9 years, and 65.7% of them were female. The mean of the capillary blood ketone levels of the patients was determined to be 0.524±0.9 mmol/L (min: 0 mmol/L, max: 6.7 mmol/L. In 29 (13.1% of the 221 patients whose urine ketone levels were negative, the finger-stick blood ketone levels were positive. Three of these patients were severely ketonemic, six were moderately ketonemic, and 20 were mildly ketonemic. Conclusions: In patients admitted to the emergency department with a blood glucose level of 150 mg/dL or higher, performing a capillary blood ketone measurement instead of a urine ketone measurement was a better predictor of ketonemia. ÖZET: Amaç: Diyabetik keto asidoz tanısında idrar ketonu (asetoasetat yerine kan ketonu (beta-hidroksibütirat ölçümü önerilmektedir. İdrar ketonu bakılması zahmetli, zaman alıcı ve yanlış yorumlara yol açabilen bir testtir. Acil servislerde kan ketonu ile ilgili yapılan çalışmalar sınırlıdır. Bu çalışmadaki amacımız serum glikoz düzeyi ≥150 mg/dl tespit edilen hastalarda idrar ketonu ile kapiller kanda keton varlığını karşılaştırmaktır. Gereç ve Y

  14. Relative utilization of fatty acids for synthesis of ketone bodies and complex lipids in the liver of developing rats.

    Science.gov (United States)

    Yeh, Y Y; Streuli, V L; Zee, P

    1977-04-01

    The regulation of hepatic ketogenesis, as related to the metabolism of fatty acids through oxidative and synthetic pathways, was studied in developing rats. [1-14C] palmitate was used as a substrate to determine the proportions of free fatty acids utilized for the production of ketone bodies, CO2 and complex lipids. Similar developmental patterns of hepatic ketogenesis were obtained by measuring the production of either [14C] acetoacetate from exogenous [1-14C] palmitate or the sum of unlabeled acetoacetate and beta-hydroxybutyrate from endogenous fatty acids. The production of total ketone bodies was low during the late fetal stage and at birth, but increased rapidly to a miximum value within 24 hr after brith. The maximal ketogenic capacity appeared to be maintained for the first 10 days of life. 14CO2 production from [1-14C] palmitate increased by two- to fourfold during the suckling period, from its initial low rate seen at birth. The capacity for synthesis of total complex lipids was low at birth and had increased by day 3 to a maximal value, which was comparable to that of adult fed rats. The high lipogenic capacity lasted throughout the remaining suckling period. When ketogenesis was inhibited by 4-pentenoic acid, the rate of synthesis of complex lipids did not increase despite an increase in unutilized fatty acids. During the mid-suckling period, approximately equal amounts of [1-14C] palmitate were utilized for the synthesis of ketone plus CO2 and for complex lipid synthesis. By contrast, in adult fed rats, the incorporation of fatty acids into complex lipids was four times higher than that of ketone plus CO2. These observations suggest that stimulated hepatic ketogenesis in suckling rats results from the rapid oxidation of fatty acids and consequent increased production of acetyl CoA, but not from impaired capacity for synthesis of complex lipids.

  15. Contribution of ketone bodies to cholesterogenesis in Morris hepatoma 7777 cells

    International Nuclear Information System (INIS)

    Hilderbrandt, L.; Elson, C.; Shrago, E.

    1990-01-01

    Cholesterol synthesis in neoplastic tissues is typically measured in incubations of minced tissue or tissue slices with 10 mM concentrations of individual substrates. Carbon incorporation into cholesterol from [ 14 C] labelled substrates by freshly isolated hepatoma cells was measured after one hour incubation with 10 mm single substrates. These observations were extended by measuring cholesterol synthesis supported by [ 14 C] substrates in a media containing a mixture of substrates at physiological concentrations: 5.0 mM glucose, 1.3 mM D(-)-3-hydroxybutyrate, 0.5 mM acetoacetate, 0.3 mM acetate, 0.3 mM oleate, 0.3 mM palmitate, 0.65 mM glutamine, 1.4 mM lactate and 0.1 mM pyruvate in Eagle's modified essential medium. Under single substrate conditions, the ketone bodies contribute substantially to cholesterogenesis. Estimates of the quantitative contribution of each substrate to total cholesterol synthesis are reported

  16. Blood ketone response to norepinephrine-induced free fatty acid in diabetes

    Energy Technology Data Exchange (ETDEWEB)

    Blackard, W G; Omori, Yoshiaki

    1963-04-18

    During 90-minute norepinephrine infusions, blood free fatty acid and ketone responses of Japanese nondiabetic and diabetic subjects were determined. Nonobese diabetic subjects with and without fasting hyperglycemia demonstrated significantly greater blood ketone elevations than nondiabetics. An inverse correlation between obesity and blood ketone response to nonrepinephrine was observed in diabetics. This correlation could not be attributed to varying degrees of fasting hyperglycemia or free fatty acid elevation. Nonobese diabetics with mild fasting hyperglycemia (90 to 150 mg%) exhibited an unexpected greater increase in blood ketones than nonobese diabetics with moderate fasting hyperglycemia (150 to 250 mg%). Differences in free fatty acid elevations were not responsible for this apparent paradox. The magnitude of the hyperketonemic response, though dependent on free fatty elevation, seemed more sensitive to the degree of obesity and the fasting blood glucose level. Fractional ketone body measurements attributed the blood ketone elevations predominantly to ..beta..-hydroxybutyric acid increases. 43 references, 6 figures, 1 table.

  17. Ketone-Based Metabolic Therapy: Is Increased NAD+ a Primary Mechanism?

    Directory of Open Access Journals (Sweden)

    Marwa Elamin

    2017-11-01

    Full Text Available The ketogenic diet’s (KD anticonvulsant effects have been well-documented for nearly a century, including in randomized controlled trials. Some patients become seizure-free and some remain so after diet cessation. Many recent studies have explored its expanded therapeutic potential in diverse neurological disorders, yet no mechanism(s of action have been established. The diet’s high fat, low carbohydrate composition reduces glucose utilization and promotes the production of ketone bodies. Ketone bodies are a more efficient energy source than glucose and improve mitochondrial function and biogenesis. Cellular energy production depends on the metabolic coenzyme nicotinamide adenine dinucleotide (NAD, a marker for mitochondrial and cellular health. Furthermore, NAD activates downstream signaling pathways (such as the sirtuin enzymes associated with major benefits such as longevity and reduced inflammation; thus, increasing NAD is a coveted therapeutic endpoint. Based on differential NAD+ utilization during glucose- vs. ketone body-based acetyl-CoA generation for entry into the tricarboxylic cycle, we propose that a KD will increase the NAD+/NADH ratio. When rats were fed ad libitum KD, significant increases in hippocampal NAD+/NADH ratio and blood ketone bodies were detected already at 2 days and remained elevated at 3 weeks, indicating an early and persistent metabolic shift. Based on diverse published literature and these initial data we suggest that increased NAD during ketolytic metabolism may be a primary mechanism behind the beneficial effects of this metabolic therapy in a variety of brain disorders and in promoting health and longevity.

  18. Effect of the Ketone Body Beta-Hydroxybutyrate on the Innate Defense Capability of Primary Bovine Mammary Epithelial Cells

    OpenAIRE

    Hillreiner, Maria;Flinspach, Claudia;Pfaffl, Michael W.;Kliem, Heike

    2017-01-01

    Negative energy balance and ketosis are thought to cause impaired immune function and to increase the risk of clinical mastitis in dairy cows. The present in vitro study aimed to investigate the effect of elevated levels of the predominant ketone body β-hydroxybutyrate on the innate defense capability of primary bovine mammary epithelial cells (pbMEC) challenged with the mastitis pathogen Escherichia coli (E. coli). Therefore, pbMEC of healthy dairy cows in mid- lactation were isolated from m...

  19. Imact of feeding and post prandial time on plasma ketone bodies in sows during transition and lactation

    DEFF Research Database (Denmark)

    Theil, Peter Kappel; Olesen, A K; Flummer, Christine

    2013-01-01

    Two experiments were conducted with the aim of studying how dietary fat source, reproductive stage (Exp. 1), and diurnal variation (Exp. 2) affect plasma ketone bodies in sows. In Exp. 1, 40 second-parity sows were fed 1 of 5 lactation diets from 7 d prepartum until 28 d postpartum, with low or h......, therefore, primary ketosis does not appear to be a major problem in sows. In addition, this study indicates that the intermediary metabolism of sows was challenged when sows were exposed to high fat diets in late gestation....

  20. SIRT3 deacetylates mitochondrial 3-hydroxy-3-methylglutaryl CoA synthase 2 and regulates ketone body production

    DEFF Research Database (Denmark)

    Shimazu, Tadahiro; Hirschey, Matthew D; Hua, Lan

    2010-01-01

    with SIRT3 and in vivo by overexpression of SIRT3. Deacetylation of HMGCS2 lysines 310, 447, and 473 by incubation with wild-type SIRT3 or by mutation to arginine enhances its enzymatic activity. Molecular dynamics simulations show that in silico deacetylation of these three lysines causes conformational...... changes of HMGCS2 near the active site. Mice lacking SIRT3 show decreased β-hydroxybutyrate levels during fasting. Our findings show SIRT3 regulates ketone body production during fasting and provide molecular insight into how protein acetylation can regulate enzymatic activity....

  1. Short-chain fatty acids and ketones directly regulate sympathetic nervous system via G protein-coupled receptor 41 (GPR41).

    Science.gov (United States)

    Kimura, Ikuo; Inoue, Daisuke; Maeda, Takeshi; Hara, Takafumi; Ichimura, Atsuhiko; Miyauchi, Satoshi; Kobayashi, Makio; Hirasawa, Akira; Tsujimoto, Gozoh

    2011-05-10

    The maintenance of energy homeostasis is essential for life, and its dysregulation leads to a variety of metabolic disorders. Under a fed condition, mammals use glucose as the main metabolic fuel, and short-chain fatty acids (SCFAs) produced by the colonic bacterial fermentation of dietary fiber also contribute a significant proportion of daily energy requirement. Under ketogenic conditions such as starvation and diabetes, ketone bodies produced in the liver from fatty acids are used as the main energy sources. To balance energy intake, dietary excess and starvation trigger an increase or a decrease in energy expenditure, respectively, by regulating the activity of the sympathetic nervous system (SNS). The regulation of metabolic homeostasis by glucose is well recognized; however, the roles of SCFAs and ketone bodies in maintaining energy balance remain unclear. Here, we show that SCFAs and ketone bodies directly regulate SNS activity via GPR41, a Gi/o protein-coupled receptor for SCFAs, at the level of the sympathetic ganglion. GPR41 was most abundantly expressed in sympathetic ganglia in mouse and humans. SCFA propionate promoted sympathetic outflow via GPR41. On the other hand, a ketone body, β-hydroxybutyrate, produced during starvation or diabetes, suppressed SNS activity by antagonizing GPR41. Pharmacological and siRNA experiments indicated that GPR41-mediated activation of sympathetic neurons involves Gβγ-PLCβ-MAPK signaling. Sympathetic regulation by SCFAs and ketone bodies correlated well with their respective effects on energy consumption. These findings establish that SCFAs and ketone bodies directly regulate GPR41-mediated SNS activity and thereby control body energy expenditure in maintaining metabolic homeostasis.

  2. Fatty acid-induced astrocyte ketone production and the control of food intake.

    Science.gov (United States)

    Le Foll, Christelle; Levin, Barry E

    2016-06-01

    Obesity and Type 2 diabetes are major worldwide public health issues today. A relationship between total fat intake and obesity has been found. In addition, the mechanisms of long-term and excessive high-fat diet (HFD) intake in the development of obesity still need to be elucidated. The ventromedial hypothalamus (VMH) is a major site involved in the regulation of glucose and energy homeostasis where "metabolic sensing neurons" integrate metabolic signals from the periphery. Among these signals, fatty acids (FA) modulate the activity of VMH neurons using the FA translocator/CD36, which plays a critical role in the regulation of energy and glucose homeostasis. During low-fat diet (LFD) intake, FA are oxidized by VMH astrocytes to fuel their ongoing metabolic needs. However, HFD intake causes VMH astrocytes to use FA to generate ketone bodies. We postulate that these astrocyte-derived ketone bodies are exported to neurons where they produce excess ATP and reactive oxygen species, which override CD36-mediated FA sensing and act as a signal to decrease short-term food intake. On a HFD, VMH astrocyte-produced ketones reduce elevated caloric intake to LFD levels after 3 days in rats genetically predisposed to resist (DR) diet-induced obesity (DIO), but not leptin-resistant DIO rats. This suggests that, while VMH ketone production on a HFD can contribute to protection from obesity, the inherent leptin resistance overrides this inhibitory action of ketone bodies on food intake. Thus, astrocytes and neurons form a tight metabolic unit that is able to monitor circulating nutrients to alter food intake and energy homeostasis. Copyright © 2016 the American Physiological Society.

  3. Metabolic Responses in Endothelial Cells Following Exposure to Ketone Bodies

    Directory of Open Access Journals (Sweden)

    Erika Meroni

    2018-02-01

    Full Text Available The ketogenic diet (KD is a high-fat, low-carbohydrate diet based on the induction of the synthesis of ketone bodies (KB. Despite its widespread use, the systemic impact of KD is not completely understood. The purpose of this study was to evaluate the effects of physiological levels of KB on HMEC-1 endothelial cells. To this aim, DNA oxidative damage and the activation of Nrf2, a known transcriptional factor involved in cell responses to oxidative stress, were assessed. The exposure of cells to KB exerted a moderate genotoxic effect, measured by a significant increase in DNA oxidative damage. However, cells pre-treated with KB for 48 h and subjected to a secondary oxidative insult (H2O2, significantly decreased DNA damage compared to control oxidized cells. This protection occurred by the activation of Nrf2 pathway. In KB-treated cells, we found increased levels of Nrf2 in nuclear extracts and higher gene expression of HO-1, a target gene of Nrf2, compared to control cells. These results suggest that KB, by inducing moderate oxidative stress, activate the transcription factor Nrf2, which induces the transcription of target genes involved in the cellular antioxidant defense system.

  4. Monte Carlo study of thermal flux profiles and body correction factors for body protein measurements of obese subjects

    International Nuclear Information System (INIS)

    McGregor, B.J.; Allen, B.J.

    1991-01-01

    In previous calculations for total body nitrogen measurements of children, the anterior/posterior thermal neutron flux profile with depth was found to be fairly flat after an initial rise. However, for obese adults significant variations are found in the flux profile with the central flux value being as low as 20% of the peak value. The significance of these flux variations is examined. Correction factors are calculated for the varying attenuation of the nitrogen and hydrogen photons by a range of obese bodies. The calculations included the effect of the thermal flux profile as well as that of an outer layer of low nitrogen content adipose tissue. The bodies are assumed to have a homogeneous hydrogen content. A study of four obese body models with varying sex and fat content shows that the correction factors do not vary much between males and females. This is surprising since the female models are assumed to have a surface fat layer twice as thick as for the male models. The correction factors are found to be only slightly sensitive to the thermal flux variations with depth. 5 refs., 1 tab., 4 figs

  5. Medium-chain fatty acids inhibit mitochondrial metabolism in astrocytes promoting astrocyte-neuron lactate and ketone body shuttle systems.

    Science.gov (United States)

    Thevenet, Jonathan; De Marchi, Umberto; Domingo, Jaime Santo; Christinat, Nicolas; Bultot, Laurent; Lefebvre, Gregory; Sakamoto, Kei; Descombes, Patrick; Masoodi, Mojgan; Wiederkehr, Andreas

    2016-05-01

    Medium-chain triglycerides have been used as part of a ketogenic diet effective in reducing epileptic episodes. The health benefits of the derived medium-chain fatty acids (MCFAs) are thought to result from the stimulation of liver ketogenesis providing fuel for the brain. We tested whether MCFAs have direct effects on energy metabolism in induced pluripotent stem cell-derived human astrocytes and neurons. Using single-cell imaging, we observed an acute pronounced reduction of the mitochondrial electrical potential and a concomitant drop of the NAD(P)H signal in astrocytes, but not in neurons. Despite the observed effects on mitochondrial function, MCFAs did not lower intracellular ATP levels or activate the energy sensor AMP-activated protein kinase. ATP concentrations in astrocytes were unaltered, even when blocking the respiratory chain, suggesting compensation through accelerated glycolysis. The MCFA decanoic acid (300 μM) promoted glycolysis and augmented lactate formation by 49.6%. The shorter fatty acid octanoic acid (300 μM) did not affect glycolysis but increased the rates of astrocyte ketogenesis 2.17-fold compared with that of control cells. MCFAs may have brain health benefits through the modulation of astrocyte metabolism leading to activation of shuttle systems that provide fuel to neighboring neurons in the form of lactate and ketone bodies.-Thevenet, J., De Marchi, U., Santo Domingo, J., Christinat, N., Bultot, L., Lefebvre, G., Sakamoto, K., Descombes, P., Masoodi, M., Wiederkehr, A. Medium-chain fatty acids inhibit mitochondrial metabolism in astrocytes promoting astrocyte-neuron lactate and ketone body shuttle systems. © FASEB.

  6. Breath Ketone Testing: A New Biomarker for Diagnosis and Therapeutic Monitoring of Diabetic Ketosis

    Directory of Open Access Journals (Sweden)

    Yue Qiao

    2014-01-01

    Full Text Available Background. Acetone, β-hydroxybutyric acid, and acetoacetic acid are three types of ketone body that may be found in the breath, blood, and urine. Detecting altered concentrations of ketones in the breath, blood, and urine is crucial for the diagnosis and treatment of diabetic ketosis. The aim of this study was to evaluate the advantages of different detection methods for ketones, and to establish whether detection of the concentration of ketones in the breath is an effective and practical technique. Methods. We measured the concentrations of acetone in the breath using gas chromatography-mass spectrometry and β-hydroxybutyrate in fingertip blood collected from 99 patients with diabetes assigned to groups 1 (−, 2 (±, 3 (+, 4 (++, or 5 (+++ according to urinary ketone concentrations. Results. There were strong relationships between fasting blood glucose, age, and diabetic ketosis. Exhaled acetone concentration significantly correlated with concentrations of fasting blood glucose, ketones in the blood and urine, LDL-C, creatinine, and blood urea nitrogen. Conclusions. Breath testing for ketones has a high sensitivity and specificity and appears to be a noninvasive, convenient, and repeatable method for the diagnosis and therapeutic monitoring of diabetic ketosis.

  7. A Ketone Ester Drink Increases Postexercise Muscle Glycogen Synthesis in Humans.

    Science.gov (United States)

    Holdsworth, David A; Cox, Peter J; Kirk, Tom; Stradling, Huw; Impey, Samuel G; Clarke, Kieran

    2017-09-01

    Physical endurance can be limited by muscle glycogen stores, in that glycogen depletion markedly reduces external work. During carbohydrate restriction, the liver synthesizes the ketone bodies, D-β-hydroxybutyrate, and acetoacetate from fatty acids. In animals and in the presence of glucose, D-β-hydroxybutyrate promotes insulin secretion and increases glycogen synthesis. Here we determined whether a dietary ketone ester, combined with plentiful glucose, can increase postexercise glycogen synthesis in human skeletal muscle. After an interval-based glycogen depletion exercise protocol, 12 well-trained male athletes completed a randomized, three-arm, blinded crossover recovery study that consisted of consumption of either a taste-matched, zero-calorie control or a ketone monoester drink, followed by a 10-mM glucose clamp or saline infusion for 2 h. The three postexercise conditions were control drink then saline infusion, control drink then hyperglycemic clamp, or ketone ester drink then hyperglycemic clamp. Skeletal muscle glycogen content was determined in muscle biopsies of vastus lateralis taken before and after the 2-h clamps. The ketone ester drink increased blood D-β-hydroxybutyrate concentrations to a maximum of 5.3 versus 0.7 mM for the control drink (P glycogen was 50% higher (246 vs 164 mmol glycosyl units per kilogram dry weight, P glycogen synthesis.

  8. A Ketone Ester Diet Increases Brain Malonyl-CoA and Uncoupling Proteins 4 and 5 while Decreasing Food Intake in the Normal Wistar Rat*

    Science.gov (United States)

    Kashiwaya, Yoshihiro; Pawlosky, Robert; Markis, William; King, M. Todd; Bergman, Christian; Srivastava, Shireesh; Murray, Andrew; Clarke, Kieran; Veech, Richard L.

    2010-01-01

    Three groups of male Wistar rats were pair fed NIH-31 diets for 14 days to which were added 30% of calories as corn starch, palm oil, or R-3-hydroxybutyrate-R-1,3-butanediol monoester (3HB-BD ester). On the 14th day, animal brains were removed by freeze-blowing, and brain metabolites measured. Animals fed the ketone ester diet had elevated mean blood ketone bodies of 3.5 mm and lowered plasma glucose, insulin, and leptin. Despite the decreased plasma leptin, feeding the ketone ester diet ad lib decreased voluntary food intake 2-fold for 6 days while brain malonyl-CoA was increased by about 25% in ketone-fed group but not in the palm oil fed group. Unlike the acute effects of ketone body metabolism in the perfused working heart, there was no increased reduction in brain free mitochondrial [NAD+]/[NADH] ratio nor in the free energy of ATP hydrolysis, which was compatible with the observed 1.5-fold increase in brain uncoupling proteins 4 and 5. Feeding ketone ester or palm oil supplemented diets decreased brain l-glutamate by 15–20% and GABA by about 34% supporting the view that fatty acids as well as ketone bodies can be metabolized by the brain. PMID:20529850

  9. A ketone ester diet increases brain malonyl-CoA and Uncoupling proteins 4 and 5 while decreasing food intake in the normal Wistar Rat.

    Science.gov (United States)

    Kashiwaya, Yoshihiro; Pawlosky, Robert; Markis, William; King, M Todd; Bergman, Christian; Srivastava, Shireesh; Murray, Andrew; Clarke, Kieran; Veech, Richard L

    2010-08-20

    Three groups of male Wistar rats were pair fed NIH-31 diets for 14 days to which were added 30% of calories as corn starch, palm oil, or R-3-hydroxybutyrate-R-1,3-butanediol monoester (3HB-BD ester). On the 14th day, animal brains were removed by freeze-blowing, and brain metabolites measured. Animals fed the ketone ester diet had elevated mean blood ketone bodies of 3.5 mm and lowered plasma glucose, insulin, and leptin. Despite the decreased plasma leptin, feeding the ketone ester diet ad lib decreased voluntary food intake 2-fold for 6 days while brain malonyl-CoA was increased by about 25% in ketone-fed group but not in the palm oil fed group. Unlike the acute effects of ketone body metabolism in the perfused working heart, there was no increased reduction in brain free mitochondrial [NAD(+)]/[NADH] ratio nor in the free energy of ATP hydrolysis, which was compatible with the observed 1.5-fold increase in brain uncoupling proteins 4 and 5. Feeding ketone ester or palm oil supplemented diets decreased brain L-glutamate by 15-20% and GABA by about 34% supporting the view that fatty acids as well as ketone bodies can be metabolized by the brain.

  10. Effect of a lucerne feeding strategy in the first week postpartum on feed intake and ketone body profiles in blood plasma, urine, and milk in Holstein cows

    DEFF Research Database (Denmark)

    Larsen, Mogens; Kristensen, Niels Bastian

    2010-01-01

    The objectives were to investigate the effects of a lucerne feeding strategy to postpartum transition dairy cows on feed intake and ketone body profiles in plasma, urine, and milk. At calving, 13 Holstein cows were assigned to one of two treatments: a control lactation diet or a lucerne haylage l...

  11. Theoretical simulation of the dual-heat-flux method in deep body temperature measurements.

    Science.gov (United States)

    Huang, Ming; Chen, Wenxi

    2010-01-01

    Deep body temperature reveals individual physiological states, and is important in patient monitoring and chronobiological studies. An innovative dual-heat-flux method has been shown experimentally to be competitive with the conventional zero-heat-flow method in its performance, in terms of measurement accuracy and step response to changes in the deep temperature. We have utilized a finite element method to model and simulate the dynamic process of a dual-heat-flux probe in deep body temperature measurements to validate the fundamental principles of the dual-heat-flux method theoretically, and to acquire a detailed quantitative description of the thermal profile of the dual-heat-flux probe. The simulation results show that the estimated deep body temperature is influenced by the ambient temperature (linearly, at a maximum rate of 0.03 °C/°C) and the blood perfusion rate. The corresponding depth of the estimated temperature in the skin and subcutaneous tissue layer is consistent when using the dual-heat-flux probe. Insights in improving the performance of the dual-heat-flux method were discussed for further studies of dual-heat-flux probes, taking into account structural and geometric considerations.

  12. Ketone Diester Ingestion Impairs Time-Trial Performance in Professional Cyclists

    Directory of Open Access Journals (Sweden)

    Jill J. Leckey

    2017-10-01

    Full Text Available We investigated the effect of pre- “race” ingestion of a 1,3-butanediol acetoacetate diester on blood ketone concentration, substrate metabolism and performance of a cycling time trial (TT in professional cyclists. In a randomized cross-over design, 10 elite male cyclists completed a ~31 km laboratory-based TT on a cycling ergometer programmed to simulate the 2017 World Road Cycling Championships course. Cyclists consumed a standardized meal [2 g/kg body mass (BM carbohydrate (CHO] the evening prior to a trial day and a CHO breakfast (2 g/kg BM CHO with 200 mg caffeine on the morning of a trial day. Cyclists were randomized to consume either the ketone diester (2 × 250 mg/kg or a placebo drink, followed immediately by 200 mL diet cola, given ~ 30 min before and immediately prior to commencing a 20 min incremental warm-up. Blood samples were collected prior to and during the warm-up, pre- and post- TT and at regular intervals after the TT. Urine samples were collected pre- and post- warm-up, immediately post TT and 60 min post TT. Pre-exercise ingestion of the diester resulted in a 2 ± 1% impairment in TT performance that was associated with gut discomfort and higher perception of effort. Serum β-hydroxybutyrate, serum acetoacetate, and urine ketone concentrations increased from rest following ketone ingestion and were higher than placebo throughout the trial. Ketone ingestion induces hyperketonemia in elite professional cyclists when in a carbohydrate fed state, and impairs performance of a cycling TT lasting ~50 min.

  13. Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes

    Science.gov (United States)

    Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei

    2017-09-01

    Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.

  14. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  15. Rhodium-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Ketones: A General Approach to Chiral α-amino Ketones.

    Science.gov (United States)

    Gao, Wenchao; Wang, Qingli; Xie, Yun; Lv, Hui; Zhang, Xumu

    2016-01-01

    Rhodium/DuanPhos-catalyzed asymmetric hydrogenation of aliphatic α-dehydroamino ketones has been achieved and afforded chiral α-amino ketones in high yields and excellent enantioselectives (up to 99 % ee), which could be reduced further to chiral β-amino alcohols by LiAlH(tBuO)3 with good yields. This protocol provides a readily accessible route for the synthesis of chiral α-amino ketones and chiral β-amino alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. GABA action in immature neocortical neurons directly depends on the availability of ketone bodies.

    Science.gov (United States)

    Rheims, Sylvain; Holmgren, Carl D; Chazal, Genevieve; Mulder, Jan; Harkany, Tibor; Zilberter, Tanya; Zilberter, Yuri

    2009-08-01

    In the early postnatal period, energy metabolism in the suckling rodent brain relies to a large extent on metabolic pathways alternate to glucose such as the utilization of ketone bodies (KBs). However, how KBs affect neuronal excitability is not known. Using recordings of single NMDA and GABA-activated channels in neocortical pyramidal cells we studied the effects of KBs on the resting membrane potential (E(m)) and reversal potential of GABA-induced anionic currents (E(GABA)), respectively. We show that during postnatal development (P3-P19) if neocortical brain slices are adequately supplied with KBs, E(m) and E(GABA) are both maintained at negative levels of about -83 and -80 mV, respectively. Conversely, a KB deficiency causes a significant depolarization of both E(m) (>5 mV) and E(GABA) (>15 mV). The KB-mediated shift in E(GABA) is largely determined by the interaction of the NKCC1 cotransporter and Cl(-)/HCO3 transporter(s). Therefore, by inducing a hyperpolarizing shift in E(m) and modulating GABA signaling mode, KBs can efficiently control the excitability of neonatal cortical neurons.

  17. Study of AMPK-Regulated Metabolic Fluxes in Neurons Using the Seahorse XFe Analyzer.

    Science.gov (United States)

    Marinangeli, Claudia; Kluza, Jérome; Marchetti, Philippe; Buée, Luc; Vingtdeux, Valérie

    2018-01-01

    AMP-activated protein kinase (AMPK) is the intracellular master energy sensor and metabolic regulator. AMPK is involved in cell energy homeostasis through the regulation of glycolytic flux and mitochondrial biogenesis. Interestingly, metabolic dysfunctions and AMPK deregulations are observed in many neurodegenerative diseases, including Alzheimer's. While these deregulations could play a key role in the development of these diseases, the study of metabolic fluxes has remained quite challenging and time-consuming. In this chapter, we describe the Seahorse XFe respirometry assay as a fundamental experimental tool to investigate the role of AMPK in controlling and modulating cell metabolic fluxes in living and intact differentiated primary neurons. The Seahorse XFe respirometry assay allows the real-time monitoring of glycolytic flux and mitochondrial respiration from different kind of cells, tissues, and isolated mitochondria. Here, we specify a protocol optimized for primary neuronal cells using several energy substrates such as glucose, pyruvate, lactate, glutamine, and ketone bodies. Nevertheless, this protocol can easily be adapted to monitor metabolic fluxes from other types of cells, tissues, or isolated mitochondria by taking into account the notes proposed for each key step of this assay.

  18. Ketone EC50 values in the Microtox test.

    Science.gov (United States)

    Chen, H F; Hee, S S

    1995-03-01

    The Microtox EC50 values for the following ketones are reported in the following homologous series: straight chain methyl ketones (acetone, 2-butanone, 2-pentanone, 2-hepatonone, 2-octanone, 2-decanone, and 2-tridecanone); methyl ketones substituted at one alpha carbon (3-methyl-2-butanone; 3,3-dimethyl-2-butanone); methyl substituted at two alpha carbons (2,4-dimethyl-3-pentanone; 2,2,4,4-tetramethyl-3-pentanone); phenyl groups replacing methyl in acetone (acetophenone; benzophenone); methyl groups substituted at the alpha carbons of cyclohexanone; and 2,3- 2,4-, and 2,5-hexanediones, most for the first time. While there were linear relationships between log EC50 and MW for the straight chain methyl ketones, and for methyl substitution at the alpha carbon for methyl ketones, there were no other linear relationships. As molecular weight increased, the EC50 values of soluble ketones decreased; as distance between two carbonyl groups decreased so too did EC50 values. Thus, for the ketones the geometry around the carbonyl group is an important determinant of toxicity as well as MW, water solubility, and octanol/water coefficient.

  19. Novel proton exchange membranes based on structure-optimized poly(ether ether ketone ketone)s and nanocrystalline cellulose

    Science.gov (United States)

    Ni, Chuangjiang; Wei, Yingcong; Zhao, Qi; Liu, Baijun; Sun, Zhaoyan; Gu, Yan; Zhang, Mingyao; Hu, Wei

    2018-03-01

    Two sulfonated fluorenyl-containing poly(ether ether ketone ketone)s (SFPEEKKs) were synthesized as the matrix of composite proton exchange membranes by directly sulfonating copolymer precursors comprising non-sulfonatable fluorinated segments and sulfonatable fluorenyl-containing segments. Surface-modified nanocrystalline cellulose (NCC) was produced as the "performance-enhancing" filler by treating the microcrystalline cellulose with acid. Two families of SFPEEKK/NCC nanocomposite membranes with various NCC contents were prepared via a solution-casting procedure. Results revealed that the insertion of NCC at a suitable ratio could greatly enhance the proton conductivity of the pristine membranes. For example, the proton conductivity of SFPEEKK-60/NCC-4 (SFPEEKK with 60% fluorenyl segments in the repeating unit, and inserted with 4% NCC) composite membrane was as high as 0.245 S cm-1 at 90 °C, which was 61.2% higher than that of the corresponding pure SFPEEKK-60 membrane. This effect could be attributed to the formation of hydrogen bond networks and proton conduction paths through the interaction between -SO3H/-OH groups on the surface of NCC particles and -SO3H groups on the SFPEEKK backbones. Furthermore, the chemically modified NCC filler and the optimized chemical structure of the SFPEEKK matrix also provided good dimensional stability and mechanical properties of the obtained nanocomposites. In conclusion, these novel nanocomposites can be promising proton exchange membranes for fuel cells at moderate temperatures.

  20. Homologation Reaction of Ketones with Diazo Compounds.

    Science.gov (United States)

    Candeias, Nuno R; Paterna, Roberta; Gois, Pedro M P

    2016-03-09

    This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.

  1. Reduction of Aldehydes and Ketones by Sodium Dithionite

    NARCIS (Netherlands)

    Vries, Johannes G. de; Kellogg, Richard M.

    1980-01-01

    Conditions have been developed for the effective reduction of aldehydes and ketones by sodium dithionite, Na2S2O4. Complete reduction of simple aldehydes and ketones can be achieved with excess Na2S2O4 in H2O/dioxane mixtures at reflux temperature. Some aliphatic ketones, for example, pentanone and

  2. Synthesis and thermal behavior of new organometallic poly ketones and co-poly ketones based on diferrocenylidene piperidone

    International Nuclear Information System (INIS)

    Aly, K.I.

    2005-01-01

    A new interesting category of organometallic poly ketones and copolyketones were synthesized via Friedel - Crafts reaction through the polymerization of 2,6-[Bis (2-ferrocenyl )methylene] N-methylpiperidone (II) with different diacid chlorides. The model compound was synthesized by reacting the monomer (II) with benzoyl chloride and characterized by HNMR, IR and elemental analyses. The poly ketones and copolyketones were insoluble in most organic solvents but soluble easily in protic solvents. The thermal properties of these poly ketones and copolyketones were evaluated and correlated to their structural units by TGA and DSC measurements, and had inherent viscosity 0.34-0.52 dl g-1. Moreover, the electrical conductivity of one of the poly ketones, as selected example, Va and copolyketone VI were investigated above the temperature range (300-500 K) and showed that it followed an Arrhenius equation with activation energy 2.09 eV, also the morphological properties of selected examples of poly-and copolyketones were detected by SEM

  3. Oxidative Umpolung α‐Alkylation of Ketones

    DEFF Research Database (Denmark)

    Shneider, O. Svetlana; Pisarevsky, Evgeni; Fristrup, Peter

    2015-01-01

    We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α...

  4. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    International Nuclear Information System (INIS)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F.

    2013-01-01

    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  5. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    Energy Technology Data Exchange (ETDEWEB)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: luizfsjr@iq.usp.br [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental

    2013-09-15

    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  6. Quantification of surface energy fluxes from a small water body using scintillometry and eddy covariance

    DEFF Research Database (Denmark)

    McGloin, Ryan; McGowan, Hamish; McJannet, David

    2014-01-01

    Accurate quantification of evaporation from small water storages is essential for water management and planning, particularly in water-scarce regions. In order to ascertain suitable methods for direct measurement of evaporation from small water bodies, this study presents a comparison of eddy......% greater than eddy covariance measurements. We suggest possible reasons for this difference and provide recommendations for further research for improving measurements of surface energy fluxes over small water bodies using eddy covariance and scintillometry. Key Points Source areas for Eddy covariance...... and scintillometry were on the water surface Reasonable agreement was shown between the sensible heat flux measurements Scintillometer estimates of latent heat flux were greater than eddy covariance...

  7. Can ketones compensate for deteriorating brain glucose uptake during aging? Implications for the risk and treatment of Alzheimer's disease.

    Science.gov (United States)

    Cunnane, Stephen C; Courchesne-Loyer, Alexandre; St-Pierre, Valérie; Vandenberghe, Camille; Pierotti, Tyler; Fortier, Mélanie; Croteau, Etienne; Castellano, Christian-Alexandre

    2016-03-01

    Brain glucose uptake is impaired in Alzheimer's disease (AD). A key question is whether cognitive decline can be delayed if this brain energy defect is at least partly corrected or bypassed early in the disease. The principal ketones (also called ketone bodies), β-hydroxybutyrate and acetoacetate, are the brain's main physiological alternative fuel to glucose. Three studies in mild-to-moderate AD have shown that, unlike with glucose, brain ketone uptake is not different from that in healthy age-matched controls. Published clinical trials demonstrate that increasing ketone availability to the brain via moderate nutritional ketosis has a modest beneficial effect on cognitive outcomes in mild-to-moderate AD and in mild cognitive impairment. Nutritional ketosis can be safely achieved by a high-fat ketogenic diet, by supplements providing 20-70 g/day of medium-chain triglycerides containing the eight- and ten-carbon fatty acids octanoate and decanoate, or by ketone esters. Given the acute dependence of the brain on its energy supply, it seems reasonable that the development of therapeutic strategies aimed at AD mandates consideration of how the underlying problem of deteriorating brain fuel supply can be corrected or delayed. © 2016 New York Academy of Sciences.

  8. Activation of liver carnitine palmitoyltransferase-1 and mitochondrial acetoacetyl-CoA thiolase is associated with elevated ketone body levels in the elasmobranch Squalus acanthias.

    Science.gov (United States)

    Treberg, Jason R; Crockett, Elizabeth L; Driedzic, William R

    2006-01-01

    Elasmobranch fishes are an ancient group of vertebrates that have unusual lipid metabolism whereby storage lipids are mobilized from the liver for peripheral oxidation largely as ketone bodies rather than as nonesterified fatty acids under normal conditions. This reliance on ketones, even when feeding, implies that elasmobranchs are chronically ketogenic. Compared to specimens sampled within 2 d of capture (recently captured), spiny dogfish Squalus acanthias that were held for 16-33 d without apparent feeding displayed a 4.5-fold increase in plasma concentration of d- beta -hydroxybutyrate (from 0.71 to 3.2 mM) and were considered ketotic. Overt activity of carnitine palmitoyltransferase-1 in liver mitochondria from ketotic dogfish was characterized by an increased apparent maximal activity, a trend of increasing affinity (reduced apparent K(m); P=0.09) for l-carnitine, and desensitization to the inhibitor malonyl-CoA relative to recently captured animals. Acetoacetyl-CoA thiolase (ACoAT) activity in isolated liver mitochondria was also markedly increased in the ketotic dogfish compared to recently captured fish, whereas no difference in 3-hydroxy-3-methylglutaryl-CoA synthase activity was found between these groups, suggesting that ACoAT plays a more important role in the activation of ketogenesis in spiny dogfish than in mammals and birds.

  9. Colorimetric Recognition of Aldehydes and Ketones.

    Science.gov (United States)

    Li, Zheng; Fang, Ming; LaGasse, Maria K; Askim, Jon R; Suslick, Kenneth S

    2017-08-07

    A colorimetric sensor array has been designed for the identification of and discrimination among aldehydes and ketones in vapor phase. Due to rapid chemical reactions between the solid-state sensor elements and gaseous analytes, distinct color difference patterns were produced and digitally imaged for chemometric analysis. The sensor array was developed from classical spot tests using aniline and phenylhydrazine dyes that enable molecular recognition of a wide variety of aliphatic or aromatic aldehydes and ketones, as demonstrated by hierarchical cluster, principal component, and support vector machine analyses. The aldehyde/ketone-specific sensors were further employed for differentiation among and identification of ten liquor samples (whiskies, brandy, vodka) and ethanol controls, showing its potential applications in the beverage industry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ketone bodies in blood of dairy cows: Prevalence and monitoring of subclinical ketosis

    Directory of Open Access Journals (Sweden)

    Marek Krempaský

    2014-01-01

    Full Text Available The aim of this study was to investigate the relationship between concentration of non-esterified fatty acid and ketone bodies in blood of dairy cows, and to evaluate these concentrations for the detection of prevalence of subclinical ketosis. The second aim was to compare the concentration of β-hydroxybutyric acid determined by an electronic handheld meter Precision Xtra® with serum concentration of β-hydroxybutyric acid analysed in laboratory with izotachometric and photometric method, respectively. Blood samples were collected from jugular vein 4–6 h after morning feeding in three groups of Holstein cows (n = 909 according to the lactation phase from 51 different herds with similar husbandry characteristics. High lipomobilization (non-esterified fatty acid ≥ 0.35 mmol·l-1, mean concentration 0.34 ± 0.15 mmol·l-1 was detected in 30.3% of antepartum cows, while increased concentrations of β-hydroxybutyric acid (≥ 1.0 mmol·l-1, prevalence of subclinical ketosis were detected in 18.5% and 14.1% of the early lactation and mid lactation cows, respectively. The correlation coefficient (r = 0.84, P P ® test and plasma or serum β-hydroxybutyric acid concentration determined by isotachophoresis and photometrical method, respectively. Our results show that the monitoring of changes in the blood concentration of β-hydroxybutyric acid in high-yielding cows in the early postpartum period by the electronic handheld meter Precision Xtra® may be effective in reducing the incidence of ketosis and health problems associated with ketosis in dairy cattle herds.

  11. Production of methyl-vinyl ketone from levulinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A [Verona, WI; West,; Ryan, M [Madison, WI

    2011-06-14

    A method for converting levulinic acid to methyl vinyl ketone is described. The method includes the steps of reacting an aqueous solution of levulinic acid, over an acid catalyst, at a temperature of from room temperature to about 1100 K. Methyl vinyl ketone is thereby formed.

  12. Fuel cell performance of pendent methylphenyl sulfonated poly(ether ether ketone ketone)s

    Science.gov (United States)

    Zhang, Hanyu; Stanis, Ronald J.; Song, Yang; Hu, Wei; Cornelius, Chris J.; Shi, Qiang; Liu, Baijun; Guiver, Michael D.

    2017-11-01

    Meta- and para-linked homopolymers bearing 3-methylphenyl (Me) pendent groups were postsulfonated to create sulfonated poly(ether ether ketone ketone) (SPEEKK) backbone isomers, which are referred to as Me-p-SPEEKK and Me-m-SPEEKK. Their thermal and oxidative stability, mechanical properties, dimensional stability, methanol permeability, and proton conductivity are characterized. Me-p-SPEEKK and Me-m-SPEEKK proton conductivities at 100 °C are 116 and 173 mS cm-1, respectively. Their methanol permeabilities are 3.3-3.9 × 10-7 cm2 s-1, and dimensional swelling at 100 °C is 16.4-17.5%. Me-p-SPEEKK and Me-m-SPEEKK were fabricated into membrane electrode assemblies (MEAs), and electrochemical properties were evaluated within a direct methanol fuel cell (DMFC) and proton-exchange membrane fuel cell (PEMFC). When O2 is used as the oxidant at 80 °C and 100% RH, the maximum power density of Me-m-SPEEKK reaches 657 mW cm-2, which is higher than those of Nafion 115 (552 mW cm-2). DMFC performance is 85 mW cm-2 at 80 °C with 2.0 M methanol using Me-p-SPEEKK due to its low MeOH crossover. In general, these electrochemical results are comparable to Nafion. These ionomer properties, combined with a potentially less expensive and scalable polymer manufacturing process, may broaden their potential for many practical applications.

  13. A new way to produce hyperketonemia: use of ketone ester in a case of Alzheimer's disease.

    Science.gov (United States)

    Newport, Mary T; VanItallie, Theodore B; Kashiwaya, Yoshihiro; King, Michael Todd; Veech, Richard L

    2015-01-01

    Providing ketone bodies to the brain can bypass metabolic blocks to glucose utilization and improve function in energy-starved neurons. For this, plasma ketones must be elevated well above the ≤ 0.2 mM default concentrations normally prevalent. Limitations of dietary methods currently used to produce therapeutic hyperketonemia have stimulated the search for better approaches. Described herein is a new way to produce therapeutic hyperketonemia, entailing prolonged oral administration of a potent ketogenic agent--ketone monoester (KME)--to a patient with Alzheimer's disease dementia and a pretreatment Mini-Mental State Examination score of 12. The patient improved markedly in mood, affect, self-care, and cognitive and daily activity performance. The KME was well tolerated throughout the 20-month treatment period. Cognitive performance tracked plasma β-hydroxybutyrate concentrations, with noticeable improvements in conversation and interaction at the higher levels, compared with predose levels. KME-induced hyperketonemia is robust, convenient, and safe, and the ester can be taken as an oral supplement without changing the habitual diet. Published by Elsevier Inc.

  14. DIRECT AMIDOALKYLATION OF KETONES

    NARCIS (Netherlands)

    TENHOEVE, W; WYNBERG, H

    1994-01-01

    In a one-pot reaction aromatic aldehydes, urethane or acetamide and a variety of ketones condense in the presence of catalytic amounts of boron trifluoride or p-toluenesulfonic acid to furnish substituted carbamates or amides in good yield.

  15. The reaction of organocerium reagents with easily enolizable ketones

    International Nuclear Information System (INIS)

    Imamoto, Tsuneo; Kusumoto, Tetsuo; Sugiura, Yasushi; Suzuki, Nobuyo; Takiyama, Nobuyuki

    1985-01-01

    Organocerium (III) reagents were conveniently generated by the reaction of organolithium compounds with anhydrous cerium (III) chloride. The reagents are less basic than organolithiums and Grignard reagents, and they react readily at -78 deg C with easily enolizable ketones such as 2-tetralone to afford addition products in high yields. Cerium (III) enolates were also generated from lithium enolates and cerium (III) chloride. The cerium (III) enolates undergo aldol addition with ketones or sterically crowded aldehyde to give the corresponding β-hydroxy ketones in good to high yields. (author)

  16. Catalyst-free dehydrative α-alkylation of ketones with alcohols: green and selective autocatalyzed synthesis of alcohols and ketones.

    Science.gov (United States)

    Xu, Qing; Chen, Jianhui; Tian, Haiwen; Yuan, Xueqin; Li, Shuangyan; Zhou, Chongkuan; Liu, Jianping

    2014-01-03

    Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by CC bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis and Consecutive Reactions of α-Azido Ketones: A Review

    Directory of Open Access Journals (Sweden)

    Sadia Faiz

    2015-08-01

    Full Text Available This review paper covers the major synthetic approaches attempted towards the synthesis of α-azido ketones, as well as the synthetic applications/consecutive reactions of α-azido ketones.

  18. Direct α-alkylation of ketones with alcohols in water.

    Science.gov (United States)

    Xu, Guoqiang; Li, Qiong; Feng, Jiange; Liu, Qiang; Zhang, Zuojun; Wang, Xicheng; Zhang, Xiaoyun; Mu, Xindong

    2014-01-01

    The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2 O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5 -C11 or longer-chain ketones and alcohols, which are precursors to fuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. On the Metabolism of Exogenous Ketones in Humans

    Directory of Open Access Journals (Sweden)

    Brianna J. Stubbs

    2017-10-01

    Full Text Available Background and aims: Currently there is considerable interest in ketone metabolism owing to recently reported benefits of ketosis for human health. Traditionally, ketosis has been achieved by following a high-fat, low-carbohydrate “ketogenic” diet, but adherence to such diets can be difficult. An alternative way to increase blood D-β-hydroxybutyrate (D-βHB concentrations is ketone drinks, but the metabolic effects of exogenous ketones are relatively unknown. Here, healthy human volunteers took part in three randomized metabolic studies of drinks containing a ketone ester (KE; (R-3-hydroxybutyl (R-3-hydroxybutyrate, or ketone salts (KS; sodium plus potassium βHB.Methods and Results: In the first study, 15 participants consumed KE or KS drinks that delivered ~12 or ~24 g of βHB. Both drinks elevated blood D-βHB concentrations (D-βHB Cmax: KE 2.8 mM, KS 1.0 mM, P < 0.001, which returned to baseline within 3–4 h. KS drinks were found to contain 50% of the L-βHB isoform, which remained elevated in blood for over 8 h, but was not detectable after 24 h. Urinary excretion of both D-βHB and L-βHB was <1.5% of the total βHB ingested and was in proportion to the blood AUC. D-βHB, but not L-βHB, was slowly converted to breath acetone. The KE drink decreased blood pH by 0.10 and the KS drink increased urinary pH from 5.7 to 8.5. In the second study, the effect of a meal before a KE drink on blood D-βHB concentrations was determined in 16 participants. Food lowered blood D-βHB Cmax by 33% (Fed 2.2 mM, Fasted 3.3 mM, P < 0.001, but did not alter acetoacetate or breath acetone concentrations. All ketone drinks lowered blood glucose, free fatty acid and triglyceride concentrations, and had similar effects on blood electrolytes, which remained normal. In the final study, participants were given KE over 9 h as three drinks (n = 12 or a continuous nasogastric infusion (n = 4 to maintain blood D-βHB concentrations greater than 1 mM. Both drinks

  20. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

    Directory of Open Access Journals (Sweden)

    Atsushi Morikawa

    2016-02-01

    Full Text Available Poly(ether ether ketone dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4′-(4-fluorobenzoyldiphenyl ether and 3,5-dihydroxy-4′-(4-fluorobenzoyldiphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy-3,5-bis(4-fluorobenzoylbenzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketones having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

  1. Contribution to the study of the structure and reactivity of ketones using deuterium substitution of the α - ketone hydrogens

    International Nuclear Information System (INIS)

    Frejaville, G.

    1966-02-01

    This work is an attempt to obtain more knowledge about the structure and the reactivity of ketones; it is also a contribution to conformational analysis based on infrared signals associated with the C-D vibration in mono-deuterated compounds. In the first chapter the various dosage and synthetic methods used in this work are described. In the second chapter the infrared spectra in the 2100-2200 cm -1 region for mono-deuterated ketones are interpreted on the basis of a simple model. This model is then studied in detail, and also critically and precisely, in the case of the mono deuterated acetone molecule. In the third chapter is studied the mechanism of the Favorskii reaction and the reactivity of all the α-ketonic hydrogens of 2 chloro-cyclohexanone are classified. In a technical appendix is described a counter-current exchange method for obtaining a great variety of solvents and deuterated pure raw materials under advantageous conditions. (author) [fr

  2. Preparation and characterization of poly (methyl methacrylate) and sulfonated poly (ether ether ketone) blend ultrafiltration membranes for protein separation applications

    International Nuclear Information System (INIS)

    Arthanareeswaran, G.; Thanikaivelan, P.; Raajenthiren, M.

    2009-01-01

    Poly (methyl methacrylate) (PMMA) and poly (methyl methacrylate)/sulfonated poly (ether ether ketone) (SPEEK) blend membranes were prepared by phase inversion technique in various composition using N,N'-dimethylformamide as solvent. The prepared membranes were characterized in terms of pure water flux, water content, porosity and thermal stability. The addition of SPEEK to the casting solution resulted in membranes with high pure water flux, water content, porosity and slightly low thermal stability. The cross sectional views of the blend membranes under electron microscope confirm the porosity and water flux results. The effect of the addition of SPEEK into the PMMA matrix on the extent of bovine serum albumin (BSA) separation was studied. It was found that the permeate flux increased significantly while the rejection of BSA from aqueous solution reduced moderately during ultrafiltration (UF) process. The effect was attributed to the increase in porosity and charge of the membrane due to the addition of SPEEK into the PMMA blend solution

  3. Silica sulfuric acid and as an efficient catalyst for the Friedlander quinoline synthesis from simple ketones and ortho - amino aryl ketones under microwave irradiation

    International Nuclear Information System (INIS)

    Zolfigol, M. A.; Salehi, P.; Shiri, M.; Faal Rastegar, T.; Ghaderi, A.

    2008-01-01

    The synthesis of quinoline derivatives via Friedlander method from ortho-amino aryl ketones in the presence of a catalytic amount of silica sulfuric acid under solvent-free condition and microwave irradiation was described. A good range of simple ketones such as cyclohexanone and deoxybenzoin were used

  4. Electronic structure and tautomerism of aryl ketones

    International Nuclear Information System (INIS)

    Novak, Igor; Klasinc, Leo; Šket, Boris; McGlynn, S.P.

    2015-01-01

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed

  5. Electronic structure and tautomerism of aryl ketones

    Energy Technology Data Exchange (ETDEWEB)

    Novak, Igor, E-mail: inovak@csu.edu.au [Charles Sturt University, POB 883, Orange, NSW 2800 (Australia); Klasinc, Leo, E-mail: klasinc@irb.hr [Physical Chemistry Department, Ruđer Bošković Institute, HR-10002 Zagreb (Croatia); Šket, Boris, E-mail: Boris.Sket@fkkt.uni-lj.si [Faculty of Chemistry and Chemical Technology, University of Ljubljana, SI-1000 (Slovenia); McGlynn, S.P., E-mail: sean.mcglynn@chemgate.chem.lsu.edu [Louisiana State University, Baton Rouge, LA 70803 (United States)

    2015-07-15

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed.

  6. Contribution to the study of gamma radiolysis of 2-furyl butyl or substituted phenyl ketones in isopropanol

    International Nuclear Information System (INIS)

    El Dessouky Aly, M.M.

    1982-03-01

    The following ketones: 2-furyl butyl ketone (I), 2 furyl phenyl ketone (II), 2-furyl p-methylphenyl ketone (III) and 2-furyl p-methoxyphenyl ketone (IV) were synthesised and characterised. The yields of hydrogen and methane obtained during radiolysis of the mixtures ketones (I to IV)-2-propanol were determined. These yields are always lower than with pure 2-propanol. Radiolysis products for ketones (I) and (II) are studied. Analysis of radiolitical products were conducted by gas chromatography. Effect of radiation dose and ketone concentration is determined. Reaction mechanisms are studied [fr

  7. Bacterial production of methyl ketones

    Energy Technology Data Exchange (ETDEWEB)

    Beller, Harry R.; Goh, Ee-Been

    2017-01-31

    The present invention relates to methods and compositions for increasing production of methyl ketones in a genetically modified host cell that overproduces .beta.-ketoacyl-CoAs through a re-engineered .beta.-oxidation pathway and overexpresses FadM.

  8. Synthesis of tritium labelled methyl vinyl ketone and its use in copolymer analysis

    International Nuclear Information System (INIS)

    Burfield, D.R.; Savariar, C.M.

    1980-01-01

    The synthesis of tritiated methyl vinyl ketone by base catalysed exchange and its use in determining the ketone content of styrene/methyl vinyl ketone copolymers are reported. Methods of assay are described in detail and the general applicability of the method is discussed. (author)

  9. Effect of the Ketone Body Beta-Hydroxybutyrate on the Innate Defense Capability of Primary Bovine Mammary Epithelial Cells.

    Science.gov (United States)

    Hillreiner, Maria; Flinspach, Claudia; Pfaffl, Michael W; Kliem, Heike

    2016-01-01

    Negative energy balance and ketosis are thought to cause impaired immune function and to increase the risk of clinical mastitis in dairy cows. The present in vitro study aimed to investigate the effect of elevated levels of the predominant ketone body β-hydroxybutyrate on the innate defense capability of primary bovine mammary epithelial cells (pbMEC) challenged with the mastitis pathogen Escherichia coli (E. coli). Therefore, pbMEC of healthy dairy cows in mid- lactation were isolated from milk and challenged in culture with 3 mM BHBA and E. coli. pbMEC stimulated with E. coli for 6 h or 30 h showed an up-regulation of several innate immune genes, whereas co-stimulation of pbMEC with 3 mM BHBA and E. coli resulted in the down-regulation of CCL2, SAA3, LF and C3 gene expression compared to the challenge with solely the bacterial stimulus. These results indicated that increased BHBA concentrations may be partially responsible for the higher mastitis susceptibility of dairy cows in early lactation. Elevated levels of BHBA in blood and milk during negative energy balance and ketosis are likely to impair innate immune function in the bovine mammary gland by attenuating the expression of a broad range of innate immune genes.

  10. Effect of the Ketone Body Beta-Hydroxybutyrate on the Innate Defense Capability of Primary Bovine Mammary Epithelial Cells.

    Directory of Open Access Journals (Sweden)

    Maria Hillreiner

    Full Text Available Negative energy balance and ketosis are thought to cause impaired immune function and to increase the risk of clinical mastitis in dairy cows. The present in vitro study aimed to investigate the effect of elevated levels of the predominant ketone body β-hydroxybutyrate on the innate defense capability of primary bovine mammary epithelial cells (pbMEC challenged with the mastitis pathogen Escherichia coli (E. coli. Therefore, pbMEC of healthy dairy cows in mid- lactation were isolated from milk and challenged in culture with 3 mM BHBA and E. coli. pbMEC stimulated with E. coli for 6 h or 30 h showed an up-regulation of several innate immune genes, whereas co-stimulation of pbMEC with 3 mM BHBA and E. coli resulted in the down-regulation of CCL2, SAA3, LF and C3 gene expression compared to the challenge with solely the bacterial stimulus. These results indicated that increased BHBA concentrations may be partially responsible for the higher mastitis susceptibility of dairy cows in early lactation. Elevated levels of BHBA in blood and milk during negative energy balance and ketosis are likely to impair innate immune function in the bovine mammary gland by attenuating the expression of a broad range of innate immune genes.

  11. Medium-chain triglycerides in infant formulas and their relation to plasma ketone body concentrations.

    Science.gov (United States)

    Wu, P Y; Edmond, J; Auestad, N; Rambathla, S; Benson, J; Picone, T

    1986-04-01

    A mild ketosis is known to prevail in the mother, fetus, and newborn infant during the 3rd trimester and in the early neonatal period. It has been shown that during an equivalent period in the rat ketone bodies are readily oxidized and serve as key substrates for lipogenesis in brain. Since medium-chain triglycerides are known to be ketogenic, preterm infants may benefit from dietary medium-chain triglycerides beyond the point of enhanced fat absorption. Our objective was to determine the ketogenic response in preterm infants (gestational age: 33 +/- 0.8 wk) fed three different isocaloric formulas by measuring the concentrations of 3-hydroxybutyrate and acetoacetate in the plasma of these infants. At the time of entrance to the study the infants were receiving 110 kcal/kg/24 h. Study I (11 infants): the infants were fed sequentially in the order; PM 60/40 (PM), Special Care Formula (SCF), and Similac 20 (SIM). In SCF greater than 50% of the fat consists of medium-chain length fatty acids while PM and SIM contain about 25%. The concentration of 3-hydroxybutyrate in plasma was significantly higher when infants were fed SCF than PM and SIM [0.14 +/- 0.03, 0.06 +/- 0.01, and 0.05 +/- 0.01 mM, respectively (p less than 0.01)]. Study II (12 infants); the infants were fed SCF, then SIM, or the reverse. The concentration of acetoacetate in plasma was 0.05 +/- 0.01 and 0.03 +/- 0.01 mM when infants were fed SCF and SIM, respectively (0.1 greater than p greater than 0.05). The concentrations of 3-hydroxybutyrate in plasma were similar to those measured in study I for the respective formulas.(ABSTRACT TRUNCATED AT 250 WORDS)

  12. Management of multifactorial idiopathic epilepsy in EL mice with caloric restriction and the ketogenic diet: role of glucose and ketone bodies

    Directory of Open Access Journals (Sweden)

    Mantis John G

    2004-10-01

    Full Text Available Abstract Background The high fat, low carbohydrate ketogenic diet (KD was developed as an alternative to fasting for seizure management. While the mechanisms by which fasting and the KD inhibit seizures remain speculative, alterations in brain energy metabolism are likely involved. We previously showed that caloric restriction (CR inhibits seizure susceptibility by reducing blood glucose in the epileptic EL mouse, a natural model for human multifactorial idiopathic epilepsy. In this study, we compared the antiepileptic and anticonvulsant efficacy of the KD with that of CR in adult EL mice with active epilepsy. EL mice that experienced at least 15 recurrent complex partial seizures were fed either a standard diet unrestricted (SD-UR or restricted (SD-R, and either a KD unrestricted (KD-UR or restricted (KD-R. All mice were fasted for 14 hrs prior to diet initiation. A new experimental design was used where each mouse in the diet-restricted groups served as its own control to achieve a 20–23% body weight reduction. Seizure susceptibility, body weights, and the levels of plasma glucose and β-hydroxybutyrate were measured once/week over a nine-week treatment period. Results Body weights and blood glucose levels remained high over the testing period in the SD-UR and the KD-UR groups, but were significantly (p Conclusions The results indicate that seizure susceptibility in EL mice is dependent on plasma glucose levels and that seizure control is more associated with the amount than with the origin of dietary calories. Also, CR underlies the antiepileptic and anticonvulsant action of the KD in EL mice. A transition from glucose to ketone bodies for energy is predicted to manage EL epileptic seizures through multiple integrated changes of inhibitory and excitatory neural systems.

  13. Baeyger-Villiger oxidation of bicyclic ketones. Study of the reaction mechanisms

    International Nuclear Information System (INIS)

    Moutin, Michel

    1968-01-01

    Steric effects occur with the substituents in the ring enlargement of ketones leading to lactones. Different theories which have been proposed are examined, the case of camphor being of particular interest. The following ketones are examined: episo- and iso-fenchone, α and β fenchocamphorone and camphenylone, and the lactone yields are predicted. The identification of the lactones produced is discussed. The case of α fencho-camphorone, which contradicts previous theory, is underlined. The synthesis of the ketones is discussed. (author) [fr

  14. Synthesis and antidiabetic activity of β-acetamido ketones

    Directory of Open Access Journals (Sweden)

    Xing-hua Zhang

    2011-08-01

    Full Text Available This paper reports the use of trifluoroacetic acid as a catalyst in the Dakin–West reaction for the synthesis of β-acetamido ketones. The method has several advantages such as requiring only mild conditions and a low concentration of catalyst. Screening of 19 β-acetamido ketones for antidiabetic activity in vitro showed that their activity as peroxisome proliferator-activated receptor (PPAR agonists and as dipeptidyl peptidase 4 (DPP-IV inhibitors was fairly weak.

  15. [Pollution Characteristics of Aldehydes and Ketones Compounds in the Exhaust of Beijing Typical Restaurants].

    Science.gov (United States)

    Cheng, Jing-chen; Cui, Tong; He, Wan-qing; Nie, Lei; Wang, Jun-ling; Pan, Tao

    2015-08-01

    Aldehydes and ketones compounds, as one of the components in the exhaust of restaurants, are a class of volatile organic compounds (VOCs) with strong chemical reactivity. However, there is no systematic study on aldehydes and ketones compounds in the exhaust of restaurants. To further clarify the food source emission levels of aldehydes and ketones compounds and controlling measures, to access city group catering VOCs emissions control decision-making basis, this study selected 8 Beijing restaurants with different types. The aldehydes and ketones compounds were sampled using DNPH-silica tube, and then ultra performance liquid chromatography was used for quantitative measurement. The aldehydes and ketones concentrations of reference volume condition from 8 restaurants in descending order were Roasted Duck restaurant, Chinese Style Barbecue, Home Dishes, Western Fast-food, School Canteen, Chinese Style Fast-food, Sichuan Cuisine, Huaiyang Cuisine. The results showed that the range of aldehydes and ketones compounds (C1-C9) concentrations of reference volume condition in the exhaust of restaurants was 115.47-1035.99 microg x m(-3). The composition of aldehydes and ketones compounds in the exhaust of sampled restaurants was obviously different. The percentages of C1-C3 were above 40% in the exhaust from Chinese style restaurants. Fast food might emit more C4-C9 aldehydes and ketones compounds. From the current situation of existing aldehydes and ketones compounds control, the removal efficiency of high voltage electrostatic purifiers widely used in Beijing is limited.

  16. Presence and potential significance of aromatic-ketone groups in aquatic humic substances

    Science.gov (United States)

    Leenheer, J.A.; Wilson, M.A.; Malcolm, R.L.

    1987-01-01

    Aquatic humic- and fulvic-acid standards of the International Humic Substances Society were characterized, with emphasis on carbonyl-group nature and content, by carbon-13 nuclear-magnetic-resonance spectroscopy, proton nuclear-magnetic-resonance spectroscopy, and infrared spectroscopy. After comparing spectral results of underivatized humic and fulvic acids with spectral results of chemically modified derivatives, that allow improved observation of the carbonyl group, the data clearly indicated that aromatic ketone groups comprised the majority of the carbonyl-group content. About one ketone group per monocyclic aromatic ring was determined for both humic and fulvic acids. Aromatic-ketone groups were hypothesized to form by photolytic rearrangements and oxidation of phenolic ester and hydrocarbon precursors; these groups have potential significance regarding haloform formation in water, reactivity resulting from active hydrogen of the methyl and methylene adjacent to the ketone groups, and formation of hemiketal and lactol structures. Aromatic-ketone groups also may be the point of attachment between aliphatic and aromatic moieties of aquatic humic-substance structure. ?? 1987.

  17. Stress state of transversally isotropic body with elliptical crack in the presence of a uniform heat flux at its surface

    International Nuclear Information System (INIS)

    Podil'chuk, Yu.N.

    1995-01-01

    An explicit solution of the state thermoelasticity problem is constructed for an infinite transversally isotropic body containing an internal elliptical crack in the isotropy plane. It is assumed that a uniform heat flux is specified at the crack surface and the body is free of external loads. Values of the stress-intensity coefficients depending on the heat flux, the crack dimensions, and the thermoelastic properties of the material are obtained. Note that the analogous problem was considered for an isotropic body. The static thermoelasticity problem for a transversally isotropic body with an internal elliptical crack at whose surface linear temperature variation is specified was solved

  18. Rhodium Catalyzed Intramolecular C-H Insertion of α-Aryl-α-diazo Ketones

    Science.gov (United States)

    Taber, Douglass F.; Tian, Weiwei

    2011-01-01

    Direct diazo transfer proceeds smoothly with α-aryl ketones. The derived α-aryl-α-diazo ketones cyclize efficiently with Rh catalysis to give the corresponding α-aryl cyclopentanones. PMID:17385917

  19. Value of point-of-care ketones in assessing dehydration and acidosis in children with gastroenteritis.

    Science.gov (United States)

    Levy, Jason A; Waltzman, Mark; Monuteaux, Michael C; Bachur, Richard G

    2013-11-01

    Children with gastroenteritis often develop dehydration with metabolic acidosis. Serum ketones are frequently elevated in this population. The goal was to determine the relationship between initial serum ketone concentration and both the degree of dehydration and the magnitude of acidosis. This was a secondary analysis of a prospective trial of crystalloid administration for rapid rehydration. Children 6 months to 6 years of age with gastroenteritis and dehydration were enrolled. A point-of-care serum ketone (beta-hydroxybutyrate) concentration was obtained at the time of study enrollment. The relationship between initial serum ketone concentration and a prospectively assigned and previously validated clinical dehydration score, and serum bicarbonate concentration, was analyzed. A total of 188 patients were enrolled. The median serum ketone concentration was elevated at 3.1 mmol/L (interquartile range [IQR] = 1.2 to 4.6 mmol/L), and the median dehydration score was consistent with moderate dehydration. A significant positive relationship was found between serum ketone concentration and the clinical dehydration score (Spearman's rho = 0.22, p = 0.003). Patients with moderate dehydration had a higher median serum ketone concentration than those with mild dehydration (3.6 mmol/L vs. 1.4 mmol/L, p = 0.007). Additionally, the serum ketone concentration was inversely correlated with serum bicarbonate concentration (ρ = -0.26, p Children with gastroenteritis and dehydration have elevated serum ketone concentrations that correlate with both degree of dehydration and magnitude of metabolic acidosis. Point-of-care serum ketone measurement may be a useful tool to inform management decisions at the point of triage or in the initial evaluation of children with gastroenteritis and dehydration. © 2013 by the Society for Academic Emergency Medicine.

  20. ESR, electrochemical and cyclodextrin-inclusion studies of triazolopyridyl pyridyl ketones and dipyridyl ketones derivatives

    Science.gov (United States)

    Olea-Azar, C.; Abarca, B.; Norambuena, E.; Opazo, L.; Jullian, C.; Valencia, S.; Ballesteros, R.; Chadlaoui, M.

    2008-11-01

    The electron spin resonance (ESR) spectra of free radicals obtained by electrolytic reduction of triazolopyridyl pyridyl ketones and dipyridyl ketones derivatives were measured in dimethylsulfoxide (DMSO). The hyperfine patterns indicate that the spin density delocalization is dependent of the rings presented in the molecule. The electrochemistry of these compounds was characterized using cyclic voltammetry, in DMSO as solvent. When one carbonyl is present in the molecule one step in the reduction mechanism was observed while two carbonyl are present two steps were detected. The first wave was assigned to the generation of the correspondent free radical species, and the second wave was assigned to the dianion derivatives. The phase-solubility measurements indicated an interaction between molecules selected and cyclodextrins in water. These inclusion complexes are 1:1 with βCD, and HP-βCD. The values of Ks showed a different kind of complexes depending on which rings are included. AM1 and DFT calculations were performed to obtain the optimized geometries, theoretical hyperfine constants, and spin distributions, respectively. The theoretical results are in complete agreement with the experimental ones.

  1. Further research on the biological activities and the safety of raspberry ketone is needed

    Directory of Open Access Journals (Sweden)

    Jungmin Lee

    2016-03-01

    Full Text Available Raspberry ketone supplements have grabbed consumer attention with the possibility that they might help burn fat and aid weight loss. While raspberry ketone occurs naturally, and is found in raspberry fruit, most is synthetically produced for use in commercial products as flavorings, fragrances, or dietary supplements. Currently, the amount of raspberry ketone in dietary supplements (currently sold in the US is well above the maximum concentration recommended for food and fragrance products, so additional toxicology work is needed to ensure that such concentrations of raspberry ketone are safe. In addition to safety data, clinical studies are also needed to validate any health benefits. Without research on the effects of consuming high concentrations of raspberry ketone, consumers should be wary of unsubstantiated claims and mindful of potential harm to their health.

  2. Decreasing the Rate of Metabolic Ketone Reduction in the Discovery of a Clinical Acetyl-CoA Carboxylase Inhibitor for the Treatment of Diabetes

    Energy Technology Data Exchange (ETDEWEB)

    Griffith, David A. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Kung, Daniel W. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Esler, William P. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Amor, Paul A. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Bagley, Scott W. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Beysen, Carine [KineMed Inc., Emeryville, CA (United States); Carvajal-Gonzalez, Santos [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Doran, Shawn D. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Limberakis, Chris [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Mathiowetz, Alan M. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); McPherson, Kirk [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Price, David A. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Ravussin, Eric [Louisiana State Univ., Baton Rouge, LA (United States); Sonnenberg, Gabriele E. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Southers, James A. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Sweet, Laurel J. [Pfizer Worldwide Research and Development, Cambridge, MA (United States); Turner, Scott M. [KineMed Inc., Emeryville, CA (United States); Vajdos, Felix F. [Pfizer Worldwide Research and Development, Cambridge, MA (United States)

    2014-12-26

    We found that Acetyl-CoA carboxylase (ACC) inhibitors offer significant potential for the treatment of type 2 diabetes mellitus (T2DM), hepatic steatosis, and cancer. However, the identification of tool compounds suitable to test the hypothesis in human trials has been challenging. An advanced series of spirocyclic ketone-containing ACC inhibitors recently reported by Pfizer were metabolized in vivo by ketone reduction, which complicated human pharmacology projections. Here, we disclose that this metabolic reduction can be greatly attenuated through introduction of steric hindrance adjacent to the ketone carbonyl. Incorporation of weakly basic functionality improved solubility and led to the identification of 9 as a clinical candidate for the treatment of T2DM. Phase I clinical studies demonstrated dose-proportional increases in exposure, single-dose inhibition of de novo lipogenesis (DNL), and changes in indirect calorimetry consistent with increased whole-body fatty acid oxidation. This demonstration of target engagement validates the use of compound 9 to evaluate the role of DNL in human disease.

  3. Phosphine-catalyzed cycloadditions of allenic ketones: new substrates for nucleophilic catalysis.

    Science.gov (United States)

    Wallace, Debra J; Sidda, Rachel L; Reamer, Robert A

    2007-02-02

    A range of phosphine-catalyzed cycloaddition reactions of allenic ketones have been studied, extending the scope of these processes from the more widely used 2,3-butadienoates to allow access to a number of synthetically useful products. Reaction of allenyl methyl ketone 4 with exo-enones afforded spirocyclic compounds in good regioselectivity and promising enantioselectivity via a [2 + 3] cycloaddtion. Aromatic allenyl ketones undergo a phosphine-promoted dimerization to afford functionalized pyrans, leading to a formal [2 + 4] Diels-Alder product, but did not react in the [2 + 3] cycloaddition. The results from other reactions that had found utility with 2,3-butadienoates are also reported.

  4. EFFICACY OF PARENTERAL ADMINISTERED KETONAL IN ARTICULAR SYNDROME OF DIFFERENT ETIOLOGY

    Directory of Open Access Journals (Sweden)

    E. I. Shmidt

    2002-01-01

    Full Text Available Objective. To assess intramuscular ketonal application efficacy in joint syndrome. Methods. 30 patients with different joint diseases were included. Intramuscular monotherapy with ketonal was given for 7 days. Before and after treatment pain at rest and at movement was assessed using visual analog scale. Results. Mean pain at movement before treatment was 76 mm, after treatment - 47 mm. Pain at rest was 54 mm and 24 mm respectively. In 14 patients efficacy was considered by the physician as good and in 15 - as fair. The drug was well tolerated in all cases. Conclusion. Intramuscular application of ketonal is highly effective and well tolerated treatment in different joint diseases.

  5. The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

    Science.gov (United States)

    Nicholson, John W.; Wilson, Alan

    2004-09-01

    This article describes the history of the reaction converting carboxylic acids to ketones. The reaction has been rediscovered several times, yet has actually been known for centuries. The best known version of the process is the Dakin West reaction (1928), which applies to α-amino acids and also involves the simultaneous conversion of the amine group to amido functionality. Unlike other examples, this particular reaction has attracted a reasonable amount of attention and it appears to be better known than the conversion of simple carboxylic acids to ketones. However, this reaction was described as long ago as 1612, when Beguin published an account of it in his book, Tyrocinium Chymicum . Since then, many chemists have rediscovered the reaction, apparently independently. One of the earliest modern accounts was by W. H. Perkin, Sr., in 1886, who made various simple ketones by refluxing the appropriate carboxylic acids with base. However, this work has been largely ignored, including by his son, W. H. Perkin, Jr., who used a more complicated base-catalyzed ketonization to prepare small ring compounds in the early years of the 20th century. Other articles detailing the application of ketonization to organic acids are discussed, including our own work, which employed the process to crosslink carboxylated polymers for possible technical application in coatings. Despite its relative obscurity, the reaction was used by Woodward et al. in the total synthesis of strychnine, reported in 1963, and this is discussed in detail at the end of the article. See Featured Molecules .

  6. Selected ion flow tube mass spectrometry of 3-hydroxybutyric acid, acetone and other ketones in the headspace of aqueous solution and urine

    Czech Academy of Sciences Publication Activity Database

    Wang, T.; Španěl, Patrik; Smith, D.

    2008-01-01

    Roč. 272, č. 1 (2008), s. 78-85 ISSN 1387-3806 R&D Projects: GA ČR GA202/06/0776 Institutional research plan: CEZ:AV0Z40400503 Keywords : ketone bodies * SIFT-MS * urine * breath Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.445, year: 2008

  7. Pyrolytic graphite gauge for measuring heat flux

    Science.gov (United States)

    Bunker, Robert C. (Inventor); Ewing, Mark E. (Inventor); Shipley, John L. (Inventor)

    2002-01-01

    A gauge for measuring heat flux, especially heat flux encountered in a high temperature environment, is provided. The gauge includes at least one thermocouple and an anisotropic pyrolytic graphite body that covers at least part of, and optionally encases the thermocouple. Heat flux is incident on the anisotropic pyrolytic graphite body by arranging the gauge so that the gauge surface on which convective and radiative fluxes are incident is perpendicular to the basal planes of the pyrolytic graphite. The conductivity of the pyrolytic graphite permits energy, transferred into the pyrolytic graphite body in the form of heat flux on the incident (or facing) surface, to be quickly distributed through the entire pyrolytic graphite body, resulting in small substantially instantaneous temperature gradients. Temperature changes to the body can thereby be measured by the thermocouple, and reduced to quantify the heat flux incident to the body.

  8. Cortical substrate oxidation during hyperketonemia in the fasted anesthetized rat in vivo.

    Science.gov (United States)

    Jiang, Lihong; Mason, Graeme F; Rothman, Douglas L; de Graaf, Robin A; Behar, Kevin L

    2011-12-01

    Ketone bodies are important alternate brain fuels, but their capacity to replace glucose and support neural function is unclear. In this study, the contributions of ketone bodies and glucose to cerebral cortical metabolism were measured in vivo in halothane-anesthetized rats fasted for 36 hours (n=6) and receiving intravenous [2,4-(13)C(2)]-D-β-hydroxybutyrate (BHB). Time courses of (13)C-enriched brain amino acids (glutamate-C4, glutamine-C4, and glutamate and glutamine-C3) were measured at 9.4 Tesla using spatially localized (1)H-[(13)C]-nuclear magnetic resonance spectroscopy. Metabolic rates were estimated by fitting a constrained, two-compartment (neuron-astrocyte) metabolic model to the (13)C time-course data. We found that ketone body oxidation was substantial, accounting for 40% of total substrate oxidation (glucose plus ketone bodies) by neurons and astrocytes. D-β-Hydroxybutyrate was oxidized to a greater extent in neurons than in astrocytes (≈ 70:30), and followed a pattern closely similar to the metabolism of [1-(13)C]glucose reported in previous studies. Total neuronal tricarboxylic acid cycle (TCA) flux in hyperketonemic rats was similar to values reported for normal (nonketotic) anesthetized rats infused with [1-(13)C]glucose, but neuronal glucose oxidation was 40% to 50% lower, indicating that ketone bodies had compensated for the reduction in glucose use.

  9. The PROMETHEE multiple criteria decision making analysis for selecting the best membrane prepared from sulfonated poly(ether ketone)s and poly(ether sulfone)s for proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Nikouei, Mohammad Ali; Oroujzadeh, Maryam; Mehdipour-Ataei, Shahram

    2017-01-01

    Proton exchange membrane as the heart of fuel cell has been the topic of many research activities in recent years. Finding a suitable alternative for Nafion membranes is one of the most important issues of interest. This study is dedicated to sulfonated poly(ether ketone) and poly(ether sulfone) membranes. For synthesis of these two groups of polymers, two different isomeric biphenols (meta- and para-) were used and each group of membranes with three different degree of sulfonation (25, 35, and 45%) was synthesized. In this way, twelve different membrane samples were obtained and their properties were evaluated. Since each membrane had some strong and some weak points of properties in comparison to the other ones, using a rational analysis for choosing the best membrane between prepared samples was inevitable. For this purpose a PROMETHEE based multiple criteria decision making approach was applied and for evaluation of the weight of each criterion, Shannon entropy method was used. Final results showed that poly(ether ketone) membranes in selected criteria were better than poly(ether sulfone) membranes and as expected, membranes with the highest degree of sulfonation (45%) were placed at the top ranking levels. - Highlights: • Sulfonated poly(ether ketone)s and Poly(ether sulfone)s were synthesized. • Related membranes for PEMFC were prepared. • The properties of membranes were measured. • Multiple criteria decision making approach was used to ranking the membranes. • PROMETHEE based approach selected poly(ether ketone)s as better choices.

  10. Ru (III) Catalyzed Oxidation of Aliphatic Ketones by N-Bromosuccinimide in Aqueous Acetic Acid: A Kinetic Study

    Science.gov (United States)

    Giridhar Reddy, P.; Ramesh, K.; Shylaja, S.; Rajanna, K. C.; Kandlikar, S.

    2012-01-01

    Kinetics of Ru (III) catalyzed oxidation of aliphatic ketones such as acetone, ethyl methyl ketone, diethyl ketone, iso-butylmethyl ketone by N-bromosuccinimide in the presence of Hg(II) acetate have been studied in aqueous acid medium. The order of [N-bromosuccinimide] was found to be zero both in catalyzed as well as uncatalyzed reactions. However, the order of [ketone] changed from unity to a fractional one in the presence of Ru (III). On the basis of kinetic features, the probable mechanisms are discussed and individual rate parameters evaluated. PMID:22654610

  11. A Convenient Synthesis of Conjugated Acetylenic Ketones by Copper(l)-Catalyzed under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    WANG; JinXian

    2001-01-01

    Alkynyl ketones are useful precursors and intermediates in synthetic organic chemistry1 and has evoked considerable interest. A number of methods for the synthesis of conjugated acetylenic ketones involve the reaction a metal acetylide with an acyl chlorides or another carboxylic acid derivative have been developed 2. Recently, the synthesis of α, β-conjugated acetylenic ketones catalyzed by Pd(Ⅱ) or by copper(Ⅰ)pd(Ⅱ) reaction of 1-alkynes and acyl chlorides have been described. The acylation of terminal alkynes by acyl chlorides in the presence of catalytic amounts copper(Ⅰ) salts leading to α, β-conjugated acetylenic ketones has also been reported. However, many of these reactions suffer from lack of high pressure (17 atm), long reaction time (30 h)and require low temperatures (-78℃). Our work involves the synthesis of conjugated acetylenic ketones via the reaction of terminal alkynes with aroyl chlorides in the presence of cuprous iodide under microwave irradiation conditions.……

  12. A Convenient Synthesis of Conjugated Acetylenic Ketones by Copper(l)-Catalyzed under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    WANG JinXian; WEI BangGuo; ZHAO LianBiao; HU YuLai; KANG LiQing

    2001-01-01

    @@ Alkynyl ketones are useful precursors and intermediates in synthetic organic chemistry1 and has evoked considerable interest. A number of methods for the synthesis of conjugated acetylenic ketones involve the reaction a metal acetylide with an acyl chlorides or another carboxylic acid derivative have been developed 2. Recently, the synthesis of α, β-conjugated acetylenic ketones catalyzed by Pd(Ⅱ) or by copper(Ⅰ)pd(Ⅱ) reaction of 1-alkynes and acyl chlorides have been described. The acylation of terminal alkynes by acyl chlorides in the presence of catalytic amounts copper(Ⅰ) salts leading to α, β-conjugated acetylenic ketones has also been reported. However, many of these reactions suffer from lack of high pressure (17 atm), long reaction time (30 h)and require low temperatures (-78℃). Our work involves the synthesis of conjugated acetylenic ketones via the reaction of terminal alkynes with aroyl chlorides in the presence of cuprous iodide under microwave irradiation conditions.

  13. On the nature of the olefination reaction involving ditungsten hexaalkoxides and aldehydes or ketones

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, M.H.; Huffman, J.C.; Lucas, E.A.; Sousa, A.; Streib, W.E. [Indiana Univ., Bloomington, IN (United States)

    1992-03-25

    Reductive coupling of aldehydes and ketones to olefins under the action of ditungsten hexaalkoxides was investigated. In these reactions, reductive cleavage of the aldehyde or ketone carbonyl is followed by formation of the olefinic C-C bond and breaking of the carbonyl C-O bond of the second aldehyde or ketone. Observations concerning the initial C-O bond cleavage and subsequent C-C bond formation are presented. 10 refs., 4 figs.

  14. Enzymatic Baeyer-Villiger Oxidation of Benzo-Fused Ketones : Formation of Regiocomplementary Lactones

    NARCIS (Netherlands)

    Rioz-Martinez, Ana; de Gonzalo, Gonzalo; Pazmino, Daniel E. Torres; Fraaije, Marco W.; Gotor, Vicente

    Baeyer-Villiger monooxygenases (BVMOs) are enzymes that are known to catalyse the Baeyer-Villiger oxidation of ketones in aqueous media using O(2) as oxidant. Herein, we describe the oxidation of a set of diverse benzo-fused ketones by three different BVMOs in both aqueous and non-conventional

  15. Effects of iron-containing minerals on hydrothermal reactions of ketones

    Science.gov (United States)

    Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

    2018-02-01

    Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

  16. Fluxes of biogenic volatile organic compounds measured and modelled above a Norway spruce forest

    Science.gov (United States)

    Juráň, Stanislav; Fares, Silvano; Pallozzi, Emanuele; Guidolotti, Gabriele; Savi, Flavia; Alivernini, Alessandro; Calfapietra, Carlo; Večeřová, Kristýna; Křůmal, Kamil; Večeřa, Zbyněk; Cudlín, Pavel; Urban, Otmar

    2016-04-01

    Fluxes of biogenic volatile organic compounds (BVOCs) were investigated at Norway spruce forest at Bílý Kříž in Beskydy Mountains of the Czech Republic during the summer 2014. A proton-transfer-reaction-time-of-flight mass spectrometer (PTR-TOF-MS, Ionicon Analytik, Austria) has been coupled with eddy-covariance system. Additionally, Inverse Lagrangian Transport Model has been used to derive fluxes from concentration gradient of various monoterpenes previously absorbed into n-heptane by wet effluent diffusion denuder with consequent quantification by gas chromatography with mass spectrometry detection. Modelled data cover each one day of three years with different climatic conditions and previous precipitation patterns. Model MEGAN was run to cover all dataset with monoterpene fluxes and measured basal emission factor. Highest fluxes measured by eddy-covariance were recorded during the noon hours, represented particularly by monoterpenes and isoprene. Inverse Lagrangian Transport Model suggests most abundant monoterpene fluxes being α- and β-pinene. Principal component analysis revealed dependencies of individual monoterpene fluxes on air temperature and particularly global radiation; however, these dependencies were monoterpene specific. Relationships of monoterpene fluxes with CO2 flux and relative air humidity were found to be negative. MEGAN model correlated to eddy-covariance PTR-TOF-MS measurement evince particular differences, which will be shown and discussed. Bi-directional fluxes of oxygenated short-chain volatiles (methanol, formaldehyde, acetone, acetaldehyde, formic acid, acetic acid, methyl vinyl ketone, methacrolein, and methyl ethyl ketone) were recorded by PTR-TOF-MS. Volatiles of anthropogenic origin as benzene and toluene were likely transported from the most benzene polluted region in Europe - Ostrava city and adjacent part of Poland around Katowice, where metallurgical and coal mining industries are located. Those were accumulated during

  17. Atmospheric fate of methyl vinyl ketone

    DEFF Research Database (Denmark)

    Praske, Eric; Crounse, John D; Bates, Kelvin H

    2015-01-01

    First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl...

  18. Novel Zero-Heat-Flux Deep Body Temperature Measurement in Lower Extremity Vascular and Cardiac Surgery.

    Science.gov (United States)

    Mäkinen, Marja-Tellervo; Pesonen, Anne; Jousela, Irma; Päivärinta, Janne; Poikajärvi, Satu; Albäck, Anders; Salminen, Ulla-Stina; Pesonen, Eero

    2016-08-01

    The aim of this study was to compare deep body temperature obtained using a novel noninvasive continuous zero-heat-flux temperature measurement system with core temperatures obtained using conventional methods. A prospective, observational study. Operating room of a university hospital. The study comprised 15 patients undergoing vascular surgery of the lower extremities and 15 patients undergoing cardiac surgery with cardiopulmonary bypass. Zero-heat-flux thermometry on the forehead and standard core temperature measurements. Body temperature was measured using a new thermometry system (SpotOn; 3M, St. Paul, MN) on the forehead and with conventional methods in the esophagus during vascular surgery (n = 15), and in the nasopharynx and pulmonary artery during cardiac surgery (n = 15). The agreement between SpotOn and the conventional methods was assessed using the Bland-Altman random-effects approach for repeated measures. The mean difference between SpotOn and the esophageal temperature during vascular surgery was+0.08°C (95% limit of agreement -0.25 to+0.40°C). During cardiac surgery, during off CPB, the mean difference between SpotOn and the pulmonary arterial temperature was -0.05°C (95% limits of agreement -0.56 to+0.47°C). Throughout cardiac surgery (on and off CPB), the mean difference between SpotOn and the nasopharyngeal temperature was -0.12°C (95% limits of agreement -0.94 to+0.71°C). Poor agreement between the SpotOn and nasopharyngeal temperatures was detected in hypothermia below approximately 32°C. According to this preliminary study, the deep body temperature measured using the zero-heat-flux system was in good agreement with standard core temperatures during lower extremity vascular and cardiac surgery. However, agreement was questionable during hypothermia below 32°C. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Ketones in Urine: MedlinePlus Lab Test Information

    Science.gov (United States)

    ... K. Brunner & Suddarth's Handbook of Laboratory and Diagnostic Tests. 2 nd Ed, Kindle. Philadelphia: Wolters Kluwer Health, Lippincott Williams & Wilkins; c2014. Ketones: Urine; p. 351. Joslin Diabetes ...

  20. Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

    NARCIS (Netherlands)

    Ortiz, Pablo; Harutyunyan, Syuzanna; del Hoyo, Ana

    Tertiary diarylmethanols are highly bioactive structural motifs. A new strategy to access chiral tertiary diarylmethanols through copper-catalyzed direct alkylation of (di)(hetero)aryl ketones by using Grignard reagents was developed. The low reactivity and the similarity of the enantiotopic faces

  1. Ketone Bodies as a Possible Adjuvant to Ketogenic Diet in PDHc Deficiency but Not in GLUT1 Deficiency.

    Science.gov (United States)

    Habarou, F; Bahi-Buisson, N; Lebigot, E; Pontoizeau, C; Abi-Warde, M T; Brassier, A; Le Quan Sang, K H; Broissand, C; Vuillaumier-Barrot, S; Roubertie, A; Boutron, A; Ottolenghi, C; de Lonlay, P

    2018-01-01

    Ketogenic diet is the first line therapy for neurological symptoms associated with pyruvate dehydrogenase deficiency (PDHD) and intractable seizures in a number of disorders, including GLUT1 deficiency syndrome (GLUT1-DS). Because high-fat diet raises serious compliance issues, we investigated if oral L,D-3-hydroxybutyrate administration could be as effective as ketogenic diet in PDHD and GLUT1-DS. We designed a partial or total progressive substitution of KD with L,D-3-hydroxybutyrate in three GLUT1-DS and two PDHD patients. In GLUT1-DS patients, we observed clinical deterioration including increased frequency of seizures and myoclonus. In parallel, ketone bodies in CSF decreased after introducing 3-hydroxybutyrate. By contrast, two patients with PDHD showed clinical improvement as dystonic crises and fatigability decreased under basal metabolic conditions. In one of the two PDHD children, 3-hydroxybutyrate has largely replaced the ketogenic diet, with the latter that is mostly resumed only during febrile illness. Positive direct effects on energy metabolism in PDHD patients were suggested by negative correlation between ketonemia and lactatemia (r 2  = 0.59). Moreover, in cultured PDHc-deficient fibroblasts, the increase of CO 2 production after 14 C-labeled 3-hydroxybutyrate supplementation was consistent with improved Krebs cycle activity. However, except in one patient, ketonemia tended to be lower with 3-hydroxybutyrate administration compared to ketogenic diet. 3-hydroxybutyrate may be an adjuvant treatment to ketogenic diet in PDHD but not in GLUT1-DS under basal metabolic conditions. Nevertheless, ketogenic diet is still necessary in PDHD patients during febrile illness.

  2. Ingested water equilibrates isotopically with the body water pool of a shorebird with unrivaled water fluxes

    NARCIS (Netherlands)

    Visser, G.H.; Dekinga, A; Achterkamp, B.; Piersma, T.

    We investigated the applicability of H-2 to measure the amount of body water (TBW) and water fluxes in relation to diet type and level of food intake in a mollusk-eating shorebird, the Red Knot (Calidris canutus). Six birds were exposed to eight experimental indoor conditions. Average fractional H-2

  3. Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

    Science.gov (United States)

    Acton, W. Joe F.; Schallhart, Simon; Langford, Ben; Valach, Amy; Rantala, Pekka; Fares, Silvano; Carriero, Giulia; Tillmann, Ralf; Tomlinson, Sam J.; Dragosits, Ulrike; Gianelle, Damiano; Hewitt, C. Nicholas; Nemitz, Eiko

    2016-06-01

    This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m-2 h-1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m-2 h-1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC-MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

  4. Fragrance material review on methyl-2,6,10-trimethylcyclododeca-2,5,9-trien-1-yl ketone.

    Science.gov (United States)

    Scognamiglio, J; Letizia, C S; Api, A M

    2013-12-01

    A toxicologic and dermatologic review of methyl 2,6,10-trimethylcyclododeca-2,5,9-trien-1-yl ketone when used as a fragrance ingredient is presented. Methyl 2,6,10-trimethylcyclododeca-2,5,9-trien-1-yl ketone is a member of the fragrance structural group Alkyl Cyclic Ketones. These fragrances can be described as being composed of an alkyl, R1, and various substituted and bicyclic saturated or unsaturated cyclic hydrocarbons, R2, in which one of the rings may include up to 12 carbons. Alternatively, R2 may be a carbon bridge of C2-C4 carbon chain length between the ketone and cyclic hydrocarbon. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for methyl 2,6,10-trimethylcyclododeca-2,5,9-trien-1-yl ketone were evaluated then summarized and includes physical properties, acute toxicity, skin irritation, mucous membrane (eye) irritation, skin sensitization, repeated dose, and genotoxicity data. A safety assessment of the entire Alkyl Cyclic Ketones will be published simultaneously with this document; please refer to Belsito et al. (Belsito, D., Bickers, D., Bruze, M., Calow, P., Dagli, M., Fryer, A.D., Greim, H., Miyachi, Y., Saurat, J.H., Sipes, I.G., 2013. A Toxicologic and Dermatologic Assessment of Alkyl Cyclic Ketones When Used as Fragrance Ingredients (submitted for publication)) for an overall assessment of the safe use of this material and all Alkyl Cyclic Ketones in fragrances. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Qiuxia [Institute for Integrated Catalysis, Pacific Northwest; College; Lopez-Ruiz, Juan A. [Institute for Integrated Catalysis, Pacific Northwest; Cooper, Alan R. [Institute for Integrated Catalysis, Pacific Northwest; Wang, Jian-guo [College; Albrecht, Karl O. [Institute for Integrated Catalysis, Pacific Northwest; Mei, Donghai [Institute for Integrated Catalysis, Pacific Northwest

    2017-12-13

    The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxyl groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley

  6. The retro Grignard addition reaction revisited: the reversible addition of benzyl reagents to ketones

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Holm, Torkil; Madsen, Robert

    2014-01-01

    transformation. The retro benzyl reaction was shown by the addition of benzylmagnesium chloride to di-tert-butyl ketone followed by exchange of both the benzyl and the ketone moiety with another substrate. Similar experiments were performed with phenylmagnesium bromide and tert-butylmagnesium chloride...

  7. Polyether ether ketone film. Polyether ether ketone film

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, S. (Sumitomo Chemical Co. Ltd., Tokyo (Japan))

    1990-07-05

    The characteristics and the film making process of polyether ether ketone (PEEK) resin, and the characteristics and the applications of PEEK film, are described. PEEK is aromatic polyketone with super thermal resistance. Though it is a crystalline polymer of which the crystallinity is controlled to 48% in a highest degree, it has also amorphous property, thus it shows unique property. The characteristics of PEEK resin are found in thermal resistance, incombusti-bility, transparency, chemical resistance, light resistance and radiation resistance. As for the film making process, casting method by T-die is generally adopted. The general properties of PEEK film are excellent in high thermal resistance, good electrical properties, chemical resistance, hydrolysis resistance, radiation resistance and imcombusti-bility. In the application of PEEK film, new development is expected in following fields; a high performance composite, flexible print substrate with high thermal resistance, insulating tape with thermal resistance, and a general film in the nuclear energy industry. 5 figs., 5 tabs.

  8. [Effect of phenolic ketones on ethanol fermentation and cellular lipid composition of Pichia stipitis].

    Science.gov (United States)

    Yang, Jinlong; Cheng, Yichao; Zhu, Yuanyuan; Zhu, Junjun; Chen, Tingting; Xu, Yong; Yong, Qiang; Yu, Shiyuan

    2016-02-01

    Lignin degradation products are toxic to microorganisms, which is one of the bottlenecks for fuel ethanol production. We studied the effects of phenolic ketones (4-hydroxyacetophenone, 4-hydroxy-3-methoxy-acetophenone and 4-hydroxy-3,5-dimethoxy-acetophenone) derived from lignin degradation on ethanol fermentation of xylose and cellular lipid composition of Pichia stipitis NLP31. Ethanol and the cellular fatty acid of yeast were analyzed by high performance liquid chromatography (HPLC) and gas chromatography/mass spectrometry (GC/MS). Results indicate that phenolic ketones negatively affected ethanol fermentation of yeast and the lower molecular weight phenolic ketone compound was more toxic. When the concentration of 4-hydroxyacetophenone was 1.5 g/L, at fermentation of 24 h, the xylose utilization ratio, ethanol yield and ethanol concentration decreased by 42.47%, 5.30% and 9.76 g/L, respectively, compared to the control. When phenolic ketones were in the medium, the ratio of unsaturated fatty acids to saturated fatty acids (UFA/SFA) of yeast cells was improved. When 1.5 g/L of three aforementioned phenolic ketones was added to the fermentation medium, the UFA/SFA ratio of yeast cells increased to 3.03, 3.06 and 3.61, respectively, compared to 2.58 of the control, which increased cell membrane fluidity and instability. Therefore, phenolic ketones can reduce the yeast growth, increase the UFA/SFA ratio of yeast and lower ethanol productivity. Effectively reduce or remove the content of lignin degradation products is the key to improve lignocellulose biorefinery.

  9. Raspberry Ketone Trifluoroacetate, a new attractant for the Queensland fruit fly (Bactrocera tryoni (Froggatt))

    Science.gov (United States)

    The Queensland fruit fly (Bactrocera tryoni, Q-fly) is a major agricultural pest in eastern Australia. The deployment of male lures comprises an important component of several control and detection strategies for this pest. A novel fluorinated analog of raspberry ketone, raspberry ketone trifluoroac...

  10. Inhalation developmental toxicology studies: Teratology study of methyl ethyl ketone in mice: Final report

    Energy Technology Data Exchange (ETDEWEB)

    Mast, T.J.; Dill, J.A.; Evanoff, J.J.; Rommereim, R.L.; Weigel, R.J.; Westerberg, R.B.

    1989-02-01

    Methyl ethyl ketone (MEK) is a widely used industrial solvent which results in considerable human exposure. In order to assess the potential for MEK to cause developmental toxicity in rodents, four groups of Swiss (CD-1) mice were exposed to 0, 400, 1000 or 3000 ppM MEK vapors, 7 h/day, 7 dy/wk. Ten virgin females and approx.30 plug-positive females per group were exposed concurrently for 10 consecutive days (6--15 dg for mated mice). Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice on 18 dg. Uterine implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. Exposure of pregnant mice to these concentrations of MEK did not result in apparent maternal toxicity, although there was a slight, treatment-correlated increase in liver to body weight ratios which was significant for the 3000-ppM group. Mild developmental toxicity was evident at 3000-ppM as a reduction in mean fetal body weight. This reduction was statistically significant for the males only, although the relative decrease in mean fetal body weight was the same for both sexes. 17 refs., 4 figs., 10 tabs.

  11. Inhalation developmental toxicology studies: Teratology study of methyl ethyl ketone in mice: Final report

    International Nuclear Information System (INIS)

    Mast, T.J.; Dill, J.A.; Evanoff, J.J.; Rommereim, R.L.; Weigel, R.J.; Westerberg, R.B.

    1989-02-01

    Methyl ethyl ketone (MEK) is a widely used industrial solvent which results in considerable human exposure. In order to assess the potential for MEK to cause developmental toxicity in rodents, four groups of Swiss (CD-1) mice were exposed to 0, 400, 1000 or 3000 ppM MEK vapors, 7 h/day, 7 dy/wk. Ten virgin females and ∼30 plug-positive females per group were exposed concurrently for 10 consecutive days (6--15 dg for mated mice). Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice on 18 dg. Uterine implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. Exposure of pregnant mice to these concentrations of MEK did not result in apparent maternal toxicity, although there was a slight, treatment-correlated increase in liver to body weight ratios which was significant for the 3000-ppM group. Mild developmental toxicity was evident at 3000-ppM as a reduction in mean fetal body weight. This reduction was statistically significant for the males only, although the relative decrease in mean fetal body weight was the same for both sexes. 17 refs., 4 figs., 10 tabs

  12. The Role of Energy Flux in Weight Management

    Directory of Open Access Journals (Sweden)

    Clemens Drenowatz

    2017-12-01

    Full Text Available Excess body weight has been identified as one of the leading threats to public health. In addition to health concerns at the individual level, the increased medical costs put a significant burden on the health care system. Even though an imbalance between energy intake and energy expenditure is ultimately responsible for changes in body weight and body composition such a simple opposition does not reflect the complex interaction of various contributors to energy balance. The limited understanding of the regulation of energy balance is also reflected by rising obesity levels, despite considerable efforts. In addition to energy balance, energy flux, which represents the rate of energy intake and energy expenditure, has been suggested to play an important role in the regulation of energy balance. Particularly a higher energy flux has been associated with a better matching of energy intake and energy expenditure resulting in stable body weight. While a high energy flux has been traditionally attributed to increased levels of physical activity it should be considered that increased body weight also affects energy expenditure and accordingly energy flux. In fact, total daily energy expenditure, and accordingly energy flux, does not differ between people in industrialized countries, living a predominantly sedentary lifestyle and people following a traditional lifestyle, characterized by high physical activity even though there are significant differences in body weight and body composition. It can, therefore, be argued that energy flux, rather than energy balance is a physiologically regulated entity. In this situation body weight and physical activity levels work in opposition to maintain a constant energy flux and weight gain would be a means to maintain a high energy flux with a sedentary lifestyle.

  13. Constituents of Artemisia gmelinii Weber ex Stechm. from Uttarakhand Himalaya: A Source of Artemisia Ketone

    Science.gov (United States)

    Haider, S. Z.; Andola, H. C.; Mohan, M.

    2012-01-01

    The essential oils isolated from the aerial parts of two different populations of Artemisia gmelinii growing in Uttarakhand Himalaya region were analysed by gas chromatography and gas chromatography/mass spectrometry (GC-MS) in order to determine the variation of concentration in their constituents. Artemisia ketone was detected as a major constituent in both the populations i.e., Niti valley and Jhelum samples. Niti oil was found to have considerably greater amounts of artemesia ketone (53.34%) followed by α-thujone (9.91%) and 1,8-cineole (6.57%), Similarly, the first major compound in Jhelum oil was artemesia ketone (40.87%), whereas ar-curcumene (8.54%) was identified as a second major compound followed by α-thujone (4.04%). Artemisia ketone can be useful for perfumery and fragrance to introduce new and interesting herbaceous notes. PMID:23439844

  14. The role of point-of-care blood testing for ketones in the diagnosis of ...

    African Journals Online (AJOL)

    estimated that the annual cost of treating DKA in the USA exceeds. 1 billion ... If urinary ketones are positive, patients are referred for further management – often ... To evaluate a hand-held electrochemical (point-of-care testing; POCT) ketone monitor and compare it with the gold-standard ..... renal failure may be present.

  15. Bedside ketone determination in diabetic children with hyperglycemia and ketosis in the acute care setting.

    Science.gov (United States)

    Ham, Melissa R; Okada, Pamela; White, Perrin C

    2004-03-01

    Diabetic ketoacidosis (DKA) is a serious complication of diabetes mellitus marked by characteristic biochemical derangements. Diagnosis and management involve frequent evaluation of these biochemical parameters. Reliable bedside equivalents for these laboratory studies may help reduce the time to treatment and reduce costs. We evaluated the precision and bias of a bedside serum ketone meter in the acute care setting. Serum ketone results using the Precision Xtra glucometer/ketone meter (Abbott Laboratories, MediSense Products Inc., Bedford, MA, USA) correlated strongly with the Children's Medical Center of Dallas' laboratory values within the meter's value range. Meter ketone values steadily decreased during the treatment of DKA as pH and CO(2) levels increased and acidosis resolved. Therefore, the meter may be useful in monitoring therapy for DKA. This meter may also prove useful in identifying patients at risk for DKA in physicians' offices or at home.

  16. An In Silico Knockout Model for Gastrointestinal Absorption Using a Systems Pharmacology Approach - Development and Application for Ketones.

    Directory of Open Access Journals (Sweden)

    Vittal Shivva

    Full Text Available Gastrointestinal absorption and disposition of ketones is complex. Recent work describing the pharmacokinetics (PK of d-β-hydroxybutyrate (BHB following oral ingestion of a ketone monoester ((R-3-hydroxybutyl (R-3-hydroxybutyrate found multiple input sites, nonlinear disposition and feedback on endogenous production. In the current work, a human systems pharmacology model for gastrointestinal absorption and subsequent disposition of small molecules (monocarboxylic acids with molecular weight < 200 Da was developed with an application to a ketone monoester. The systems model was developed by collating the information from the literature and knowledge gained from empirical population modelling of the clinical data. In silico knockout variants of this systems model were used to explore the mechanism of gastrointestinal absorption of ketones. The knockouts included active absorption across different regions in the gut and also a passive diffusion knockout, giving 10 gut knockouts in total. Exploration of knockout variants has suggested that there are at least three distinct regions in the gut that contribute to absorption of ketones. Passive diffusion predominates in the proximal gut and active processes contribute to the absorption of ketones in the distal gut. Low doses are predominantly absorbed from the proximal gut by passive diffusion whereas high doses are absorbed across all sites in the gut. This work has provided mechanistic insight into the absorption process of ketones, in the form of unique in silico knockouts that have potential for application with other therapeutics. Future studies on absorption process of ketones are suggested to substantiate findings in this study.

  17. Ultraviolet-induced surface grafting of octafluoropentyl methacrylate on polyether ether ketone for inducing antibiofilm properties.

    Science.gov (United States)

    Amdjadi, Parisa; Nojehdehian, Hanieh; Najafi, Farhood; Ghasemi, Amir; Seifi, Massoud; Dashtimoghadam, Erfan; Fahimipour, Farahnaz; Tayebi, Lobat

    2017-07-01

    Since octafluoropentyl methacrylate is an antifouling polymer, surface modification of polyether ether ketone with octafluoropentyl methacrylate is a practical approach to obtaining anti-biofilm biocompatible devices. In the current study, the surface treatment of polyether ether ketone by the use of ultraviolet irradiation, so as to graft (octafluoropentyl methacrylate) polymer chains, was initially implemented and then investigated. The Fourier-transform infrared and nuclear magnetic resonance spectra corroborated the appearance of new signals associated with the fluoroacrylate group. Thermogravimetric curves indicated enhanced asymmetry in the polymer structure due to the introduction of the said new groups. Measuring the peak area in differential scanning calorimetry experiments also showed additional bond formation. Static water contact angle measurements indicated a change in wettability to the more hydrophobic surface. The polyether ether ketone-octafluoropentyl methacrylate surface greatly reduced the protein adsorption. This efficient method can modulate and tune the surface properties of polyether ether ketone according to specific applications.

  18. Excess enthalpies and (vapour + liquid) equilibrium data for the binary mixtures of dimethylsulphoxide with ketones

    International Nuclear Information System (INIS)

    Radhamma, M.; Venkatesu, P.; Rao, M.V. Prabhakara; Prasad, D.H.L.

    2007-01-01

    Excess enthalpies (H E ), at ambient pressure and T = 298.15 K, have been measured by using a solution calorimeter for the binary liquid mixtures of dimethyl sulphoxide (DMSO) with ketones, as a function of composition. The ketones chosen in the present investigation were methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CH). The H E values are positive over the entire composition range for the three binary mixtures. Furthermore, the (vapour + liquid) equilibrium (VLE) was measured at 715 Torr for these mixtures, of different compositions, with the help of Swietoslawski-ebulliometer. The experimental temperature-mole fraction (t-x) data were used to compute Wilson parameters and then used to calculate the equilibrium vapour-phase compositions as well as the theoretical points for these binary mixtures. These Wilson parameters are used to calculate activity coefficients (γ) and these in turn to calculate excess Gibbs free energy (G E ). The intermolecular interactions and structural effects were analyzed on the basis of the measured and derived properties

  19. Candida tropicalis CE017: a new Brazilian enzymatic source for the bioreduction of aromatic prochiral ketones

    International Nuclear Information System (INIS)

    Vieira, Gizelle A.B.; Araujo, Daniel M. de Freitas; Lemos, Telma L.G.; Mattos, Marcos Carlos de; Oliveira, Maria da Conceicao F. de; Melo, Vania M.M.; Gonzalo, Gonzalo de; Gotor-Fernandez, Vicente; Gotor, Vicente

    2010-01-01

    The reactivity and stereoselectivity showed by a new strain of Candida tropicalis in the reduction of prochiral ketones have been compared with the ones previously attained in our laboratory using microorganisms from the Brazilian biodiversity. In this manner, Candida tropicalis has demonstrated its versatility as stereoselective agent in the bioreduction of a series of aromatic ketones. These prochiral compounds were converted into their corresponding optically alcohols with moderate to excellent stereopreference depending on the substrate structure. Among ketones tested, nitroacetophenones were enzymatically reduced to enantiopure (S)-alcohol with complete conversion. (author)

  20. Synthetic Applications and Mechanistic Studies of the Hydroxide-Mediated Cleavage of Carbon-Carbon Bonds in Ketones

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Makarov, Ilya S.; Fristrup, Peter

    2017-01-01

    The hydroxide-mediated cleavage of ketones into alkanes and carboxylic acids has been reinvestigated and the substrate scope extended to benzyl carbonyl compounds. The transformation is performed with a 0.05 M ketone solution in refluxing xylene in the presence of 10 equiv of potassium hydroxide....... The studies were complemented by a theoretical investigation where two possible pathways were characterized by DFT/M06-2X. The calculations showed that the scission takes place by nucleophilic attack of hydroxide on the ketone followed by fragmentation of the resulting oxyanion into the carboxylic acid...

  1. Candida tropicalis CE017: a new Brazilian enzymatic source for the bioreduction of aromatic prochiral ketones

    Energy Technology Data Exchange (ETDEWEB)

    Vieira, Gizelle A.B.; Araujo, Daniel M. de Freitas; Lemos, Telma L.G.; Mattos, Marcos Carlos de; Oliveira, Maria da Conceicao F. de; Melo, Vania M.M., E-mail: mcdmatto@ufc.b [Universidade Federal do Ceara (DQOI/UFC), Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica; Gonzalo, Gonzalo de; Gotor-Fernandez, Vicente; Gotor, Vicente [Universidad de Oviedo, Oviedo (Spain). Inst. Univ. de Biotecnologia de Asturias. Dept. de Quimica Organica e Inorganica

    2010-07-01

    The reactivity and stereoselectivity showed by a new strain of Candida tropicalis in the reduction of prochiral ketones have been compared with the ones previously attained in our laboratory using microorganisms from the Brazilian biodiversity. In this manner, Candida tropicalis has demonstrated its versatility as stereoselective agent in the bioreduction of a series of aromatic ketones. These prochiral compounds were converted into their corresponding optically alcohols with moderate to excellent stereopreference depending on the substrate structure. Among ketones tested, nitroacetophenones were enzymatically reduced to enantiopure (S)-alcohol with complete conversion. (author)

  2. Process for conversion of levulinic acid to ketones

    Energy Technology Data Exchange (ETDEWEB)

    Dagle, Vanessa M.; Dagle, Robert A.

    2017-05-30

    A method for generating desired platform chemicals from feedstocks such as cellulosic biomass feedstocks containing levulinic acid by decarboxylating a feed stock comprising levulinic acid to generate ketones. This is done by passing a feed stock comprising levulinic acid in a gas phase over a non-precious metal catalyst on a neutral support.

  3. Biofiltration of odours - industrial pilot to treat methyl ethyl ketone and toluene

    International Nuclear Information System (INIS)

    Otten, L.; Elsie, K.

    2002-01-01

    Methyl ethyl ketone and toluene in the off-gases of a plant producing polyvinyl chloride sheeting for the automotive industry and swimming pools caused frequent odour complaints from the neighbourhood. A pilot project was developed to investigate the removal of the compounds under actual operating conditions by passing part of the exhaust through a compost-based, three-stage biofilter. It was determined over the 156 days of operation that the removal efficiencies of methyl ethyl ketone and toluene averaged 73% and 49%, respectively. It was also shown that shutdowns and disruptions of the laminating process for short and extended periods did not affect the biofilter performance. Addition of 100g/L solution of KNO 3 as a nitrogen source did not improve the performance. Carbon dioxide concentration data and the presence of an average microbial population of 52 million colony forming units per gram provided evidence that biological degradation played a significant role in the reduction of methyl ethyl ketone and toluene in the off-gases of the laminator. (author)

  4. Photochemical studies on aromatic γ,δ-epoxy ketones: efficient synthesis of benzocyclobutanones and indanones.

    Science.gov (United States)

    Shao, Yutian; Yang, Chao; Gui, Weijun; Liu, Yang; Xia, Wujiong

    2012-04-11

    Irradiation of terminal aromatic γ,δ-epoxy ketones with a 450 W UV lamp led to Norrish type II cyclization/semi-pinacol rearrangement cascade reaction which formed the benzocyclobutanones containing a full-carbon quaternary center, whereas irradiation of substituted aromatic γ,δ-epoxy ketones led to the indanones through a photochemical epoxy rearrangement and 1,5-biradicals cyclization tandem reaction. This journal is © The Royal Society of Chemistry 2012

  5. Evaluation of crystallization kinetics of poly (ether-ketone-ketone and poly (ether-ether-ketone by DSC

    Directory of Open Access Journals (Sweden)

    Gibran da Cunha Vasconcelos

    2010-08-01

    Full Text Available The poly (aryl ether ketones are used as matrices in advanced composites with high performance due to its high thermal stability, excellent environmental performance and superior mechanical properties. Most of the physical, mechanical and thermodynamic properties of semi-crystalline polymers depend on the degree of crystallinity and morphology of the crystalline regions. Thus, a study on the crystallization process promotes a good prediction of how the manufacturing parameters affect the developed structure, and the properties of the final product. The objective of this work was to evaluate the thermoplastics polymers PEKK e PEEK by DSC, aiming to obtain the relationship between kinetics, content, nucleation and geometry of the crystalline phases, according to the parameters of the Avrami and Kissinger models. The analysis of the Avrami exponents obtained for the studied polymers indicates that both showed the formation of crystalline phases with heterogeneous nucleation and growth geometry of the type sticks or discs, depending on the cooling conditions. It was also found that the PEEK has a higher crystallinity than PEKK.

  6. Anxiolytic Effect of Exogenous Ketone Supplementation Is Abolished by Adenosine A1 Receptor Inhibition in Wistar Albino Glaxo/Rijswijk Rats.

    Science.gov (United States)

    Kovács, Zsolt; D'Agostino, Dominic P; Ari, Csilla

    2018-01-01

    Anxiety disorders are one of the most common mental health problems worldwide, but the exact pathophysiology remains largely unknown. It has been demonstrated previously that administration of exogenous ketone supplement KSMCT (ketone salt/KS + medium chain triglyceride/MCT oil) by intragastric gavage for 7 days decreased the anxiety level in genetically absence epileptic Wistar Albino Glaxo/Rijswijk (WAG/Rij) rats. To investigate the potential role of the adenosinergic system in the pathomechanism of anxiety we tested whether the inhibition of adenosine A 1 receptors (A 1 Rs) influence the anxiolytic effect of the exogenous ketone supplement. As A 1 Rs may mediate such an effect, in the present study we used a specific A 1 R antagonist, DPCPX (1,3-dipropyl-8-cyclopentylxanthine) to test whether it modulates the anxiolytic effect of sub-chronically (7 days) applied KSMCT in the previously tested animal model by using elevated plus maze (EPM) test. We administered KSMCT (2.5 g/kg/day) alone by intragastric gavage and in combination with intraperitoneally (i.p.) injected of DPCPX in two doses (lower: 0.15 mg/kg, higher: 0.25 mg/kg). Control groups represented i.p saline and water gavage with or without i.p. DPCPX administration (2.5 g/kg/day). After treatments, the level of blood glucose and beta-hydroxybutyrate (βHB), as well as body weight were recorded. KSMCT alone significantly increased the time spent in the open arms and decreased the time spent in the closed arms, supporting our previous results. Injection of lower dose of DPCPX decreased, while higher dose of DPCPX abolished the effect of KSMCT administration on EPM. Blood βHB levels were significantly increased after administration of KSMCT, while DPCPX did not change the KSMCT induced increase in blood βHB levels. These results demonstrate that A 1 R inhibition modified (decreased) the anti-anxiety effect of KSMCT administration implying that the adenosinergic system, likely via A 1 Rs, may modulate the

  7. Anxiolytic Effect of Exogenous Ketone Supplementation Is Abolished by Adenosine A1 Receptor Inhibition in Wistar Albino Glaxo/Rijswijk Rats

    Directory of Open Access Journals (Sweden)

    Zsolt Kovács

    2018-02-01

    Full Text Available Anxiety disorders are one of the most common mental health problems worldwide, but the exact pathophysiology remains largely unknown. It has been demonstrated previously that administration of exogenous ketone supplement KSMCT (ketone salt/KS + medium chain triglyceride/MCT oil by intragastric gavage for 7 days decreased the anxiety level in genetically absence epileptic Wistar Albino Glaxo/Rijswijk (WAG/Rij rats. To investigate the potential role of the adenosinergic system in the pathomechanism of anxiety we tested whether the inhibition of adenosine A1 receptors (A1Rs influence the anxiolytic effect of the exogenous ketone supplement. As A1Rs may mediate such an effect, in the present study we used a specific A1R antagonist, DPCPX (1,3-dipropyl-8-cyclopentylxanthine to test whether it modulates the anxiolytic effect of sub-chronically (7 days applied KSMCT in the previously tested animal model by using elevated plus maze (EPM test. We administered KSMCT (2.5 g/kg/day alone by intragastric gavage and in combination with intraperitoneally (i.p. injected of DPCPX in two doses (lower: 0.15 mg/kg, higher: 0.25 mg/kg. Control groups represented i.p saline and water gavage with or without i.p. DPCPX administration (2.5 g/kg/day. After treatments, the level of blood glucose and beta-hydroxybutyrate (βHB, as well as body weight were recorded. KSMCT alone significantly increased the time spent in the open arms and decreased the time spent in the closed arms, supporting our previous results. Injection of lower dose of DPCPX decreased, while higher dose of DPCPX abolished the effect of KSMCT administration on EPM. Blood βHB levels were significantly increased after administration of KSMCT, while DPCPX did not change the KSMCT induced increase in blood βHB levels. These results demonstrate that A1R inhibition modified (decreased the anti-anxiety effect of KSMCT administration implying that the adenosinergic system, likely via A1Rs, may modulate the

  8. 40 CFR 63.61 - Deletion of methyl ethyl ketone from the list of hazardous air pollutants.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Deletion of methyl ethyl ketone from the list of hazardous air pollutants. 63.61 Section 63.61 Protection of Environment ENVIRONMENTAL... Designations, Source Category List § 63.61 Deletion of methyl ethyl ketone from the list of hazardous air...

  9. A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

    Directory of Open Access Journals (Sweden)

    Viviane P. de Souza

    2016-11-01

    Full Text Available Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

  10. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  11. OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

    Energy Technology Data Exchange (ETDEWEB)

    Byrn, Marianne; Calvin, Melvin

    1965-12-01

    Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

  12. Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects

    Directory of Open Access Journals (Sweden)

    Axel G. Griesbeck

    2014-05-01

    Full Text Available The homogeneous titanium- and dye-catalyzed as well as the heterogeneous semiconductor particle-catalyzed photohydroxymethylation of ketones by methanol were investigated in order to evaluate the most active photocatalyst system. Dialkoxytitanium dichlorides are the most efficient species for chemoselective hydroxymethylation of acetophenone as well as other aromatic and aliphatic ketones. Pinacol coupling is the dominant process for semiconductor catalysis and ketone reduction dominates the Ti(OiPr4/methanol or isopropanol systems. Application of dilution effects on the TiO2 catalysis leads to an increase in hydroxymethylation at the expense of the pinacol coupling.

  13. The catalystic asymmetric synthesis of optically active epoxy ketones

    NARCIS (Netherlands)

    Marsman, Bertha Gerda

    1981-01-01

    In this thesis the use of catalytic asymmetric synthesis to prepare optically active epoxy ketones is described. This means that the auxiliary chirality, necessary to obtain an optically active product, is added in a catalytic quantity . In principle this is a very efficient way to make opticlly

  14. Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyldiphenylsulfonium salts/copper system

    Directory of Open Access Journals (Sweden)

    Satoshi Okusu

    2013-10-01

    Full Text Available Regioselective conjugate 1,4-trifluoromethylation of α,β-unsaturated ketones by the use of shelf-stable electrophilic trifluoromethylating reagents, S-(trifluoromethyldiphenylsulfonium salts and copper under mild conditions is described. A wide range of acyclic aryl–aryl–enones and aryl–alkyl–enones were converted into β-trifluoromethylated ketones in low to moderate yields.

  15. Solvation effect on decomposition rate of 10-methyl-10-phenylphenoxarsonium iodide in some alcohols and ketones

    International Nuclear Information System (INIS)

    Gavrilov, V.I.; Gumerov, N.S.; Rakhmatullin, R.R.

    1989-01-01

    By the method of conductometry decomposition kinetics of 10-methyl-10phenylphenoxarsonium iodide in methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and methyl ethyl ketone at initial concentration of the salt 0.00024-0.003 mol/l, is studied. It is shown that at the temperatures up to 80-95 deg C practically no decomposition of arsonium salt in methanol and ethanol is observed. With an increase in the length of alcohol alkyl radical the decomposition rate increases. The values of activation enrgy both for alcohols and ketone are approximately the same. At the same time, decomposition rate in alcohol proved much slower than in ketone, which is related to iodide-ion solvation in protic solvents

  16. Solvation effect on decomposition rate of 10-methyl-10-phenylphenoxarsonium iodide in some alcohols and ketones

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilov, V I; Gumerov, N S; Rakhmatullin, R R [Kazanskij Khimiko-Tekhnologicheskij Inst., Kazan (USSR)

    1989-03-01

    By the method of conductometry decomposition kinetics of 10-methyl-10phenylphenoxarsonium iodide in methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and methyl ethyl ketone at initial concentration of the salt 0.00024-0.003 mol/l, is studied. It is shown that at the temperatures up to 80-95 deg C practically no decomposition of arsonium salt in methanol and ethanol is observed. With an increase in the length of alcohol alkyl radical the decomposition rate increases. The values of activation enrgy both for alcohols and ketone are approximately the same. At the same time, decomposition rate in alcohol proved much slower than in ketone, which is related to iodide-ion solvation in protic solvents.

  17. A potent trifluoromethyl ketone histone deacetylase inhibitor exhibits class-dependent mechanism of action

    DEFF Research Database (Denmark)

    Madsen, Andreas Stahl; Olsen, Christian Adam

    2016-01-01

    Histone deacetylase (HDAC) enzymes are validated targets for treatment of certain cancers and have potential as targets for pharmacological intervention in a number of other diseases. Thus, inhibitors of these enzymes have received considerable attention, but these are often evaluated by IC50 value......-on–fast-off mechanism was observed, but the trifluoromethyl ketone compound exhibited differential mechanisms depending on the enzyme isoform. The trifluoromethyl ketone compound displayed a fast-on–fast-off mechanism against class-IIa HDACs 4 and 7, but slow-binding mechanisms against class-I and class-IIb enzymes...

  18. Raspberry ketone in food supplements – High intake, few toxicity data – A cause for safety concern?

    DEFF Research Database (Denmark)

    Bredsdorff, Lea; Wedebye, Eva Bay; Nikolov, Nikolai Georgiev

    2015-01-01

    Raspberry ketone (4-(4-hydroxyphenyl)-2-butanone) is marketed on the Internet as a food supplement. The recommended intake is between 100 and 1400 mg per day. The substance is naturally occurring in raspberries (up to 4.3 mg/kg) and is used as a flavouring substance. Toxicological studies...... on raspberry ketone are limited to acute and subchronic studies in rats. When the lowest recommended daily dose of raspberry ketone (100 mg) as a food supplement is consumed, it is 56 times the established threshold of toxicological concern (TTC) of 1800 μg/day for Class 1 substances. The margin of safety (MOS......) based on a NOAEL of 280 mg/kg bw/day for lower weight gain in rats is 165 at 100 mg and 12 at 1400 mg. The recommended doses are a concern taking into account the TTC and MOS. Investigations of raspberry ketone in quantitative structure-activity relationship (QSAR) models indicated potential cardiotoxic...

  19. Rocha com espodumênio como fundente para massas cerâmicas tradicionais Spodumene rock as a flux for traditional ceramic bodies

    Directory of Open Access Journals (Sweden)

    S. R. Bragança

    2010-07-01

    Full Text Available Investigou-se a atuação de uma rocha com espodumênio como fundente em massas cerâmicas, analisando-se sua reatividade com outras matérias-primas, como quartzo e caulim. Primeiramente, caracterizou-se petrograficamente o pegmatito de onde se extrai esse fundente. Posteriormente avaliou-se o comportamento de moabilidade, fundência e deformação piroplástica da rocha com espodumênio. Analisou-se então sua influência nas propriedades tecnológicas finais das peças, principalmente em relação à temperatura de queima, às fases e à microestrutura. Comparou-se a gresificação com outros fundentes comerciais como a albita e o feldspato. O espodumênio mostrou maior capacidade de reduzir a temperatura de gresificação das peças que os fundentes tradicionais, promovendo a densificação por fluxo viscoso.A spodumene rock was used as a flux in ceramic bodies, analyzing its reactivity to other raw materials such as quartz and kaolin. The petrology properties of the pegmatite (parent rock from which the flux is extracted was characterized. The grindability, fluxing strength and pyroplastic deformation of the spodumene rock were investigated. The influence on technological properties of the final pieces, mainly in relation to the firing temperature, phases formation and microstructure were also further analyzed. The firing behavior to other commercial flux such as albite and feldspar were then compared. The spodumene rock was considered an effective flux, capable of reducing the firing temperatures of the tested bodies by viscous flow.

  20. Adenosine A1 Receptor Antagonism Abolished the Anti-seizure Effects of Exogenous Ketone Supplementation in Wistar Albino Glaxo Rijswijk Rats

    Directory of Open Access Journals (Sweden)

    Zsolt Kovács

    2017-07-01

    Full Text Available The state of therapeutic ketosis can be achieved by using the ketogenic diet (KD or exogenous ketone supplementation. It was suggested previously that the adenosinergic system may be involved in the mediating effect of KD on suppressing seizure activity in different types of epilepsies, likely by means of adenosine A1 receptors (A1Rs. Thus, we tested in the present study whether exogenous ketone supplements (ketone ester: KE, 2.5 g/kg/day; ketone salt/KS + medium chain triglyceride/MCT: KSMCT, 2.5 g/kg/day applied sub-chronically (for 7 days by intragastric gavage can modulate absence epileptic activity in genetically absence epileptic Wistar Albino Glaxo/Rijswijk (WAG/Rij rats. The number of spike-wave discharges (SWDs significantly and similarly decreased after both KE and KSMCT treatment between 3rd and 7th days of gavage. Moreover, blood beta-hydroxybutyrate (βHB levels were significantly increased alike after KE and KSMCT gavage, compared to control levels. The SWD number and βHB levels returned to the baseline levels on the first day without ketone supplementation. To determine whether A1Rs can modify ketone supplement-evoked changes in absence epileptic activity, we applied a non-pro-epileptic dose of a specific A1R antagonist DPCPX (1,3-dipropyl-8-cyclopentylxanthine (intraperitoneal/i.p. 0.2 mg/kg in combination with KSMCT (2.5 g/kg/day, gavage. As expected, DPCPX abolished the KSMCT-evoked decrease in SWD number. Thus, we concluded that application of exogenous ketone supplements may decrease absence epileptic activity in WAG/Rij rats. Moreover, our results suggest that among others the adenosinergic system, likely via A1Rs, may modulate the exogenous ketone supplements-evoked anti-seizure effects.

  1. Atmospheric mixing ratios of methyl ethyl ketone (2-butanone in tropical, boreal, temperate and marine environments

    Directory of Open Access Journals (Sweden)

    A. M. Yáñez-Serrano

    2016-09-01

    Full Text Available Methyl ethyl ketone (MEK enters the atmosphere following direct emission from vegetation and anthropogenic activities, as well as being produced by the gas-phase oxidation of volatile organic compounds (VOCs such as n-butane. This study presents the first overview of ambient MEK measurements at six different locations, characteristic of forested, urban and marine environments. In order to understand better the occurrence and behaviour of MEK in the atmosphere, we analyse diel cycles of MEK mixing ratios, vertical profiles, ecosystem flux data, and HYSPLIT back trajectories, and compare with co-measured VOCs. MEK measurements were primarily conducted with proton-transfer-reaction mass spectrometer (PTR-MS instruments. Results from the sites under biogenic influence demonstrate that vegetation is an important source of MEK. The diel cycle of MEK follows that of ambient temperature and the forest structure plays an important role in air mixing. At such sites, a high correlation of MEK with acetone was observed (e.g. r2 = 0.96 for the SMEAR Estonia site in a remote hemiboreal forest in Tartumaa, Estonia, and r2 = 0.89 at the ATTO pristine tropical rainforest site in central Amazonia. Under polluted conditions, we observed strongly enhanced MEK mixing ratios. Overall, the MEK mixing ratios and flux data presented here indicate that both biogenic and anthropogenic sources contribute to its occurrence in the global atmosphere.

  2. Fumigant toxicity of five essential oils rich in ketones against Sitophilus zeamais (Motschulsky

    Directory of Open Access Journals (Sweden)

    J.M Herrera

    2014-06-01

    Full Text Available Essential oils (EOs and individual compounds act as fumigants against insects found in stored products. In fumigant assays, Sitophilus zeamais Motschulsky adults were treated with essential oils derived from Aphyllocladus decussatus Hieron, Aloysia polystachya Griseb, Minthostachys verticillata Griseb Epling and Tagetes minuta L , which are rich in ketones and their major components: a- thujone, R-carvone, S-carvone, (- menthone, R (+ pulegone and E-Z- ocimenone. M. verticillata oil was the most toxic ( LC50: 116.6 µl /L air characterized by a high percentage of menthone (40.1% and pulegone (43.7%. All ketones showed insecticidal activity against S. zeamais. However, pulegone (LC50: 11.8 µl/L air, R- carvone (LC50: 17.5 µl/L air, S-carvone (LC50: 28.1 µl/L air and E-Z-ocimenone (LC50: 42.3 µl/L air were the most toxic. These ketones are a,b-unsaturated carbonyl. This feature could play a fundamental role in the increase of insecticidal activity against S. zeamais.

  3. A rational approach to predict and modulate stereolability of chiral alpha substituted ketones.

    Science.gov (United States)

    Cirilli, Roberto; Costi, Roberta; Di Santo, Roberto; Gasparrini, Francesco; La Torre, Francesco; Pierini, Marco; Siani, Gabriella

    2009-01-01

    An effective strategy to assess and modulate the stereolability of chiral alpha substituted ketones (C alpha SKs) is presented. The tendency of C alpha SKs to retain or change their configuration in water is analyzed as a function of thermodynamic proton-release attitude of alpha asymmetric atoms inside the structures by linear Brønsted correlations. A molecular modeling procedure was developed to analyze and suggest chemical modifications of C alpha SKs in view to obtain the desired grade of stereochemical stability. The approach was employed to predict the tendency to enantiomerize in water of two ketones (1 and 2) endowed with inhibitory activity against monoamine oxidases (MAOs) and the results were confirmed by experimental kinetics measurements performed in organic medium. As a demonstration of practical potentialities of the approach, four new structures, conceived as simple chemical modifications of 1 and 2, were designed to improve/reduce the stereostability grade of the starting anti-MAO ketones. The possibility to extend easily the procedure to other classes of C-H acids appears of interest.

  4. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

    A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.

  5. Efficient Baeyer-Villiger electro-oxidation of ketones with molecular ...

    African Journals Online (AJOL)

    A new and efficient method for the synthesis of lactones and esters involving the application of an molecular oxygen-based electro-catalytic oxidation system and ionic liquid [bmim][OTf] as electrolyte has been developed. The reaction between various ketones with molecular oxygen proceeds in a three-electrode cell under ...

  6. The incorporation of [1-14C] acetate into the methyl ketones that occur in steam-distillates of bovine milk fat.

    Science.gov (United States)

    Lawrence, R C; Hawke, J C

    1966-01-01

    1. The (14)C-labelling of the fatty acids and the methyl ketones in steam-distillates of milk fat from a lactating cow that had been injected intravenously with [1-(14)C]acetate was determined. 2. The labelling patterns of the C(6)-C(16) fatty acids and the corresponding methyl ketones with one fewer carbon atoms were similar, particularly so for the C(5)-C(10) compounds at 9 and 22hr. after the injection of [1-(14)C]acetate. The isolation of (14)C-labelled methyl ketones in the range C(3)-C(15) is evidence that the beta-oxo acid precursors, which are glyceride-bound in the milk fat, are synthesized in the mammary gland from acetate. The absence of heptadecan-2-one in steam-distillates and the extremely low specific radioactivity of stearic acid are further evidence for this biosynthetic pathway. 3. The specific radioactivities of the C(5)-C(15) methyl ketones were higher (with the exception of C(9) methyl ketone in the second milking) than the specific activities of the corresponding fatty acids with one more carbon atom. This is consistent with the methyl ketone precursors' being formed during the biosynthesis of fatty acids rather than being products of beta-oxidation of fatty acids.

  7. N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

    KAUST Repository

    Du, Guang-Fen; Wang, Ying; Xing, Fen; Xue, Mei; Guo, Xu-Hong; Huang, Kuo-Wei; Dai, Bin

    2015-01-01

    © Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.

  8. Ketone bodies metabolism during ischemic and reperfusion brain injuries following bilateral occlusion of common carotid arteries in rats Metabolismo dos corpos cetônicos durante as lesões de isquemia e reperfusão cerebrais após oclusão bilateral das artérias carótidas comuns em ratos

    Directory of Open Access Journals (Sweden)

    Mário Henrique Girão Faria

    2007-04-01

    Full Text Available PURPOSE: To evaluate the in vivo alterations on ketone bodies metabolism after cerebral ischemia/reperfusion through an experimental model of brain ischemia induced by simple occlusion of common carotid arteries (CCAs in Wistar rats. METHODS: Forty-eight male Wistar rats were randomly distributed on two groups (S - Sham; T - Test and further redistributed into four times sets of study. After bilateral occlusion of CCAs for 30min, the animals of group T were allowed reperfusion for 0, 5, 10 and 15min. Samples of cerebral tissue and systemic arterial blood were collected and the metabolites acetoacetate (ACT and beta-hydroxybutyrate (BHB were determined. RESULTS: Cerebral ACT and BHB levels increased significantly in Group T after 30min of carotid occlusion (time 0. The highest brain ketone bodies (ACT+BHB concentration was verified at 5min of reperfusion, decreasing after 10min of recirculation. Systemic ketone bodies levels increased similarly between test and sham groups. Group S demonstrated a significant increase in cerebral and systemic ACT and BHB concentrations mainly after 40-45min of study. CONCLUSIONS: The partial transient acute global brain ischemia induced by the bilateral carotid occlusion in Wistar rats triggered ketogenesis probably due to a central stimulation of catecholamine secretion. There was an increased cerebral uptake of ketone bodies following brain ischemia, reaffirming these metabolites as alternative energy substrates under conditions of cerebral metabolic stress as well as its potential role on neuroprotection. The greatest changes in ketone bodies metabolism were verified at initial minutes of recirculation as a result of the reperfusion injury phenomenon.OBJETIVO: Avaliar as alterações in vivo no metabolismo dos corpos cetônicos após isquemia/reperfusão cerebral através de um modelo experimental de isquemia cerebral induzido pela simples oclusão das artérias carótidas comuns (CCAs em ratos Wistar. M

  9. Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries

    Science.gov (United States)

    Chen, Liyun; Zhang, Shouhai; Chen, Yuning; Jian, Xigao

    2017-07-01

    A series of novel sulfonated poly(phthalazinone ether ketone)s containing pendant phenyl moieties (SPPEK-Ps) are synthesized and thoroughly characterized. The chemical structures of the polymers are confirmed by 1H NMR and FTIR analysis. The physicochemical properties and single cell performance of SPPEK-P membranes are systematically evaluated, revealing that the membranes are thermally, chemically and mechanically stable. The area resistances of SPPEK-P-90 and SPPEK-P-100 are 0.75 Ω cm2 and 0.34 Ω cm2, respectively. SPPEK-P membranes are impermeable to the bulky hydrated VO2+ ion and exhibited low V3+ ion permeability (SPPEK-P-90, 2.53 × 10-5 cm min-1) (Nafion 115 membrane: 9.0 × 10-4 cm min-1). Tests of SPPEK-P-90 in vanadium redox flow batteries (VRFBs) demonstrate a comparable columbic efficiency (CE) and energy efficiency (EE) to that of Nafion 115, where the CE is 98% and the EE is 83% at 60 mA cm-2. Moreover, the SPPEK-P-90 membrane exhibits stable performance in cell over 100 charge-discharge cycles (∼450 h).

  10. Iodine-Promoted Deoxygenative Iodization/Olefination/Sulfenylation of Ketones with Sulfonyl Hydrazides: Access to β-Iodoalkenyl Sulfides.

    Science.gov (United States)

    Bao, Yishu; Yang, Xiuqin; Zhou, Qingfa; Yang, Fulai

    2018-04-06

    A highly regio- and stereoselective synthesis of β-haloalkenyl sulfides using commercially available ketones and sulfonyl hydrazides as starting materials has been developed. This protocol obviates the need for alkynes and traditional sulfenylating agents and therefore opens up a new door to construct β-iodoalkenyl sulfides in a highly simple manner. This study reveals that ketones could be used as vinyl iodide precursors in organic synthesis.

  11. Investigation of Body Force Effects on Flow Boiling Critical Heat Flux

    Science.gov (United States)

    Zhang, Hui; Mudawar, Issam; Hasan, Mohammad M.

    2002-01-01

    The bubble coalescence and interfacial instabilities that are important to modeling critical heat flux (CHF) in reduced-gravity systems can be sensitive to even minute body forces. Understanding these complex phenomena is vital to the design and safe implementation of two-phase thermal management loops proposed for space and planetary-based thermal systems. While reduced gravity conditions cannot be accurately simulated in 1g ground-based experiments, such experiments can help isolate the effects of the various forces (body force, surface tension force and inertia) which influence flow boiling CHF. In this project, the effects of the component of body force perpendicular to a heated wall were examined by conducting 1g flow boiling experiments at different orientations. FC-72 liquid was boiled along one wall of a transparent rectangular flow channel that permitted photographic study of the vapor-liquid interface at conditions approaching CHF. High-speed video imaging was employed to capture dominant CHF mechanisms. Six different CHF regimes were identified: Wavy Vapor Layer, Pool Boiling, Stratification, Vapor Counterflow, Vapor Stagnation, and Separated Concurrent Vapor Flow. CHF showed great sensitivity to orientation for flow velocities below 0.2 m/s, where very small CHF values where measured, especially with downflow and downward-facing heated wall orientations. High flow velocities dampened the effects of orientation considerably. Figure I shows representative images for the different CHF regimes. The Wavy Vapor Layer regime was dominant for all high velocities and most orientations, while all other regimes were encountered at low velocities, in the downflow and/or downward-facing heated wall orientations. The Interfacial Lift-off model was modified to predict the effects of orientation on CHF for the dominant Wavy Vapor Layer regime. The photographic study captured a fairly continuous wavy vapor layer travelling along the heated wall while permitting liquid

  12. Catecholamine, Corticosteroid and Ketone Excretion in Exercise and Hypoxia,

    Science.gov (United States)

    OHCS excretion tended to be higher during the experimental period and subsequently lower overnight during the hypoxia week. Ketosis occurred in two...subjects. In one of these it could be readily related to previous extraneous stress. Excretion of unidentified ketones in overnight urines was sometimes suspected and occurred beyond doubt following gross ketosis . (Author)

  13. Reaction rate constants of H-abstraction by OH from large ketones: measurements and site-specific rate rules.

    Science.gov (United States)

    Badra, Jihad; Elwardany, Ahmed E; Farooq, Aamir

    2014-06-28

    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (C=O) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (C=O), and the prime is used to differentiate different neighboring environments of a methylene group):

  14. Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations.

    Science.gov (United States)

    Mehta, Meera; Holthausen, Michael H; Mallov, Ian; Pérez, Manuel; Qu, Zheng-Wang; Grimme, Stefan; Stephan, Douglas W

    2015-07-06

    Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Taming Radical Pairs in Nanocrystalline Ketones: Photochemical Syn-thesis of Compounds with Vicinal Stereogenic All-Carbon Quaternary Centers.

    Science.gov (United States)

    Dotson, Jordan J; Perez-Estrada, Salvador; Garcia-Garibay, Miguel A

    2018-05-29

    Here we describe the use of crystalline ketones to control the fate of the radical pair intermediates generated in the Norrish type I photodecarbonylation reaction to render it a powerful tool in the challenging synthesis of sterically congested carbon-carbon bonds. This methodology makes the synthetically more accessible hexasusbtituted ketones as ideal synthons for the construction of adjacent, all-carbon substituted, stereogenic quaternary stereocenters. We describe here the structural and thermochemical parameters required of the starting ketone in order to react in the solid state. Finally, the scope and scalability of the reaction and its application in the total synthesis of two natural products is described.

  16. Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    C. Spirig

    2005-01-01

    Full Text Available Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK and methacrolein (MACR were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.

  17. Synthetic Applications and Mechanistic Studies of the Hydroxide-Mediated Cleavage of Carbon-Carbon Bonds in Ketones

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Makarov, Ilya S.; Fristrup, Peter

    2017-01-01

    The hydroxide-mediated cleavage of ketones into alkanes and carboxylic acids has been reinvestigated and the substrate scope extended to benzyl carbonyl compounds. The transformation is performed with a 0.05 M ketone solution in refluxing xylene in the presence of 10 equiv of potassium hydroxide....... The reaction constitutes a straightforward protocol for the synthesis of certain phenyl-substituted carboxylic acids from 2-phenylcycloalkanones. The mechanism was investigated by kinetic experiments which indicated a first order reaction in hydroxide and a full negative charge in the rate-determining step....... The studies were complemented by a theoretical investigation where two possible pathways were characterized by DFT/M06-2X. The calculations showed that the scission takes place by nucleophilic attack of hydroxide on the ketone followed by fragmentation of the resulting oxyanion into the carboxylic acid...

  18. Synthetic Applications and Mechanistic Studies of the Hydroxide-Mediated Cleavage of Carbon-Carbon Bonds in Ketones.

    Science.gov (United States)

    Mazziotta, Andrea; Makarov, Ilya S; Fristrup, Peter; Madsen, Robert

    2017-06-02

    The hydroxide-mediated cleavage of ketones into alkanes and carboxylic acids has been reinvestigated and the substrate scope extended to benzyl carbonyl compounds. The transformation is performed with a 0.05 M ketone solution in refluxing xylene in the presence of 10 equiv of potassium hydroxide. The reaction constitutes a straightforward protocol for the synthesis of certain phenyl-substituted carboxylic acids from 2-phenylcycloalkanones. The mechanism was investigated by kinetic experiments which indicated a first order reaction in hydroxide and a full negative charge in the rate-determining step. The studies were complemented by a theoretical investigation where two possible pathways were characterized by DFT/M06-2X. The calculations showed that the scission takes place by nucleophilic attack of hydroxide on the ketone followed by fragmentation of the resulting oxyanion into the carboxylic acid and a benzyl anion.

  19. Novel deep cavity calix[4]pyrroles derived from steroidal ketones

    Czech Academy of Sciences Publication Activity Database

    Dukh, Mykhaylo; Drašar, Pavel; Černý, Ivan; Pouzar, Vladimír; Shriver, J. A.; Král, V.; Sessler, J. L.

    2002-01-01

    Roč. 14, 2-3 (2002), s. 237-244 ISSN 1061-0278 R&D Projects: GA MŠk OC D12.20 Grant - others:NIH(US) GM58907 Institutional research plan: CEZ:AV0Z4055905 Keywords : ketones * steroid Subject RIV: CC - Organic Chemistry Impact factor: 1.820, year: 2002

  20. Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries

    DEFF Research Database (Denmark)

    Nicolaou, K C; Montagnon, T; Ulven, T

    2002-01-01

    New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacemen...

  1. Cs2CO3-Initiated Trifluoro-Methylation of Chalcones and Ketones for Practical Synthesis of Trifluoromethylated Tertiary Silyl Ethers

    Directory of Open Access Journals (Sweden)

    Cheng Dong

    2017-05-01

    Full Text Available It was found that 1,2-trifluoromethylation reactions of ketones, enones, and aldehydes were easily accomplished using the Prakash reagent in the presence of catalytic amounts of cesium carbonate, which represents an experimentally convenient, atom-economic process for this anionic trifluoromethylation of non-enolisable aldehydes and ketones.

  2. Arene activation by a nonheme iron(III)-hydroperoxo complex: pathways leading to phenol and ketone products.

    Science.gov (United States)

    Faponle, Abayomi S; Banse, Frédéric; de Visser, Sam P

    2016-07-01

    Iron(III)-hydroperoxo complexes are found in various nonheme iron enzymes as catalytic cycle intermediates; however, little is known on their catalytic properties. The recent work of Banse and co-workers on a biomimetic nonheme iron(III)-hydroperoxo complex provided evidence of its involvement in reactivity with arenes. This contrasts the behavior of heme iron(III)-hydroperoxo complexes that are known to be sluggish oxidants. To gain insight into the reaction mechanism of the biomimetic iron(III)-hydroperoxo complex with arenes, we performed a computational (density functional theory) study. The calculations show that iron(III)-hydroperoxo reacts with substrates via low free energies of activation that should be accessible at room temperature. Moreover, a dominant ketone reaction product is observed as primary products rather than the thermodynamically more stable phenols. These product distributions are analyzed and the calculations show that charge interaction between the iron(III)-hydroxo group and the substrate in the intermediate state pushes the transferring proton to the meta-carbon atom of the substrate and guides the selectivity of ketone formation. These studies show that the relative ratio of ketone versus phenol as primary products can be affected by external interactions of the oxidant with the substrate. Moreover, iron(III)-hydroperoxo complexes are shown to selectively give ketone products, whereas iron(IV)-oxo complexes will react with arenes to form phenols instead.

  3. Use of ketonal in lumbago

    Directory of Open Access Journals (Sweden)

    P. R. Kamchatnov

    2014-01-01

    Full Text Available Lumbago is one of the most common musculoskeletal pain syndromes. The course of lumbago shows a tendency towards frequent relapses and is associated with the significant material costs of medical care. A wide range of analgesics, nonsteroidal anti-inflammatory drugs in particular, whose administration may be linked with an increased risk for adverse visceral reactions, is used to treat patient with lumbago. The risk of their side effects may be reduced by the extensive use of non-drug treatments and the early expansion of a motor regimen in a patient. Therapeutic effectiveness in reducing the likelihood of adverse reactions may be provided by short-term treatment with effective drugs. The advantages of using ketoprofen (ketonal formulations in patients with lumbago are considered.

  4. Analysis of Ketones by Selected Ion Flow Tube Mass Spectrometry

    Czech Academy of Sciences Publication Activity Database

    Smith, D.; Wang, T.; Španěl, Patrik

    2003-01-01

    Roč. 17, - (2003), s. 2655-2660 ISSN 0951-4198 R&D Projects: GA ČR GA202/03/0827; GA ČR GA203/02/0737 Institutional research plan: CEZ:AV0Z4040901 Keywords : mass spectrometry * selected ion flow tube * ketones Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.789, year: 2003

  5. Elimination of ketone vapors by adsorption on spherical MCM-41 and MCM-48 silicas decorated with thermally activated poly(furfuryl alcohol)

    Energy Technology Data Exchange (ETDEWEB)

    Machowski, Kamil [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Kuśtrowski, Piotr, E-mail: kustrows@chemia.uj.edu.pl [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Dudek, Barbara [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Michalik, Marek [Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, 30-063 Kraków (Poland)

    2015-09-01

    Spherical MCM-41 and MCM-48 silicas with different arrangements of mesopores were synthesized in a water–alcohol solution of surfactant by the hard-templating method. The pore structure and morphology of the obtained materials were confirmed by powder X-ray diffraction (XRD), low-temperature adsorption of nitrogen and scanning electron microscopy (SEM). The surface of mesoporous silicas was decorated with small amounts of poly(furfuryl alcohol) (PFA), which was introduced by the precipitation polymerization and subsequently thermally activated at 523 K to form stable C=O surface species detected by FTIR spectroscopy. The adsorption capacity of the PFA/silica composites in the elimination of various ketone (acetone, methyl-ethyl ketone and methyl-isobutyl ketone) vapors was compared to the effectiveness of pristine silicas. It was found that the modification of silicas by thermally degraded PFA enhanced their adsorption capacity. This effect was attributed to the appearance of another type of surface centers (namely carbonyl groups), which beside silanols interact with ketone molecules via hydrogen bonds. DRIFT spectra showed that a ketone molecule is bonded on silanol species in its keto form, whereas on carbonyl functionalities in enol one. - Highlights: • Surface of spherical MCM-type silicas was decorated with poly(furfuryl alcohol). • Thermal degradation of deposited polymer resulted in formation of C=O species. • Carbonyl groups enhanced adsorption capacity of MCM-41 and MCM-48 silicas. • Adsorption of ketones in enol or keto forms was revealed by DRIFT measurements.

  6. Elimination of ketone vapors by adsorption on spherical MCM-41 and MCM-48 silicas decorated with thermally activated poly(furfuryl alcohol)

    International Nuclear Information System (INIS)

    Machowski, Kamil; Kuśtrowski, Piotr; Dudek, Barbara; Michalik, Marek

    2015-01-01

    Spherical MCM-41 and MCM-48 silicas with different arrangements of mesopores were synthesized in a water–alcohol solution of surfactant by the hard-templating method. The pore structure and morphology of the obtained materials were confirmed by powder X-ray diffraction (XRD), low-temperature adsorption of nitrogen and scanning electron microscopy (SEM). The surface of mesoporous silicas was decorated with small amounts of poly(furfuryl alcohol) (PFA), which was introduced by the precipitation polymerization and subsequently thermally activated at 523 K to form stable C=O surface species detected by FTIR spectroscopy. The adsorption capacity of the PFA/silica composites in the elimination of various ketone (acetone, methyl-ethyl ketone and methyl-isobutyl ketone) vapors was compared to the effectiveness of pristine silicas. It was found that the modification of silicas by thermally degraded PFA enhanced their adsorption capacity. This effect was attributed to the appearance of another type of surface centers (namely carbonyl groups), which beside silanols interact with ketone molecules via hydrogen bonds. DRIFT spectra showed that a ketone molecule is bonded on silanol species in its keto form, whereas on carbonyl functionalities in enol one. - Highlights: • Surface of spherical MCM-type silicas was decorated with poly(furfuryl alcohol). • Thermal degradation of deposited polymer resulted in formation of C=O species. • Carbonyl groups enhanced adsorption capacity of MCM-41 and MCM-48 silicas. • Adsorption of ketones in enol or keto forms was revealed by DRIFT measurements.

  7. Treatment of two different water resources in desalination and microbial fuel cell processes by poly sulfone/Sulfonated poly ether ether ketone hybrid membrane

    International Nuclear Information System (INIS)

    Ghasemi, Mostafa; Wan Daud, Wan Ramli; Alam, Javed; Ilbeygi, Hamid; Sedighi, Mehdi; Ismail, Ahmad Fauzi; Yazdi, Mohammad H.; Aljlil, Saad A.

    2016-01-01

    The PS (Polysulfone)/SPEEK (sulfonated poly ether ether ketone) hybrid membranes were fabricated and modified with low and high DS (degrees of sulfonation) for the desalination of brackish water and proton exchange membrane in microbial fuel cell. The results illustrated that SPEEK has changed the morphology of membranes and increase their hydrophilicity. PS/SPEEK with lower DS (29%) had the rejection percentage of 62% for NaCl and 68% for MgSO_4; while it was 67% and 81% for PS/SPEEK (76%) at 4 bars. Furthermore, the water flux for PS at 10 bar was 12.41 L m"−"2 h"−"1. It was four times higher for PS/SPEEK (29%) which means 49.5 L m"−"2 h"−"1 and 13 times higher for PS/SPEEK (76%) with means 157.76 L m"−"2 h"−"1. However, in MFC (microbial fuel cell), the highest power production was 97.47 mW/m"2 by PS/SPEEK (29%) followed by 41.42 mW/m"2 for PS/SPEEK (76%), and 9.4 mW/m"2 for PS. This revealed that the sulfonation of PEEK (poly ether ether ketone) made it a better additive for PS for desalination, because it created a membrane with higher hydrophilicity, better pore size and better for salt rejection. Although for the separator, the degree of sulfonation was limited; otherwise it made a membrane to transfer some of the unwanted ions. - Highlights: • Fabrication of a composite membrane for desalination and MFC. • PS/SPEEK (76%) had the lowest contact angle (48.8) and highest hydrophilicity than PS and PS/SPEEK (29%). • PS/SPEEK (29%) was the best separator for use in MFC. • PS/SPEEK (76%) had the highest flux (61.3 L m"−"2 h"−"1) for desalination.

  8. Activation of Acetone and Other Simple Ketones in Anaerobic Bacteria.

    Science.gov (United States)

    Heider, Johann; Schühle, Karola; Frey, Jasmin; Schink, Bernhard

    2016-01-01

    Acetone and other ketones are activated for subsequent degradation through carboxylation by many nitrate-reducing, phototrophic, and obligately aerobic bacteria. Acetone carboxylation leads to acetoacetate, which is subsequently activated to a thioester and degraded via thiolysis. Two different types of acetone carboxylases have been described, which require either 2 or 4 ATP equivalents as an energy supply for the carboxylation reaction. Both enzymes appear to combine acetone enolphosphate with carbonic phosphate to form acetoacetate. A similar but more complex enzyme is known to carboxylate the aromatic ketone acetophenone, a metabolic intermediate in anaerobic ethylbenzene metabolism in denitrifying bacteria, with simultaneous hydrolysis of 2 ATP to 2 ADP. Obligately anaerobic sulfate-reducing bacteria activate acetone to a four-carbon compound as well, but via a different process than bicarbonate- or CO2-dependent carboxylation. The present evidence indicates that either carbon monoxide or a formyl residue is used as a cosubstrate, and that the overall ATP expenditure of this pathway is substantially lower than in the known acetone carboxylase reactions. © 2016 S. Karger AG, Basel.

  9. Thermality of the Hawking flux

    Energy Technology Data Exchange (ETDEWEB)

    Visser, Matt [School of Mathematics, Statistics, and Operations Research,Victoria University of Wellington, PO Box 600, Wellington 6140 (New Zealand)

    2015-07-03

    Is the Hawking flux “thermal”? Unfortunately, the answer to this seemingly innocent question depends on a number of often unstated, but quite crucial, technical assumptions built into modern (mis-)interpretations of the word “thermal”. The original 1850’s notions of thermality — based on classical thermodynamic reasoning applied to idealized “black bodies” or “lamp black surfaces” — when supplemented by specific basic quantum ideas from the early 1900’s, immediately led to the notion of the black-body spectrum, (the Planck-shaped spectrum), but without any specific assumptions or conclusions regarding correlations between the quanta. Many (not all) modern authors (often implicitly and unintentionally) add an extra, quite unnecessary, assumption that there are no correlations in the black-body radiation; but such usage is profoundly ahistorical and dangerously misleading. Specifically, the Hawking flux from an evaporating black hole, (just like the radiation flux from a leaky furnace or a burning lump of coal), is only approximately Planck-shaped over an explicitly bounded range of frequencies. Standard physics (phase space and adiabaticity effects) explicitly bound the frequency range over which the Hawking flux is approximately Planck-shaped from both above and below — the Hawking flux is certainly not exactly Planckian, and there is no compelling physics reason to assume the Hawking photons are uncorrelated.

  10. Thermality of the Hawking flux

    International Nuclear Information System (INIS)

    Visser, Matt

    2015-01-01

    Is the Hawking flux “thermal”? Unfortunately, the answer to this seemingly innocent question depends on a number of often unstated, but quite crucial, technical assumptions built into modern (mis-)interpretations of the word “thermal”. The original 1850’s notions of thermality — based on classical thermodynamic reasoning applied to idealized “black bodies” or “lamp black surfaces” — when supplemented by specific basic quantum ideas from the early 1900’s, immediately led to the notion of the black-body spectrum, (the Planck-shaped spectrum), but without any specific assumptions or conclusions regarding correlations between the quanta. Many (not all) modern authors (often implicitly and unintentionally) add an extra, quite unnecessary, assumption that there are no correlations in the black-body radiation; but such usage is profoundly ahistorical and dangerously misleading. Specifically, the Hawking flux from an evaporating black hole, (just like the radiation flux from a leaky furnace or a burning lump of coal), is only approximately Planck-shaped over an explicitly bounded range of frequencies. Standard physics (phase space and adiabaticity effects) explicitly bound the frequency range over which the Hawking flux is approximately Planck-shaped from both above and below — the Hawking flux is certainly not exactly Planckian, and there is no compelling physics reason to assume the Hawking photons are uncorrelated.

  11. Comprehensive in Vitro Analysis of Acyltransferase Domain Exchanges in Modular Polyketide Synthases and Its Application for Short-Chain Ketone Production

    DEFF Research Database (Denmark)

    Yuzawa, Satoshi; Deng, Kai; Wang, George

    2017-01-01

    AT domain replacements in most type I PKS modules. To further demonstrate the utility of the optimized AT domain boundary, we have constructed hybrid PKSs to produce industrially important short-chain ketones. Our in vitro and in vivo analysis demonstrated production of predicted ketones without significant...

  12. Poor adherence to ketone testing in patients with Type 1 Diabetes

    Science.gov (United States)

    Diabetic ketoacidosis (DKA) is an acute, still common, and preventable complication of type 1 diabetes (T1D) associated with increased health care costs, morbidity, and mortality. Clinical recommendations advise self-monitoring of ketones in people with T1D during hyperglycemia and illness to allow ...

  13. Reduction of , -Unsaturated Ketones Using a Zn/NiCl System in ...

    African Journals Online (AJOL)

    NJD

    Reduction of , -Unsaturated Ketones Using a Zn/NiCl. 2. System in Aqueous Media in the Presence of Anionic and. Cationic Surfactants. Hocine Ilikti*, Tayeb Benabdallah, Kamel Bentayeb, Adil A. Othman and Zoubir Derriche. Organic Chemistry and Electrochemistry Laboratory, Department of Chemistry, Faculty of Science, ...

  14. The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins.

    Science.gov (United States)

    Miles-Barrett, Daniel M; Neal, Andrew R; Hand, Calum; Montgomery, James R D; Panovic, Isabella; Ojo, O Stephen; Lancefield, Christopher S; Cordes, David B; Slawin, Alexandra M Z; Lebl, Tomas; Westwood, Nicholas J

    2016-10-25

    Understanding the structure of technical lignins resulting from acid-catalysed treatment of lignocellulosic biomass is important for their future applications. Here we report an investigation into the fate of lignin under acidic aqueous organosolv conditions. In particular we examine in detail the formation and reactivity of non-native Hibbert ketone structures found in isolated organosolv lignins from both Douglas fir and beech woods. Through the use of model compounds combined with HSQC, HMBC and HSQC-TOCSY NMR experiments we demonstrate that, depending on the lignin source, both S and G lignin-bound Hibbert ketone units can be present. We also show that these units can serve as a source of novel mono-aromatic compounds following an additional lignin depolymerisation reaction.

  15. Thermodynamic properties of donor-acceptor complexes of tertiary amine with aryl ketones in hexane medium

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, R. [Department of Physics, The New College, Chennai 600 014 (India); Jayakumar, S. [Department of Physics, R.K.M. Vivekananda College, Chennai 600 004 (India); Kannappan, V., E-mail: vkannappan@hotmail.com [Department of Chemistry, Presidency College, Chennai 600 005 (India)

    2012-05-20

    Highlights: Black-Right-Pointing-Pointer Ultrasonic scan is carried out on ternary systems of aromatic tertiary amine and three aryl ketones. Black-Right-Pointing-Pointer Formation of CT complexes is found between tertiary amine with aryl ketones. Black-Right-Pointing-Pointer Stability constant values are computed by ultrasonic and spectral methods are compared. Black-Right-Pointing-Pointer The trend in the 'K' suggests that substituents in ketones influence the stabilities of these complexes. Black-Right-Pointing-Pointer The thermodynamic parameters suggest CT interaction is exothermic and the complexes are thermodynamically stable. - The thermodynamic stability of complexes formed between N,N-dimethylaniline (DMANI) and three ketones, namely, acetophenone (ACP), 4-chloroactophenone (ClACP) and 4-methylacetophenone (MACP) in n-hexane is extensively investigated by spectral and ultrasonic methods. The ultrasound scan was carried out in the temperature range 208.15-313.15 K and at atmospheric pressure on solutions containing equimolar concentrations of components ranging from 0.025 to 0.2 M. The existence of solute-solute interactions has also been confirmed through electronic absorption spectra analyzed with Benesi-Hildebrand theory at 303.15 K. The stability constants of the donor-acceptor complexes determined both by spectroscopic and ultrasonic methods are comparable and follow similar trends. The trend in the formation constants is discussed with structures of the components. The thermodynamic behavior of the systems was explained through the computed values of the free energy ({Delta}G), enthalpy ({Delta}H) and entropy ({Delta}S) changes for complex formation are computed and discussed.

  16. Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,β-dehydrogenation of β-heteroatom-substituted ketones.

    Science.gov (United States)

    Yoshii, Daichi; Jin, Xiongjie; Yatabe, Takafumi; Hasegawa, Jun-Ya; Yamaguchi, Kazuya; Mizuno, Noritaka

    2016-12-06

    In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of β-heteroatom-substituted α,β-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,β-dehydrogenation of the corresponding saturated ketones using O 2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.

  17. Microbial transformation of sesquitepenoid ketone, (+) Nootkatone by Macrophomia phaseolina

    OpenAIRE

    Vajira P. Bulugahapitiya; Syed Ghulam Musharaff

    2009-01-01

    Microbial transformation is an effective tool for the structural modification of bioactive natural and synthetic compounds leading to synthesis of more potent derivatives. Its application in asymmetric synthesis is increasing due to its versatility and ease. This article presents biotransformation of sesquiterpenoid ketone, (+)-Nootkatone (1) by M. phaseolina, a plant pathogenic fungus. The transformation afforded four main compounds. They were determined to be 1:6 stereoisomeric mixture of 1...

  18. Robust and efficient, yet uncatalysed synthesis of trialkylsilyl-protected cyanohydrins from ketones

    Czech Academy of Sciences Publication Activity Database

    Cabirol, F. L.; Lim, A. E. C.; Hanefeld, U.; Sheldon, R. A.; Lyapkalo, Ilya

    2008-01-01

    Roč. 73, č. 6 (2008), s. 2446-2449 ISSN 0022-3263 Institutional research plan: CEZ:AV0Z40550506 Keywords : ketones * cyanosilylation * silyl protection * anionic reactivity * dimethylsulfoxide Subject RIV: CC - Organic Chemistry Impact factor: 3.952, year: 2008

  19. Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

    Science.gov (United States)

    Chen, Wenyong; Chen, Ming; Hartwig, John F

    2014-11-12

    We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

  20. Composition of secondary alcohols, ketones, alkanediols, and ketols in Arabidopsis thaliana cuticular waxes

    Science.gov (United States)

    Wen, Miao; Jetter, Reinhard

    2009-01-01

    Arabidopsis wax components containing secondary functional groups were examined (i) to test the biosynthetic relationship between secondary alcohols and ketols and (ii) to determine the regiospecificity and substrate preference of the enzyme involved in ketol biosynthesis. The stem wax of Arabidopsis wild type contained homologous series of C27 to C31 secondary alcohols (2.4 μg cm−2) and C28 to C30 ketones (6.0 μg cm−2) dominated by C29 homologues. In addition, compound classes containing two secondary functional groups were identified as C29 diols (∼0.05 μg cm−2) and ketols (∼0.16 μg cm−2). All four compound classes showed characteristic isomer distributions, with functional groups located between C-14 and C-16. In the mah1 mutant stem wax, diols and ketols could not be detected, while the amounts of secondary alcohols and ketones were drastically reduced. In two MAH1-overexpressing lines, equal amounts of C29 and C31 secondary alcohols were detected. Based on the comparison of homologue and isomer compositions between the different genotypes, it can be concluded that biosynthetic pathways lead from alkanes to secondary alcohols, and via ketones or diols to ketols. It seems plausible that MAH1 is the hydroxylase enzyme involved in all these conversions in Arabidopsis thaliana. PMID:19346242

  1. Interactions of bluff-body obstacles with turbulent airflows affecting evaporative fluxes from porous surfaces

    Science.gov (United States)

    Haghighi, Erfan; Or, Dani

    2015-11-01

    Bluff-body obstacles interacting with turbulent airflows are common in many natural and engineering applications (from desert pavement and shrubs over natural surfaces to cylindrical elements in compact heat exchangers). Even with obstacles of simple geometry, their interactions within turbulent airflows result in a complex and unsteady flow field that affects surface drag partitioning and transport of scalars from adjacent evaporating surfaces. Observations of spatio-temporal thermal patterns on evaporating porous surfaces adjacent to bluff-body obstacles depict well-defined and persistent zonation of evaporation rates that were used to construct a simple mechanistic model for surface-turbulence interactions. Results from evaporative drying of sand surfaces with isolated cylindrical elements (bluff bodies) subjected to constant turbulent airflows were in good agreement with model predictions for localized exchange rates. Experimental and theoretical results show persistent enhancement of evaporative fluxes from bluff-rough surfaces relative to smooth flat surfaces under similar conditions. The enhancement is attributed to formation of vortices that induce a thinner boundary layer over part of the interacting surface footprint. For a practical range of air velocities (0.5-4.0 m/s), low-aspect ratio cylindrical bluff elements placed on evaporating sand surfaces enhanced evaporative mass losses (relative to a flat surface) by up to 300% for high density of elements and high wind velocity, similar to observations reported in the literature. Concepts from drag partitioning were used to generalize the model and upscale predictions to evaporation from surfaces with multiple obstacles for potential applications to natural bluff-rough surfaces.

  2. Preparation and DMFC performance of a sulfophenylated poly(arylene ether ketone) polymer electrolyte membrane

    Energy Technology Data Exchange (ETDEWEB)

    Liu Baijun, E-mail: liubj@jlu.edu.c [College of Chemistry, Jilin University, Changchun 130012 (China); Hu Wei [College of Chemistry, Jilin University, Changchun 130012 (China); Kim, Yu Seung [Los Alamos National Laboratory, Electronic and Electrochemical Materials and Devices, Los Alamos, NM 87545 (United States); Zou Haifeng [College of Chemistry, Jilin University, Changchun 130012 (China); Robertson, Gilles P. [Institute for Chemical Process and Environmental Technology, National Research Council, Ottawa, Ontario K1A 0R6 (Canada); Jiang Zhenhua [College of Chemistry, Jilin University, Changchun 130012 (China); Guiver, Michael D. [Institute for Chemical Process and Environmental Technology, National Research Council, Ottawa, Ontario K1A 0R6 (Canada); Department of Energy Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of)

    2010-04-15

    A sulfonated poly(aryl ether ether ketone ketone) (PEEKK) having a well-defined rigid homopolymer-like chemical structure was synthesized from a readily prepared PEEKK by post-sulfonation with concentrated sulfuric acid at room temperature within several hours. The polymer electrolyte membrane (PEM) cast from the resulting polymer exhibited an excellent combination of thermal resistance, oxidative and dimensional stability, low methanol fuel permeability and high proton conductivity. Furthermore, membrane electrode assemblies (MEAs) were successfully fabricated and good direct methanol fuel cell (DMFC) performance was observed. At 2 M MeOH feed, the current density at 0.5 V reached 165 mA/cm, which outperformed our reported similarly structured analogues and MEAs derived from comparative Nafion membranes.

  3. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill

    2013-01-16

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  4. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  5. Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

    KAUST Repository

    Ye, Min

    2016-10-01

    A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

  6. Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

    KAUST Repository

    Ye, Min; Wen, Yuelu; Li, Huifang; Fu, Yejuan; Wang, Qinghao

    2016-01-01

    A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

  7. Efficient hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-polyoxometalate catalyst.

    Science.gov (United States)

    Alotaibi, Mshari A; Kozhevnikova, Elena F; Kozhevnikov, Ivan V

    2012-07-21

    Acidic heteropoly salt Cs(2.5)H(0.5)PW(12)O(40) doped with Pt nanoparticles is a highly active and selective catalyst for one-step hydrogenation of methyl isobutyl and diisobutyl ketones to the corresponding alkanes in the gas phase at 100 °C with 97-99% yield via metal-acid bifunctional catalysis.

  8. Forging C-C Bonds Through Decarbonylation of Aryl Ketones.

    Science.gov (United States)

    Somerville, Rosie J; Martin, Ruben

    2017-06-06

    The ability of nickel to cleave strong σ-bonds is again in the spotlight after a recent report that demonstrates the feasibility of using nickel complexes to promote decarbonylation of diaryl ketones. This transformation involves the cleavage of two strong C-C(O) bonds and avoids the use of noble metals, hence reinforcing the potential of decarbonylation as a technique for forging C-C bonds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. The failure of poly (ether ether ketone) in high speed contacts

    Science.gov (United States)

    Briscoe, B. J.; Stuart, B. H.; Sebastian, S.; Tweedale, P. J.

    1993-04-01

    The paper describes an experimental study, with an associated analysis incorporating supplementary data, of the anti-boundary lubricating action of an alkane-aliphatic carboxylic acid lubricant system in a poly (ether ether ketone)-mild steel contact. The experiments involve progressively increasing the load in a contact formed between a polymer plate and a rotating steel shaft and estimating the frictional work dissipated. Scuffing is identified when a rapid increase in frictional work is noted at a characteristic normal load. It is shown that the additive induces premature scuffing. Subsidiary data is provided using Raman spectroscopy and hardness probes, and confirms that certain additives such as decanoic acid and dodecylamine will induce surface plasticization in poly (ether ether ketone). The trends in the frictional data have been interpreted using the adhesive model of friction in conjunction with temperature-dependent interfacial theology and bulk mechanical property data. It is proposed that the scuffing process is induced prematurely as a consequence of excessive additive-induced subsurface plasticization. Restricted surface plasticization in this system provides an enhanced self-lubricating capacity.

  10. Studies on the production of hydrocarbon mixtures from waste methyl ethyl ketone

    International Nuclear Information System (INIS)

    Kokitkar, P.B.; Roth, O.B.; Debelak, K.A.

    1992-01-01

    Large quantities of waste solvents are generated annually around the world in a large number of diverse industries, the paints and plastics industry being the largest consumer. The management of these waste solvents is becoming more and more difficult due to stricter environmental regulations by the EPA. The paint and allied products industry is expected to shift its solvent use from aliphatics and aromatics to oxygenated solvents to meet emissions and disposal standards. Many researchers have studied the dehydration reactions of oxygenated solvents to produce dehydration. However, most researchers have obtained only low molecular weight compounds (C 3 - C 4 hydrocarbons) from C 1 - C 4 alcohols and ketones. The kinetics of this class of reactions are not available in the open literature. The objective of this paper is to investigate the thermodynamic feasibility of this class of reactions and to compare the hydrocarbon products obtained using methylethyl ketone with regular unleaded gasoline

  11. Synthesis of β-phenylchalcogeno-α, β-unsaturated esters, ketones and nitriles using microwave and solvent-free conditions

    International Nuclear Information System (INIS)

    Lenardao, Eder J.; Silva, Marcio S.; Mendes, Samuel R.; Azambuja, Francisco de; Jacob, Raquel G.; Perin, Gelson; Santos, Paulo Cesar Silva dos

    2007-01-01

    A simple, clean and efficient solvent-free protocol was developed for hydrochalcogenation of alkynes containing a Michael acceptor (ester, ketone and nitrile) with phenylchalcogenolate anions generated in situ from the respective diphenyl dichalcogenide (Se, Te, S), using alumina supported sodium borohydride. This efficient and improved method is general and furnishes the respective (Z)-β-phenylchalcogeno-α,β-unsaturated esters, ketones and nitriles, in good yield and higher selectivity, compared with those that use organic solvent and inert atmosphere. The use of microwave (MW) irradiation facilitates the procedure and accelerates the reaction. (author)

  12. γ-Sultam-cored N,N-ligands in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation of aryl ketones.

    Science.gov (United States)

    Rast, Slavko; Modec, Barbara; Stephan, Michel; Mohar, Barbara

    2016-02-14

    The synthesis of new enantiopure syn- and anti-3-(α-aminobenzyl)-benzo-γ-sultam ligands 6 and their application in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation (ATH) of ketones using formic acid/triethylamine is described. In particular, benzo-fused cyclic ketones afforded excellent enantioselectivities in reasonable time employing a low loading of the syn ligand-containing catalyst. A never-before-seen dynamic kinetic resolution (DKR) during reduction of a γ-keto carboxylic ester (S7) derivative of 1-indanone is realized leading as well to excellent induction.

  13. Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia

    Directory of Open Access Journals (Sweden)

    P. K. Misztal

    2011-09-01

    Full Text Available This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS, measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 % of all emitted BVOCs measured, at up to 30 mg m−2 h−1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK and methacrolein (MACR exhibited clear deposition of 1 mg m−2 h−1, with a small average canopy resistance of 230 s m−1. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m−2 h−1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m−2 h−1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010, we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.

  14. Design, synthesis and biological activity of novel peptidyl benzyl ketone FVIIa inhibitors

    DEFF Research Database (Denmark)

    Storgaard, Morten; Henriksen, Signe Teuber; Zaragoza, Florencio

    2011-01-01

    Herein is described the synthesis of a novel class of peptidyl FVIIa inhibitors having a C-terminal benzyl ketone group. This class is designed to be potentially suitable as stabilization agents of liquid formulations of rFVIIa, which is a serine protease used for the treatment of hemophilia...

  15. Baeyer-Villiger Oxidation of Cyclic Ketones by Using Tin-Silica Pillared Catalysts

    Czech Academy of Sciences Publication Activity Database

    Přech, Jan; Carretero, M. A.; Čejka, Jiří

    2017-01-01

    Roč. 9, č. 15 (2017), s. 3063-3072 ISSN 1867-3880 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : heterogeneous catalysis * ketones * layered * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.803, year: 2016

  16. Effects of High-Flux versus Low-Flux Membranes on Pulmonary Function Tests in Hemodialysis Patients.

    Science.gov (United States)

    Momeni, Ali; Rouhi, Hamid; Kiani, Glareh; Amiri, Masoud

    2013-01-01

    Several studies have been carried out to evaluate the effects of dialysis on pulmonary function tests (PFT). Dialysis procedure may reduce lung volumes and capacities or cause hypoxia; however, to the best of our knowledge, there is no previous study evaluating the effects of membrane type (high flux vs. low flux) on PFT in these patients. The aim of this study was the evaluation of this relationship. In this cross-sectional study, 43 hemodialysis patients without pulmonary disease were enrolled. In these patients dialysis was conducted by low-and high-flux membranes and before and after the procedure, spirometry was done and the results were evaluated by t-test and chi square test. The mean age of patients was 56.34 years. Twenty-three of them were female (53.5%). Type of membrane (high flux vs. low flux) had no effect on spirometry results of patients despite the significant decrease in the body weight during the dialysis session. High flux membrane had no advantage over low flux membrane in terms of improvement in spirometry findings; thus, we could not offer these expensive membranes for this purpose.

  17. Methylenation of perfluoroalkyl ketones using a Peterson olefination approach.

    Science.gov (United States)

    Hamlin, Trevor A; Kelly, Christopher B; Cywar, Robin M; Leadbeater, Nicholas E

    2014-02-07

    An operationally simple, inexpensive, and rapid route for the olefination of a wide array of trifluoromethyl ketones to yield 3,3,3-trifluoromethylpropenes is reported. Using a Peterson olefination approach, the reaction gives good to excellent yields of the alkene products and can be performed without purification of the β-hydroxysilyl intermediate. The reaction can be extended to other perfluoroalkyl substituents and is easily scaled up. The alkenes prepared can be readily transformed into a variety of other perfluoroalkyl-containing compounds.

  18. Toxicity of Aromatic Ketone to Yeast Cell and Improvement of the Asymmetric Reduction of Aromatic Ketone Catalyzed by Yeast Cell with the Introduction of Resin Adsorption

    Directory of Open Access Journals (Sweden)

    Zhong-Hua Yang

    2008-01-01

    Full Text Available Asymmetric reduction of the prochiral aromatic ketone catalyzed by yeast cells is one of the most promising routes to produce its corresponding enantiopure aromatic alcohol, but the space-time yield does not meet people’s expectations. Therefore, the toxicity of aromatic ketone and aromatic alcohol to the yeast cell is investigated in this work. It has been found that the aromatic compounds are poisonous to the yeast cell. The activity of yeast cell decreases steeply when the concentration of acetophenone (ACP is higher than 30.0 mmol/L. Asymmetric reduction of acetophenone to chiral S-α-phenylethyl alcohol (PEA catalyzed by the yeast cell was chosen as the model reaction to study in detail the promotion effect of the introduction of the resin adsorption on the asymmetric reduction reaction. The resin acts as the substrate reservoir and product extraction agent in situ. It has been shown that this reaction could be remarkably improved with this technique when the appropriate kind of resin is applied. The enantioselectivity and yield are acceptable even though the initial ACP concentration reaches 72.2 mmol/L.

  19. Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.

    Science.gov (United States)

    Skillinghaug, Bobo; Sköld, Christian; Rydfjord, Jonas; Svensson, Fredrik; Behrends, Malte; Sävmarker, Jonas; Sjöberg, Per J R; Larhed, Mats

    2014-12-19

    A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle.

  20. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

    Science.gov (United States)

    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

    2014-10-22

    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

  1. New Measurements of Methyl Ethyl Ketone (MEK) Photolysis Rates and Their Relevance to Global Oxidative Capacity

    Science.gov (United States)

    Brewer, J.; Ravishankara, A. R.; Mellouki, A.; Fischer, E. V.; Kukui, A.; Véronique, D.; Ait-helal, W.; Leglise, J.; Ren, Y.

    2017-12-01

    Methyl ethyl ketone (MEK) is one of the most abundant ketones in the atmosphere. MEK can be emitted directly into the atmosphere from both anthropogenic and natural sources, and it is also formed during the gas-phase oxidation of volatile organic compounds (VOCs). MEK is lost via reaction with OH, photolysis and deposition to the surface. Similar to the other atmospheric ketones, the photolysis of MEK may represent a source of HOx (OH + HO2) radicals in the upper troposphere. The degradation of MEK also leads to the atmospheric formation of acetaldehyde and formaldehyde. This work presents a new analysis of the temperature dependence of MEK photolysis cross-sections and a quantification of MEK photolysis rates under surface pressures using the CNRS HELIOS outdoor atmospheric chamber (Chambre de simulation atmosphérique à irradiation naturelle d'Orléans; http://www.era-orleans.org/ERA-TOOLS/helios-project.html). Additionally, we use the GEOS-Chem 3-D CTM (version 10-01, www.geos-chem.org) to investigate the impact of these newly measured rates and cross-sections on the global distribution and seasonality of MEK, as well as its importance to the tropospheric oxidative capacity.

  2. Laboratory Studies of Aedes aegypti Attraction to Ketones, Sulfides, and Primary Chloroalkanes Tested Alone and in Combination with L-Lactic Acid.

    Science.gov (United States)

    Bernier, Ulrich R; Kline, Daniel L; Allan, Sandra A; Barnard, Donald R

    2015-03-01

    The attraction of female Aedes aegypti to single compounds and binary compositions containing L-lactic acid and an additional saturated compound from a set of ketones, sulfides, and chloroalkanes was studied using a triple-cage dual-port olfactometer. These chemical classes were studied because of their structural relation to acetone, dimethyl disulfide, and dichloromethane, which have all been reported to synergize attraction to L-lactic acid. Human odors, carbon dioxide, and the binary mixture of L-lactic acid and CO₂served as controls for comparison of attraction responses produced by the binary mixtures. All tested mixtures that contained chloroalkanes attracted mosquitoes at synergistic levels, as did L-lactic acid and CO₂. Synergism was less frequent in mixtures of L-lactic acid with sulfides and ketones; in the case of ketones, synergistic attraction was observed only for L-lactic acid combined with acetone or butanone. Suppression or inhibition of attraction response was observed for combinations that contained ketones of C7-C12 molecular chain length (optimum in the C8-C10 range). This inhibition effect is similar to that observed previously for specific ranges of carboxylic acids, aldehydes, and alcohols.

  3. A Comparative study on VOCs and aldehyde-ketone emissions from a spark Ignition vehicle fuelled on compressed natural gas and gasoline

    International Nuclear Information System (INIS)

    Shah, A.N.

    2012-01-01

    In this work, an experimental study was conducted on a spark ignition (SI) vehicle fuelled on compressed natural gas (CNG), and gasoline to compare the unregulated emissions such as volatile organic compounds (VOCs) and aldehyde-ketones or carbonyls. In the meantime, ozone forming potential (OFP) of pollutants was also calculated on the basis of their specific reactivity (SR). The vehicle was run on a chassis dynamometer following the Chinese National Standards test scheduled for light duty vehicle (LDV) emissions. According to the results, total aldehyde-ketones were increased by 39.4% due to the substantial increase in formaldehyde and acrolein + acetone emissions, while VOCs and BTEX (benzene, toluene, ethyl benzene, and xylene) reduced by 85.2 and 86% respectively, in case of CNG fuelled vehicle as compared to gasoline vehicle. Although total aldehyde-ketones were higher with CNG relative to gasoline, their SR was lower due decrease in acetaldehyde, propionaldehyde, crotonaldehyde, and methacrolein species having higher maximum incremental reactivity (MIR) values. The SR of VOCs and aldehyde-ketones emitted from CNG fuelled vehicle was decreased by above 10% and 32% respectively, owing to better physicochemical properties and more complete burning of CNG as compared to gasoline. (author)

  4. Polyether ether ketone encased monolith frits made of polyether ether ketone tubing with a 0.25 mm opening resulting in an improved separation performance in liquid chromatography.

    Science.gov (United States)

    Park, Sin Young; Cheong, Won Jo

    2016-05-01

    Tiny polyether ether ketone encased monolith frits have been prepared by modified catalytic sulfonation of the inner surface of polyether ether tubing (1.6 mm od, 0.25 mm id) followed by modified formation of organic monolith and cutting of the tubing into slices. The frit was placed below the central hole of the column outlet union and supported by a combination of a silica capillary (0.365 mm od, 0.05 mm id) and a polyether ether ketone sleeve (1.6 mm od, 0.38 mm id) tightened with a nut and a ferrule when the column was packed to prevent sinking of the frit element into the union hole (0.25 mm opening) otherwise. The column packed this way with the frits investigated in this study has shown better separation performance owing to the reduced frit volume in comparison to the column packed with a commercial stainless-steel screen frit. This study establishes the strategy of disposable microcolumns in which cheap disposable frits are used whenever the column is re-packed to yield columns of even better chromatographic performance than the columns with commercial frits. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water

    KAUST Repository

    Czerwiński, Paweł

    2016-05-04

    An efficient and easily scalable NHC-copper(I) halide-catalyzed addition of terminal alkynes to 1,1,1-trifluoromethyl ketones, carried out on water for the first time, is reported. A series of addition reactions were performed with as little as 0.1-2.0mol% of [(NHC)CuX] (X=Cl, Br, I, OAc, OTf) complexes, providing tertiary propargylic trifluoromethyl alcohols in high yields and with excellent chemoselectivity from a broad range of aryl- and more challenging alkyl-substituted trifluoromethyl ketones (TFMKs). DFT calculations were performed to rationalize the correlation between the yield of catalytic alkynylation and the sterics of N-heterocyclic carbenes (NHCs), expressed as buried volume (%VBur), indicating that steric effects dominate the yield of the reaction. Additional DFT calculations shed some light on the differential reactivity of [(NHC)CuX] complexes in the alkynylation of TFMKs. The first enantioselective version of a direct alkynylation in the presence of C1-symmetric NHC-copper(I) complexes is also presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Inverse relationship between brain glucose and ketone metabolism in adults during short-term moderate dietary ketosis: A dual tracer quantitative positron emission tomography study.

    Science.gov (United States)

    Courchesne-Loyer, Alexandre; Croteau, Etienne; Castellano, Christian-Alexandre; St-Pierre, Valérie; Hennebelle, Marie; Cunnane, Stephen C

    2017-07-01

    Ketones (principally β-hydroxybutyrate and acetoacetate (AcAc)) are an important alternative fuel to glucose for the human brain, but their utilisation by the brain remains poorly understood. Our objective was to use positron emission tomography (PET) to assess the impact of diet-induced moderate ketosis on cerebral metabolic rate of acetoacetate (CMRa) and glucose (CMRglc) in healthy adults. Ten participants (35 ± 15 y) received a very high fat ketogenic diet (KD) (4.5:1; lipid:protein plus carbohydrates) for four days. CMRa and CMRglc were quantified by PET before and after the KD with the tracers, 11 C-AcAc and 18 F-fluorodeoxyglucose ( 18 F-FDG), respectively. During the KD, plasma ketones increased 8-fold ( p = 0.005) while plasma glucose decreased by 24% ( p = 0.005). CMRa increased 6-fold ( p = 0.005), whereas CMRglc decreased by 20% ( p = 0.014) on the KD. Plasma ketones were positively correlated with CMRa (r = 0.93; p < 0.0001). After four days on the KD, CMRa represented 17% of whole brain energy requirements in healthy adults with a 2-fold difference across brain regions (12-24%). The CMR of ketones (AcAc and β-hydroxybutyrate combined) while on the KD was estimated to represent about 33% of brain energy requirements or approximately double the CMRa. Whether increased ketone availability raises CMR of ketones to the same extent in older people as observed here or in conditions in which chronic brain glucose hypometabolism is present remains to be determined.

  7. Energetic effects of ether and ketone functional groups in 9,10-dihydroanthracene compound

    International Nuclear Information System (INIS)

    Freitas, Vera L.S.; Gomes, Jose R.B.; Ribeiro da Silva, Maria D.M.C.

    2010-01-01

    The energetic effects caused by replacing one of the methylene groups in the 9,10-dihydroanthracene by ether or ketone functional groups yielding xanthene and anthrone species, respectively, were determined from direct comparison of the standard (p o = 0.1 MPa) molar enthalpies of formation in the gaseous phase, at T = 298.15 K, of these compounds. The experimental static-bomb combustion calorimetry and Calvet microcalorimetry and the computational G3(MP2)//B3LYP method were used to get the standard molar gas-phase enthalpies of formation of xanthene, (41.8 ± 3.5) kJ . mol -1 , and anthrone, (31.4 ± 3.2) kJ . mol -1 . The enthalpic increments for the substitution of methylene by ether and ketone in the parent polycyclic compound (9,10-dihydroanthracene) are -(117.9 ± 5.5) kJ . mol -1 and -(128.3 ± 5.4) kJ . mol -1 , respectively.

  8. Silane Cross-Linked Sulfonted Poly(Ether Ketone/Ether Benzimidazoles for Fuel Cell Applications

    Directory of Open Access Journals (Sweden)

    Zilu Yao

    2017-11-01

    Full Text Available γ-(2,3-epoxypropoxy propyltrimethoxysilane (KH-560 was incorporated in various proportions into side-chain-type sulfonated poly(ether ketone/ether benzimidazole (SPEKEBI as a crosslinker, to make membranes with high ion exchange capacities and excellent performance for direct methanol fuel cells (DMFCs. Systematical measurements including Fourier transform infrared (FT-IR, scanning electron microscopy-energy-dispersive and X-ray photoelectron spectroscopy (XPS proved the complete disappearance of epoxy groups in KH-560 and the existence of Si in the membranes. The resulting membranes showed increased mechanical strength and thermal stability compared to the unmodified sulfonated poly(ether ketone/ether benzimidazole membrane in appropriate doping amount. Meanwhile, the methanol permeability has decreased, leading to the increase of relative selectivities of SPEKEBI-x-SiO2 membranes. Furthermore, the H2/O2 cell performance of SPEKEBI-2.5-SiO2 membrane showed a much higher peak power density compared with the pure SPEKEBI memrbrane.

  9. Synthesis and structure of aromatic and heterocyclic tellurium compounds 33. Synthesis of [2-(aryltelluro)vinyl]aldehydes and ketones and stereochemistry of nucleophilic substitution under vinyl atom of carbon

    International Nuclear Information System (INIS)

    Sadekov, I.D.; Rivkin, B.B.; Zakharov, A.V.; Minkin, V.I.

    1996-01-01

    By means of interaction of (2-vinylchlorida) carbonyl compounds and (2-acylvinyl) triethylammonium chlorides and arenetellurolate-anions certain, [2-(aryltelluro)vinyl]ketones and [2-(aryltelluro)vinyl]aldehydes have been synthesized, while by means of reaction between 2-aroylvinyl chlorides and Li 2 Te some di(2-aroylvinyl)tellurides have been prepared. Interaction of (2-vinylchloride)ketones with arenetellurolate-anions always gives rise to Z-isomers of [2-(aryltelluro)vinyl]ketones as a result of stabilization of intermediate carbanion by intramolecular coordination O→Te. Nucleophilic addition of arenetellurolate-anions to α-acetylene aldehydes and ketones occurs as trans-addition. 36 refs., 2 figs., 1 tab

  10. Dermal absorption and disposition of musk ambrette, musk ketone and musk xylene in human subjects.

    Science.gov (United States)

    Hawkins, David R; Elsom, Lionel F; Kirkpatrick, David; Ford, Richard A; Api, Anne Marie

    2002-05-28

    Musk ambrette, musk ketone and musk xylene have a long history of use as fragrance ingredients, although musk ambrette is no longer used in fragrances. As part of the review of the safety of these uses, it is important to consider the systemic exposure that results from these uses. Since the primary route of exposure to fragrances is on the skin, dermal doses of carbon-14 labelled musk ambrette, musk ketone and musk xylene were applied to the backs (100 cm2) of healthy human volunteers (two to three subjects) at a nominal dose level of 10-20 microg/cm2 and excess material removed at 6 h. Means of 2.0% musk ambrette, 0.5% musk ketone and 0.3% musk xylene were absorbed based on the amounts excreted in urine and faeces during 5 days. Most of the material was excreted in the urine with less than 10% of the amount excreted being found in faeces. No radioactivity was detected in any plasma sample, consistent with low absorption, and no radioactivity was detected (<0.02% dose) in skin strips taken at 120 h. Analysis of urine samples indicated that all three compounds were excreted mainly as single glucuronide conjugates. The aglycones were chromatographically different, but of similar polarity, to the major rat metabolites excreted in bile also as glucuronides.

  11. Asymmetric reduction of ketones with catecholborane using 2,6-BODOL complexes of titanium(IV) as catalysts.

    Science.gov (United States)

    Sarvary, I; Almqvist, F; Frejd, T

    2001-05-18

    Reductions performed with Ti(IV) complexes of ligands based on bicyclo[2.2.2]octane diols 5 and 6 are effective catalysts in the reduction of prochiral ketones to optically active alcohols, with catecholborane as the reducing agent. Methyl ketones are favored and enantiomeric excesses (ee) of octanone, which gave 2-octanol in 87% ee. Further details of the method were examined, for example, temperature, solvent composition, amount of molecular sieves (4 A), and catecholborane quality, as well as the sensitivity of the ligands towards acids. NMR spectroscopic methods were used to gain some insight into the complexes formed between the ligands and [Ti(OiPr)4]. A dimeric structure is proposed for the pre-catalyst.

  12. A low-carbohydrate diet is more effective in reducing body weight than healthy eating in both diabetic and non-diabetic subjects.

    Science.gov (United States)

    Dyson, P A; Beatty, S; Matthews, D R

    2007-12-01

    Low-carbohydrate diets are effective for weight reduction in people without diabetes, but there is limited evidence for people with Type 2 diabetes. Aims To assess the impact of a low-carbohydrate diet on body weight, glycated haemoglobin (HbA(1c)), ketone and lipid levels in diabetic and non-diabetic subjects. Thirteen Type 2 diabetic subjects (on diet or metformin) and 13 non-diabetic subjects were randomly allocated to either a low-carbohydrate diet (diet following Diabetes UK nutritional recommendations and were seen monthly for 3 months. Subjects (25% male) were (mean +/- sd) age 52 +/- 9 years, weight 96.3 +/- 16.6 kg, body mass index 35.1 kg/m(2), HbA(1c) 6.6 +/- 1.1%, total cholesterol 5.1 +/- 1.1 mmol/l, high-density lipoprotein cholesterol 1.3 +/- 0.4 mmol/l, low-density lipoprotein cholesterol 3.1 +/- 0.9 mmol/l, triglycerides (geometric mean) 1.55 (1.10, 2.35) mmol/l and ketones range 0.0-0.2 mmol/l. Analysis was by intention to treat with last observation carried forward. Twenty-two of the participants (85%) completed the study. Weight loss was greater (6.9 vs. 2.1 kg, P = 0.003) in the low-carbohydrate group, with no difference in changes in HbA(1c), ketone or lipid levels. The diet was equally effective in those with and without diabetes.

  13. Reaction rate constants of H-abstraction by OH from large ketones: Measurements and site-specific rate rules

    KAUST Repository

    Badra, Jihad

    2014-01-01

    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (CO) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (CO), and the prime is used to differentiate different neighboring environments of a methylene group):P1,CO = 7.38 × 10-14 exp(-274 K/T) + 9.17 × 10-12 exp(-2499 K/T) (285-1355 K)S10,CO = 1.20 × 10-11 exp(-2046 K/T) + 2.20 × 10-13 exp(160 K/T) (222-1464 K)S11,CO = 4.50 × 10-11 exp(-3000 K/T) + 8.50 × 10-15 exp(1440 K/T) (248-1302 K)S11′,CO = 3.80 × 10-11 exp(-2500 K/T) + 8.50 × 10-15 exp(1550 K/T) (263-1370 K)S 21,CO = 5.00 × 10-11 exp(-2500 K/T) + 4.00 × 10-13 exp(775 K/T) (297-1376 K) © 2014 the Partner Organisations.

  14. Potentiometric titrations of para and nitro substituted aromatic acids and their mixtures in methylethyl ketone

    International Nuclear Information System (INIS)

    Ozeroglu, C.; Karahan, M.

    2011-01-01

    In this study, it was the purpose to examine the potentiometric titrations of para and nitro substituted aromatic acids in methylethyl ketone (MEK) as a non-aqueous solvent. Good analytical results were obtained in determining the amount of each acid and the amounts of acids in their ternary mixtures by using 0.0964 N tetrabuthylammoniumhydroxyde (TBAH) as a standard titrant. Methylethyl ketone (MEK) which is a good solvent for many organic compounds and has a convenient liquid range of -86 to 80 deg. C was used for titration of the para and nitro substituted aromatic acids. A linear relationship has been found between pKa values of the para and nitro substituted aromatic acids in water and the half neutralization potential (HNP) values determined by potentiometric titration curves of the same acids in MEK. (author)

  15. A SENSITIZED PHOTOINITIATION SYSTEM——BIS (7- DIETHYLAMINO COUMARIN )KETONE- 3 AND DIPHENYLIODONIUM SALT COMBINATION

    Institute of Scientific and Technical Information of China (English)

    LI Jun; WANG Xiuzhi; YANG Yongyung; LI Miaozhen; WANG Erjian

    1993-01-01

    Bis (7- diethylaminocoumarin ) ketone- 3(DACK) and diphenyliodonium salt (DPIO)combination as an effective photoinitiation system for radical polymerization has been investigated. The sensitized photolysis of DACK/DPIO leads to bleaching of DACK and decomposition of DPIO to generate initiating radical species. The electron transfer sensitization occurs mainly from the triplet state of DACK. The photobleaching obeyed a second-order kinetics and the rate constant was evaluated to be 31.3mol-1.l.s-1. Photopolymerization of MMA initiated by DACK/DPIO was carried out in acetonitrile solution. The polymerization rate was found to be proportional to the concentration of DACK, DPIO and MMA with the exponents of 0.34, 0.40 and 1.0 respectively. The initiated efficiency is comparable to those of small molecular ketones. The sensitized photoinitiation mechanism has been discussed.

  16. Developed a needle trap device with PDMS sorbent for microextraction of toluene and methyl ethyl ketone from aquatic samples using dynamic headspace

    Directory of Open Access Journals (Sweden)

    Sara Karimi Zeverdegani

    2016-09-01

    Full Text Available Introduction: Due to the widespread use of toxic chemicals in most workplaces that can lead to toxic effects on human, various chemical extraction technique have been defined for analysis these toxic substances in air, water and biological samples. The purpose of this research is extraction of  toluene and methyl ethyl ketone from aquatic samples with needle trap device and  one commercial sorbent. Methods: In this research, needle trap device was used to extraction of  toluene and methyl ethyl ketone in aquatic samples, so needles(size 20 were packed with PDMS and extraction was done with dynamic headspace needle trap device. Gas chromatography with - flame ionization detector was used to analysis and optimized extraction of two substances were obtained. Results: Results show that the optimum temperature and time extraction was similar for toluene and methyl ethyl ketone (30 ° C, 30 min, but the reproducibility of results and calibration curve that obtained for toluene was better than methyl ethyl ketone. Conclusion: Needle trap technique is inexpensive, sensitive and portable also this method has good recovery to extract small amounts of  toluene and methyl ethyketon from aquatic samples with polydimethylsiloxane.

  17. Information-flux approach to multiple-spin dynamics

    International Nuclear Information System (INIS)

    Di Franco, C.; Paternostro, M.; Kim, M. S.; Palma, G. M.

    2007-01-01

    We introduce and formalize the concept of information flux in a many-body register as the influence that the dynamics of a specific element receive from any other element of the register. By quantifying the information flux in a protocol, we can design the most appropriate initial state of the system and, noticeably, the distribution of coupling strengths among the parts of the register itself. The intuitive nature of this tool and its flexibility, which allow for easily manageable numerical approaches when analytic expressions are not straightforward, are greatly useful in interacting many-body systems such as quantum spin chains. We illustrate the use of this concept in quantum cloning and quantum state transfer and we also sketch its extension to nonunitary dynamics

  18. The effect of RO3201195 and a pyrazolyl ketone P38 MAPK inhibitor library on the proliferation of Werner syndrome cells.

    Science.gov (United States)

    Bagley, Mark C; Dwyer, Jessica E; Baashen, Mohammed; Dix, Matthew C; Murziani, Paola G S; Rokicki, Michal J; Kipling, David; Davis, Terence

    2016-01-21

    Microwave-assisted synthesis of the pyrazolyl ketone p38 MAPK inhibitor RO3201195 in 7 steps and 15% overall yield, and the comparison of its effect upon the proliferation of Werner Syndrome cells with a library of pyrazolyl ketones, strengthens the evidence that p38 MAPK inhibition plays a critical role in modulating premature cellular senescence in this progeroid syndrome and the reversal of accelerated ageing observed in vitro on treatment with SB203580.

  19. Cyclodextrin ketones as oxidation catalysts: investigation of bridged derivatives

    DEFF Research Database (Denmark)

    Fenger, Thomas Hauch; Marinescu, Lavinia; Bols, Mikael

    2009-01-01

    A series of alpha-cyclodextrin derivatives containing a 3, 4 or 5 membered ether-linked bridge between the 6A and 6D oxygen atoms, with and without a ketone, were prepared. The synthesis used perbenzylated alpha-cyclodextrin A,D-diol as a starting material upon which O-alkylation and further modi...... derivatives were also made. The 6A,6D-di-O-(propa-2-on-1,3-diyl)-6C,6F-di-O-methyl and di-O-pivaloyl derivatives were also prepared. The new compounds were analysed for catalysis of the oxidation of amines and alcohols....

  20. The Microwave Spectrum of Methyl Vinyl Ketone Revisited

    Science.gov (United States)

    Wilcox, David S.; Shirar, Amanda J.; Williams, Owen L.; Dian, Brian C.

    2011-06-01

    A chirped-pulse Fourier transform microwave spectrometer was used to record the rotational spectrum of methyl vinyl ketone (MVK, 3-butene-2-one) from 6 to 18.9 GHz. Two stable conformations were identified: the previously documented antiperiplanar (ap) conformer and synperiplanar (sp), which is reported for the first time in this microwave study. Methyl torsional analysis with XIAM resulted in V3 barrier heights of 433.8(1) and 376.6(2) Cm-1 for ap- and sp-MVK, respectively. Heavy atom isotopic species were detected in natural abundance allowing bond lengths and angles of the molecular frames to be calculated through Kraitchman analysis. A comparison with ab initio calculations is included.

  1. Poly (ether ether ketone) membranes for fuel cells

    International Nuclear Information System (INIS)

    Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D.; Hui, Wang S.; Oliveira, Vivianna S. de

    2015-01-01

    Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

  2. All solid supercapacitor based on polyaniline and crosslinked sulfonated poly[ether ether ketone

    International Nuclear Information System (INIS)

    Sivaraman, P.; Kushwaha, R.K.; Shashidhara, K.; Hande, V.R.; Thakur, A.P.; Samui, A.B.; Khandpekar, M.M.

    2010-01-01

    All solid supercapacitor based on polyaniline (PANI) and crosslinked sulfonated poly[ether ether ketone] (XSPEEK,) is reported in this paper. The crosslinker used for sulfonated poly[ether ether ketone] (SPEEK) is 1,4-bis(hydroxymethyl) benzene. The XSPEEK is used as both solid electrolyte and separator membrane. Supercapacitors are fabricated using various PANI/XSPEEK weight ratios. These are characterized by cyclic voltammetry and galvanostatic charge-discharge studies. The supercapacitor with PANI/XSPEEK weight ratio 1:0.5, exhibit a specific capacitance of 480 F g -1 of PANI. To the best of authors' knowledge, the value reported here is the highest for a supercapacitor based on a proton conducting solid polymer electrolyte and PANI. Detailed electrochemical impedance spectroscopy analysis is carried out. The analysis shows that the complex capacitance of the supercapacitor depends on the XSPEEK content. The time constant (t 0 ), derived from the imaginary part of complex capacitance decreases with increase in the XSPEEK content in the supercapacitor. Cycle life characteristics of the supercapacitor show a decrease in specific capacitance during initial cycles and get stabilized during later cycles.

  3. Ketones and brain development: Implications for correcting deteriorating brain glucose metabolism during aging

    Directory of Open Access Journals (Sweden)

    Nugent Scott

    2016-01-01

    Full Text Available Brain energy metabolism in Alzheimer’s disease (AD is characterized mainly by temporo-parietal glucose hypometabolism. This pattern has been widely viewed as a consequence of the disease, i.e. deteriorating neuronal function leading to lower demand for glucose. This review will address deteriorating glucose metabolism as a problem specific to glucose and one that precedes AD. Hence, ketones and medium chain fatty acids (MCFA could be an alternative source of energy for the aging brain that could compensate for low brain glucose uptake. MCFA in the form of dietary medium chain triglycerides (MCT have a long history in clinical nutrition and are widely regarded as safe by government regulatory agencies. The importance of ketones in meeting the high energy and anabolic requirements of the infant brain suggest they may be able to contribute in the same way in the aging brain. Clinical studies suggest that ketogenesis from MCT may be able to bypass the increasing risk of insufficient glucose uptake or metabolism in the aging brain sufficiently to have positive effects on cognition.

  4. Acyclic ketones in the defensive secretion of a "daddy longlegs" (Leiobunum vittatum).

    Science.gov (United States)

    Meinwald, J; Kluge, A F; Carrel, J E; Eisner, T

    1971-07-01

    The defensive secretion of the "daddy longlegs" Leiobunum vittatum was analyzed and found to contain the acyclic ketones 4-methylheptan-3-one and E-4,6-dimethyl-6-octen-3-one as its major organic components. Although 4-methylheptan-3-one has been found previously as an alarm substance in certain ant genera, the second component, whose structure is confirmed by synthesis, is new.

  5. α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Meifen; Xin, Hui; Guo, Zhi; Guo, Dapeng; Wang, Yan; Zhao, Peng; Li, Jingyi, E-mail: lijingyicn@163.com

    2017-01-01

    Highlights: • The catalysts were prepared by reduction method at room temperature. • α-Alkylation of ketones and primary alcohols occurred on Au-Pd/CeO{sub 2} in visible light. • Superior catalytic activities were shown on bimetallic Au-Pd/CeO{sub 2} catalysts. • The catalyst can be reused for 4 times. • The mechanism of the synthesis for ketones was proposed. - Abstract: The direct α-alkylation of ketones with primary alcohols to obtain the corresponding saturated coupled ketones was achieved with bimetallic gold(Au)-palladium(Pd) nanoparticles(NPs) supported on a transition metal oxide (such as CeO{sub 2}). This system demonstrated a higher catalytic property than Au/CeO{sub 2} and Pd/CeO{sub 2} under visible light irradiation at 40 ± 3 °C in an Ar atmosphere. Such phenomenon was caused by the synergistic effect between Au and Pd. Isopropyl alcohol was used as the solvent and CH{sub 3}ONa as the base. The effect of the bimetallic Au-Pd mass ratio and the two different transition metal oxide supports (such as CeO{sub 2} or ZrO{sub 2}) during the reaction process was studied. The highest catalytic activity of those examined happened with the 1.5 wt% Au-1.5 wt% Pd (Au and Pd mass ratio 1:1)/CeO{sub 2} photo-catalyst. The intensity and wavelength of the visible light had a strong influence on the system. The catalyst can be reused for four times. A reaction mechanism was proposed for the α-alkylation of ketones with primary alcohols.

  6. Comparison of breath gases, including acetone, with blood glucose and blood ketones in children and adolescents with type 1 diabetes.

    Science.gov (United States)

    Blaikie, Tom P J; Edge, Julie A; Hancock, Gus; Lunn, Daniel; Megson, Clare; Peverall, Rob; Richmond, Graham; Ritchie, Grant A D; Taylor, David

    2014-11-25

    Previous studies have suggested that breath gases may be related to simultaneous blood glucose and blood ketone levels in adults with type 2 and type 1 diabetes. The aims of this study were to investigate these relationships in children and young people with type 1 diabetes in order to assess the efficacy of a simple breath test as a non-invasive means of diabetes management. Gases were collected in breath bags and measurements were compared with capillary blood glucose and ketone levels taken at the same time on a single visit to a routine hospital clinic in 113 subjects (59 male, age 7 years 11 months-18 years 3 months) with type 1 diabetes. The patients were well-controlled with relatively low concentrations of the blood ketone measured (β hydroxybutyrate, 0-0.4 mmol l(-1)). Breath acetone levels were found to increase with blood β hydroxybutyrate levels and a significant relationship was found between the two (Spearman's rank correlation ρ = 0.364, p acetone (ρ = 0.16, p = 0.1), but led to the conclusion that single breath measurements of acetone do not provide a good measure of blood glucose levels in this cohort. This result suggests a potential to develop breath gas analysis to provide an alternative to blood testing for ketone measurement, for example to assist with the management of type 1 diabetes.

  7. Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

    Science.gov (United States)

    Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

    2011-07-14

    Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

  8. Ketogenic diet metabolites reduce firing in central neurons by opening K(ATP) channels.

    Science.gov (United States)

    Ma, Weiyuan; Berg, Jim; Yellen, Gary

    2007-04-04

    A low-carbohydrate ketogenic diet remains one of the most effective (but mysterious) treatments for severe pharmacoresistant epilepsy. We have tested for an acute effect of physiological ketone bodies on neuronal firing rates and excitability, to discover possible therapeutic mechanisms of the ketogenic diet. Physiological concentrations of ketone bodies (beta-hydroxybutyrate or acetoacetate) reduced the spontaneous firing rate of neurons in slices from rat or mouse substantia nigra pars reticulata. This region is thought to act as a "seizure gate," controlling seizure generalization. Consistent with an anticonvulsant role, the ketone body effect is larger for cells that fire more rapidly. The effect of ketone bodies was abolished by eliminating the metabolically sensitive K(ATP) channels pharmacologically or by gene knock-out. We propose that ketone bodies or glycolytic restriction treat epilepsy by augmenting a natural activity-limiting function served by K(ATP) channels in neurons.

  9. Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations.

    Science.gov (United States)

    Kajiya, Daisuke; Saitow, Ken-ichi

    2013-08-07

    Carbonyl compounds are solutes that are highly soluble in supercritical CO2 (scCO2). Their solubility governs the efficiency of chemical reactions, and is significantly increased by changing a chromophore. To effectively use scCO2 as solvent, it is crucial to understand the high solubility of carbonyl compounds, the solvation structure, and the solute-solvent intermolecular interactions. We report Raman spectroscopic data, for three prototypical ketones dissolved in scCO2, and four theoretical analyses. The vibrational Raman spectra of the C=O stretching modes of ketones (acetone, acetophenone, and benzophenone) were measured in scCO2 along the reduced temperature Tr = T∕Tc = 1.02 isotherm as a function of the reduced density ρr = ρ∕ρc in the range 0.05-1.5. The peak frequencies of the C=O stretching modes shifted toward lower energies as the fluid density increased. The density dependence was analyzed by using perturbed hard-sphere theory, and the shift was decomposed into attractive and repulsive energy components. The attractive energy between the ketones and CO2 was up to nine times higher than the repulsive energy, and its magnitude increased in the following order: acetone attractive energy and optimized the relative configuration between each solute and CO2. According to theoretical calculations for the dispersion energy, the dipole-induced-dipole interaction energy, and the frequency shift due to their interactions, the experimentally determined attractive energy differences in the three solutes were attributed to the dispersion energies that depended on a chromophore attached to the carbonyl groups. It was found that the major intermolecular interaction with the attractive shift varied from dipole-induced dipole to dispersion depending on the chromophore in the ketones in scCO2. As the common conclusion for the Raman spectral measurements and the four theoretical calculations, solute polarizability, modified by the chromophore, was at the core of

  10. The Effect of Ketone Defects on the Charge Transport and Charge Recombination in Polyfluorenes

    NARCIS (Netherlands)

    Kuik, Martijn; Wetzelaer, Gert-Jan A. H.; Ladde, Jurre G.; Nicolai, Herman T.; Wildeman, Jurjen; Sweelssen, Jorgen; Blom, Paul W. M.; Sweelssen, Jörgen

    2011-01-01

    The effect of on-chain ketone defects on the charge transport of the polyfluorene derivative poly(9,9-dioctylfluorene) (PFO) is investigated. Using MoO3 as ohmic hole contact, the hole transport in a pristine PFO diode is observed to be limited by space-charge, whereas fluorenone contaminated PFO

  11. The effect of ketone defects on the charge transport and charge recombination in polyfluorenes

    NARCIS (Netherlands)

    Kuik, M.; Wetzelaer, G.-J.A.H.; Laddé, J.G.; Nicolai, H.T.; Wildeman, J.; Sweelssen, J.; Blom, P.W.M.

    2011-01-01

    The effect of on-chain ketone defects on the charge transport of the polyfluorene derivative poly(9,9-dioctylfluorene) (PFO) is investigated. Using MoO3 as ohmic hole contact, the hole transport in a pristine PFO diode is observed to be limited by space-charge, whereas fluorenone contaminated PFO

  12. KoFlux: Korean Regional Flux Network in AsiaFlux

    Science.gov (United States)

    Kim, J.

    2002-12-01

    AsiaFlux, the Asian arm of FLUXNET, held the Second International Workshop on Advanced Flux Network and Flux Evaluation in Jeju Island, Korea on 9-11 January 2002. In order to facilitate comprehensive Asia-wide studies of ecosystem fluxes, the meeting launched KoFlux, a new Korean regional network of long-term micrometeorological flux sites. For a successful assessment of carbon exchange between terrestrial ecosystems and the atmosphere, an accurate measurement of surface fluxes of energy and water is one of the prerequisites. During the 7th Global Energy and Water Cycle Experiment (GEWEX) Asian Monsoon Experiment (GAME) held in Nagoya, Japan on 1-2 October 2001, the Implementation Committee of the Coordinated Enhanced Observing Period (CEOP) was established. One of the immediate tasks of CEOP was and is to identify the reference sites to monitor energy and water fluxes over the Asian continent. Subsequently, to advance the regional and global network of these reference sites in the context of both FLUXNET and CEOP, the Korean flux community has re-organized the available resources to establish a new regional network, KoFlux. We have built up domestic network sites (equipped with wind profiler and radiosonde measurements) over deciduous and coniferous forests, urban and rural rice paddies and coastal farmland. As an outreach through collaborations with research groups in Japan, China and Thailand, we also proposed international flux sites at ecologically and climatologically important locations such as a prairie on the Tibetan plateau, tropical forest with mixed and rapid land use change in northern Thailand. Several sites in KoFlux already begun to accumulate interesting data and some highlights are presented at the meeting. The sciences generated by flux networks in other continents have proven the worthiness of a global array of micrometeorological flux towers. It is our intent that the launch of KoFlux would encourage other scientists to initiate and

  13. Hydrogen storage by functionalised Poly(ether ether ketone)

    Energy Technology Data Exchange (ETDEWEB)

    Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

    2010-07-01

    In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

  14. Electron impact ionization of cycloalkanes, aldehydes, and ketones

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Dhanoj; Antony, Bobby, E-mail: bka.ism@gmail.com [Department of Applied Physics, Indian School of Mines, Dhanbad, JH 826 004 (India)

    2014-08-07

    The theoretical calculations of electron impact total ionization cross section for cycloalkane, aldehyde, and ketone group molecules are undertaken from ionization threshold to 2 keV. The present calculations are based on the spherical complex optical potential formalism and complex scattering potential ionization contribution method. The results of most of the targets studied compare fairly well with the recent measurements, wherever available and the cross sections for many targets are predicted for the first time. The correlation between the peak of ionization cross sections with number of target electrons and target parameters is also reported. It was found that the cross sections at their maximum depend linearly with the number of target electrons and with other target parameters, confirming the consistency of the values reported here.

  15. Preparation of poly (imine imine ketone) s microshells

    International Nuclear Information System (INIS)

    Cui Yi; Luo Xuan; Fan Yongheng; Zhang Lin; Liu Lei; Lin Runxiong

    2010-01-01

    Large diameter (0.6 ∼ 2.0 mm) microshells of poly (imine imine ketone) s (PIIKs) were prepared by micro-liquid technique and double-layer latex technique. A double T-channel droplet generator was designed and developed for the fabrication of PIIKs microshells of controlled size continuously. Manipulative conditions of the diameter and thickness of shells were studied, and the effect of density mismatch on shell quality was discussed. Phase separation during the preparation process affects the morphology of shells. Spinodal phase separation tends to occur at the outer surface of the shells, while binodal phase separation at the inner surface. The diameters of PIIKs shells were measured, 88% of which vary in ± 5% of the average diameter. The sphericity is better than 99%. (authors)

  16. Organic Solvent-Tolerant Marine Microorganisms as Catalysts for Kinetic Resolution of Cyclic β-Hydroxy Ketones

    NARCIS (Netherlands)

    Chen, B.; Liu, Hui; Zeferino Ribeiro De Souza, F.; Liu, Lan

    2017-01-01

    Chiral cyclic β-hydroxy ketones represent key motifs in the production of natural products of biological interest. Although the molecules are structurally simple, they require cumbersome synthetic steps to get access to them and their synthesis remains a challenge in organic chemistry. In this

  17. Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

    NARCIS (Netherlands)

    Koziara, B.T.; Nijmeijer, K.; Benes, N.E.

    2015-01-01

    The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (≤5 wt%) and not too low spin speeds

  18. Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

    NARCIS (Netherlands)

    Koziara, Beata; Nijmeijer, Dorothea C.; Benes, Nieck Edwin

    2015-01-01

    The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (B5 wt%) and not too low spin speeds

  19. Syntheses of Calix[4]Pyrroles by Amberlyst-15 Catalyzed Cyclocondensations of Pyrrole with Selected Ketones

    Directory of Open Access Journals (Sweden)

    Tanuja Bisht

    2007-11-01

    Full Text Available A facile and efficient protocol is reported for the synthesis of calix[4]pyrrolesand N-confused calix[4]pyrroles in moderate to excellent yields by reaction of dialkyl orcycloalkyl ketones with pyrrole catalyzed by reusable AmberlystTM-15 under eco-friendlyconditions.

  20. Ligand-controlled reactivity, selectivity, and mechanism of cationic ruthenium-catalyzed hydrosilylations of alkynes, ketones, and nitriles: a theoretical study.

    Science.gov (United States)

    Yang, Yun-Fang; Chung, Lung Wa; Zhang, Xinhao; Houk, K N; Wu, Yun-Dong

    2014-09-19

    Density functional theory calculations with the M06 functional have been performed on the reactivity, selectivity, and mechanism of hydrosilylations of alkynes, ketones, and nitriles catalyzed by cationic ruthenium complexes [CpRu(L)(MeCN)2](+), with L = P(i)Pr3 or MeCN. The hydrosilylation of alkynes with L = P(i)Pr3 involves an initial silyl migration mechanism to generate the anti-Markovnikov product, in contrast to the Markovnikov product obtained with L = MeCN. The bulky phosphine ligand directs the silyl group to migrate to Cβ of the alkyne. This explains the anti-Markovnikov selectivity of the catalyst with L = P(i)Pr3. By contrast, the silane additions to either ketone or nitrile proceed through an ionic SN2-Si outer-sphere mechanism, in which the substrate attacks the Si center. The P(i)Pr3 ligand facilitates the activation of the Si-H bond to furnish a η(2)-silane complex, whereas a η(1)-silane complex is formed for the MeCN ligand. This property of the phosphine ligand enables the catalytic hydrosilylation of ketones and nitriles in addition to that of alkynes.

  1. Not Good, but Not All Bad: Dehydration Effects on Body Fluids, Organ Masses, and Water Flux through the Skin of Rhinella schneideri (Amphibia, Bufonidae).

    Science.gov (United States)

    Anderson, Rodolfo C O; Bovo, Rafael P; Eismann, Carlos E; Menegario, Amauri A; Andrade, Denis V

    Because of their permeable skin, terrestrial amphibians are constantly challenged by the potential risk of dehydration. However, some of the physiological consequences associated with dehydration may affect aspects that are themselves relevant to the regulation of water balance. Accordingly, we examined the effects of graded levels of dehydration on the rates of evaporative water loss and water absorption through the skin in the terrestrial Neotropical toad, Rhinella schneideri. Concomitantly, we monitored the effects of dehydration on the mass of visceral organs; hematocrit and hemoglobin content; plasma osmolality; and plasma concentration of urea, sodium, chloride, and potassium. We found that dehydration caused an increase in the concentration of body fluids, as indicated by virtually all the parameters examined. There was a proportional change in the relative masses of visceral organs, except for the liver and kidneys, which exhibited a decrease in their relative masses greater than the whole-body level of dehydration. Changes-or the preservation-of relative organ masses during dehydration may be explained by organ-specific physiological adjustments in response to the functional stress introduced by the dehydration itself. As dehydration progressed, evaporative water loss diminished and water reabsorption increased. In both cases, the increase in body fluid concentration associated with the dehydration provided the osmotic driver for these changes in water flux. Additionally, dehydration-induced alterations on the cutaneous barrier may also have contributed to the decrease in water flux. Dehydration, therefore, while posing a considerable challenge on the water balance regulation of anurans, paradoxically facilitates water conservation and absorption.

  2. Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

    Energy Technology Data Exchange (ETDEWEB)

    Davidson, Stephen D. [Energy and Environmental; Spies, Kurt A. [Energy and Environmental; Mei, Donghai [Energy and Environmental; Kovarik, Libor [Energy and Environmental; Kutnyakov, Igor [Energy and Environmental; Li, Xiaohong S. [Energy and Environmental; Lebarbier Dagle, Vanessa [Energy and Environmental; Albrecht, Karl O. [Energy and Environmental; Dagle, Robert A. [Energy and Environmental

    2017-09-11

    We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, and activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.

  3. Growth of superconductor material in a fluxed melt, and article of manufacture

    International Nuclear Information System (INIS)

    Jackson, K.A.; Schneemeyer, L.F.

    1991-01-01

    This patent describes a method for making a body of bismuth-strontium calcium cuprate, lead-substituted bismuth strontium calcium cuprate, or thallium-barium calcium cuprate superconductor material. It comprises cooling a melt at least locally, the melt comprising constituents of the material, characterized in that the melts further comprises a flux component comprising at least one fluxing agent selected from the group consisting of sodium chloride and potassium chloride, such that the cuprate body has superconductor properties at a temperature of 77 K

  4. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

    2013-10-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

  5. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    International Nuclear Information System (INIS)

    Chiu, K.-F.; Su, S.-H.

    2013-01-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

  6. Miscibility and Hydrogen Bonding in Blends of Poly(4-vinylphenol/Poly(vinyl methyl ketone

    Directory of Open Access Journals (Sweden)

    Hana Bourara

    2014-10-01

    Full Text Available The miscibility and phase behavior of poly(4-vinylphenol (PVPh with poly(vinyl methyl ketone (PVMK was investigated by differential scanning calorimetry (DSC, Fourier transform infrared spectroscopy (FTIR and scanning electron microscopy (SEM. It was shown that all blends of PVPh/PVMK are totally miscible. A DSC study showed the apparition of a single glass transition (Tg over their entire composition range. When the amount of PVPh exceeds 50% in blends, the obtained Tgs are found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are capable of forming interpolymer complexes. FTIR analysis revealed the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and carbonyl groups, which intensified when the amount of PVPh was increased in blends. Furthermore, the quantitative FTIR study carried out for PVPh/PVMK blends was also performed for the vinylphenol (VPh and vinyl methyl ketone (VMK functional groups. These results were also established by scanning electron microscopy study (SEM.

  7. Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine.

    Science.gov (United States)

    Zhou, Ji-Ning; Fang, Qiang; Hu, Yi-Hu; Yang, Li-Yao; Wu, Fei-Fei; Xie, Lin-Jie; Wu, Jing; Li, Shijun

    2014-02-14

    A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.

  8. Reactions of uranium (III) and (IV) compounds with ketones, nitriles and acid chlorides. Towards a use of uranium complexes in organic synthesis

    International Nuclear Information System (INIS)

    Adam, Raymond

    1993-01-01

    In this research thesis, the author shows that various organic molecules can be interestingly transformed into uranium complexes with degrees of oxidation of +3 or +4. In a first part, the author describes reactions of carbonyl compounds with the UCl 4 -Na(Hg) reducing system. Then, he addresses reductions of ketones, nitriles and acid chlorides by a uranium (III) complex: Cp 3 U(THF). The third part reports a detailed study of the reduction of ketones by U(BH 4 ) 4 [fr

  9. Ruthenium-catalyzed direct C3 alkylation of indoles with α,β-unsaturated ketones.

    Science.gov (United States)

    Li, Shuai-Shuai; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin

    2015-01-28

    In this paper, a simple and highly efficient ruthenium-catalyzed direct C3 alkylation of indoles with various α,β-unsaturated ketones without chelation assistance has been developed. This novel C-H activation methodology exhibits a broad substrate scope such as different substituted indoles, pyrroles, and other azoles. Further synthetic applications of the alkylation products can lead to more attractive 3,4-fused tricyclic indoles.

  10. Acyclic Ketones in the Defensive Secretion of a “Daddy Longlegs” (Leiobunum vittatum)

    Science.gov (United States)

    Meinwald, J.; Kluge, A. F.; Carrel, J. E.; Eisner, T.

    1971-01-01

    The defensive secretion of the “daddy longlegs” Leiobunum vittatum was analyzed and found to contain the acyclic ketones 4-methylheptan-3-one and E-4,6-dimethyl-6-octen-3-one as its major organic components. Although 4-methylheptan-3-one has been found previously as an alarm substance in certain ant genera, the second component, whose structure is confirmed by synthesis, is new. PMID:5283937

  11. Analyzing urine ketone of 235 medical examiners%232例体检者尿酮体阳性结果分析

    Institute of Scientific and Technical Information of China (English)

    王会敏; 何柯新

    2012-01-01

    目的 探讨尿酮体在体检人群不同年龄段、不同性别的分布及其与血糖的相关性.方法 对232例尿酮体为阳性的体检者按年龄及性别分组进行分析,同时与其同期检测的血糖结果 进行对比分析.结果 尿酮体阳性者以1+和2+为主;主要出现在20~50岁年龄段中;大多数尿酮体阳性者其血糖不高(≤6.1).结论 在体检人群中尿酮体阳性与血糖高低不存在相关性,尿酮体阳性并不能准确反映患者的血糖水平;尿酮体阳性主要集中在20~50岁年龄组.%Objective Objective: To explore the relationship between urine ketone and different age and gender and plasma glucose detected in the same time with urine ketone. Methods The results of totally 232 medical examiners whose urine ketone were positive were analyzed according to different ages and genders. Results The urine ketone results which are positive are 1+ and 2 + , mainly distribute the ages of 20 to 50. And great majority of them has a normal or low level of fasting plasma glucose. Conclusion The urine ketone which are positive has no relationship with plasma glucose,it can't accurately reflect the level of plasma glucose. We found that most of the groups distribute the ages of 20 to 50. The reasons probably are they have heavy work pressure and imbalanced diet. People need to pay attention to the quality of life. Having a balanced nutrition diet and eating on time will be a good life style.

  12. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Rueping, Magnus

    2017-01-01

    . By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high

  13. Thermal stability of sulfonated Poly(Ether Ether Ketone) films : on the role of Protodesulfonation

    NARCIS (Netherlands)

    Koziara, B.T.; Kappert, E.J.; Ogieglo, W.; Nijmeijer, Kitty; Hempenius, M.A.; Benes, N.E.

    Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material,

  14. Biaxial deformation behaviour of poly-ether-ether-ketone

    Science.gov (United States)

    Turner, Josh; Menary, Gary; Martin, Peter

    2018-05-01

    The biaxial tensile properties of thin poly-ether-ether-ketone (PEEK) films are presented. Investigation into the biaxial mechanical behaviour of PEEK films will provide a preliminary insight into the anticipated stress/strain response, and potential suitability, to the possible fabrication of thin walled parts through stretch blow moulding and thermoforming processes - with the multi-axial state of strain imposed onto the heated thermoplastic sheet representative of the expected strain history experienced during these material forming processes. Following identification of the prospective forming temperature window, the biaxial mechanical behaviour of the material is characterized under differing modes of deformation, at a nominal strain rate of 1 s-1. The temperature dependence is outlined within - with an appreciable increase in flow behaviour correlated with specimen temperature exceeding its glass transition temperature (Tg).

  15. Reduction of Aldehydes and Ketones to Corresponding Alcohols Using Diammonium Hydrogen Phosphite and Commercial Zinc Dust

    Directory of Open Access Journals (Sweden)

    K. Anil Kumar

    2011-01-01

    Full Text Available A mild and an efficient system has been developed for the reduction of aromatic aldehydes and ketones to their corresponding alcohols in good yield using inexpensive commercial zinc dust as catalyst and diammonium hydrogen phosphite as a hydrogen donor.

  16. Force-free thin flux tubes: Basic equations and stability

    International Nuclear Information System (INIS)

    Zhugzhda, Y.D.

    1996-01-01

    The thin flux tube approximation is considered for a straight, symmetrical, force-free, rigidly rotating flux tube. The derived set of equations describes tube, body sausage, and Alfveacute charn wave modes and is valid for any values of Β. The linear waves and instabilities of force-free flux tubes are considered. The comparison of approximate and exact solutions for an untwisted, nonrotating flux tube is performed. It is shown that the approximate and exact dispersion equations coincides, except the 20% discrepancy of sausage frequencies. An effective cross section is proposed to introduce the removal of this discrepancy. It makes the derived approximation correct for the force-free thin flux tube dynamics, except the detailed structure of radial eigenfunction. The dispersion of Alfveacute charn torsional waves in a force-free tubes appears. The valve effect of one directional propagation of waves in rotating twisted tube is revealed. The current and rotational sausage instabilities of a force-free, thin flux tube are considered. copyright 1996 American Institute of Physics

  17. Accelerated simulations of aromatic polymers: application to polyether ether ketone (PEEK)

    Science.gov (United States)

    Broadbent, Richard J.; Spencer, James S.; Mostofi, Arash A.; Sutton, Adrian P.

    2014-10-01

    For aromatic polymers, the out-of-plane oscillations of aromatic groups limit the maximum accessible time step in a molecular dynamics simulation. We present a systematic approach to removing such high-frequency oscillations from planar groups along aromatic polymer backbones, while preserving the dynamical properties of the system. We consider, as an example, the industrially important polymer, polyether ether ketone (PEEK), and show that this coarse graining technique maintains excellent agreement with the fully flexible all-atom and all-atom rigid bond models whilst allowing the time step to increase fivefold to 5 fs.

  18. Critical flux determination by flux-stepping

    DEFF Research Database (Denmark)

    Beier, Søren; Jonsson, Gunnar Eigil

    2010-01-01

    In membrane filtration related scientific literature, often step-by-step determined critical fluxes are reported. Using a dynamic microfiltration device, it is shown that critical fluxes determined from two different flux-stepping methods are dependent upon operational parameters such as step...... length, step height, and.flux start level. Filtrating 8 kg/m(3) yeast cell suspensions by a vibrating 0.45 x 10(-6) m pore size microfiltration hollow fiber module, critical fluxes from 5.6 x 10(-6) to 1.2 x 10(-5) m/s have been measured using various step lengths from 300 to 1200 seconds. Thus......, such values are more or less useless in itself as critical flux predictors, and constant flux verification experiments have to be conducted to check if the determined critical fluxes call predict sustainable flux regimes. However, it is shown that using the step-by-step predicted critical fluxes as start...

  19. Mechanism of inactivation of human leukocyte elastase by a chloromethyl ketone: kinetic and solvent isotope effect studies

    International Nuclear Information System (INIS)

    Stein, R.L.; Trainor, D.A.

    1986-01-01

    The mechanism of inactivation of human leukocyte elastase (HLE) by the chloromethyl ketone MeOSuc-Ala-Ala-Pro-Val-CH 2 Cl was investigated. The dependence of the first-order rate constant for inactivation on concentration of chloromethyl ketone is hyperbolic and suggests formation of a reversible Michaelis complex prior to covalent interaction between the enzyme and inhibitor. However, the observed Ki value is 10 microM, at least 10-fold lower than dissociation constants for complexes formed from interaction of HLE with structurally related substrates or reversible inhibitors, and suggests that Ki is a complex kinetic constant, reflecting the formation and accumulation of both the Michaelis complex and a second complex. It is proposed that this second complex is a hemiketal formed from attack of the active site serine on the carbonyl carbon of the inhibitor. The accumulation of this intermediate may be a general feature of reactions of serine proteases and chloromethyl ketones derived from specific peptides and accounts for the very low Ki values observed for these reactions. The solvent deuterium isotope effect (SIE) on the inactivation step (ki) is 1.58 +/- 0.07 and is consistent with rate-limiting, general-catalyzed attack of the active site His on the methylene carbon of the inhibitor with displacement of chloride anion. The general catalyst is thought to be the active site Asp. In contrast, the SIE on the second-order rate constant for HLE inactivation, ki/Ki, is inverse and equals 0.64 +/- 0.05

  20. Analytical characterization of selective benthic flux components in estuarine and coastal waters

    Science.gov (United States)

    King, Jeffrey N.

    2011-01-01

    Benthic flux is the rate of flow across the bed of a water body, per unit area of bed. It is forced by component mechanisms, which interact. For example, pressure gradients across the bed, forced by tide, surface gravity waves, density gradients, bed–current interaction, turbulence, and terrestrial hydraulic gradients, drive an advective benthic flux of water and constituents between estuarine and coastal waters, and surficial aquifers. Other mechanisms also force benthic flux, such as chemical gradients, bioturbation, and dispersion. A suite of component mechanisms force a total benthic flux at any given location, where each member of the suite contributes a component benthic flux. Currently, the types and characteristics of component interactions are not fully understood. For example, components may interact linearly or nonlinearly, and the interaction may be constructive or destructive. Benthic flux is a surface water–groundwater interaction process. Its discharge component to a marine water body is referred to, in some literature, as submarine groundwater discharge. Benthic flux is important in characterizing water and constituent budgets of estuarine and coastal systems. Analytical models to characterize selective benthic flux components are reviewed. Specifically, these mechanisms are for the component associated with the groundwater tidal prism, and forced by surface gravity wave setup, surface gravity waves on a plane bed, and the terrestrial hydraulic gradient. Analytical models are applied to the Indian River Lagoon, Florida; Great South Bay, New York; and the South Atlantic Bight in South Carolina and portions of North Carolina.

  1. Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail: shinj@kaeri.re.kr

    2014-02-15

    Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

  2. Preparation and characterization of electrospun poly(phthalazinone ether nitrile ketone) membrane with novel thermally stable properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gang; Zhang, Hao; Qian, Bingqing [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Wang, Jinyan, E-mail: wangjinyan@dlut.edu.cn [Department of Polymer Science and Materials, Dalian University of Technology, Dalian 116024 (China); Jian, Xigao [Department of Polymer Science and Materials, Dalian University of Technology, Dalian 116024 (China); Qiu, Jieshan, E-mail: jqiu@dlut.edu.cn [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

    2015-10-01

    Highlights: • Poly (phthalazinone ether nitrile ketone) (PPENK) was used to successfully prepare nanofiber membranes by electrospinning. • Electrospun membrane exhibits a good thermostability. • Electrospun membrane. - Abstract: Electrospun nanofibrous membranes have several applications because of their excellent properties, such as high porosity, small fiber diameter, and large surface area. However, high-temperature resistant electrospun membranes remain a challenge because of the absence of precursors that offer spinnability, scalability, and superior thermal stability. In this study, poly(phthalazinone ether nitrile ketone) (PPENK) was used to successfully prepare nanofiber membranes by electrospinning. Electrospun PPENK membranes were characterized by scanning electron microscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, and tensile stress–strain tests. Results indicated that the prepared electrospun membranes had a very high glass transition temperature, superior chemical resistance, and excellent mechanical strength. These desirable properties broaden their potential application in membranes and treatment of various hot fluid streams without strict temperature control.

  3. Optical activities of steroid ketones - Elucidation of the octant rule.

    Science.gov (United States)

    Hatanaka, Masashi; Sayama, Daisuke; Miyasaka, Makoto

    2018-04-21

    Theoretical calculations of optical activities in steroid ketones are presented by using modern semi-empirical PM7 wavefunctions. Both circular dichroism (CD) and specific rotation, which is proportional to optical rotation dispersion (ORD), are well simulated, and signs of the Cotton effect at the most long-wavelength region are fully in accordance with the experimental results. The good accordance is related to the octant rule, which is deduced within the framework of the perturbation theory. Our treatment is promising to predict the signs of the Cotton effect of large molecules, and thus, the absolute configurations can also be grasped without demanding procedures. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Water flux in animals: analysis of potential errors in the tritiated water method

    International Nuclear Information System (INIS)

    Nagy, K.A.; Costa, D.

    1979-03-01

    Laboratory studies indicate that tritiated water measurements of water flux are accurate to within -7 to +4% in mammals, but errors are larger in some reptiles. However, under conditions that can occur in field studies, errors may be much greater. Influx of environmental water vapor via lungs and skin can cause errors exceeding +-50% in some circumstances. If water flux rates in an animal vary through time, errors approach +-15% in extreme situations, but are near +-3% in more typical circumstances. Errors due to fractional evaporation of tritiated water may approach -9%. This error probably varies between species. Use of an inappropriate equation for calculating water flux from isotope data can cause errors exceeding +-100%. The following sources of error are either negligible or avoidable: use of isotope dilution space as a measure of body water volume, loss of nonaqueous tritium bound to excreta, binding of tritium with nonaqueous substances in the body, radiation toxicity effects, and small analytical errors in isotope measurements. Water flux rates measured with tritiated water should be within +-10% of actual flux rates in most situations

  5. Water flux in animals: analysis of potential errors in the tritiated water method

    Energy Technology Data Exchange (ETDEWEB)

    Nagy, K.A.; Costa, D.

    1979-03-01

    Laboratory studies indicate that tritiated water measurements of water flux are accurate to within -7 to +4% in mammals, but errors are larger in some reptiles. However, under conditions that can occur in field studies, errors may be much greater. Influx of environmental water vapor via lungs and skin can cause errors exceeding +-50% in some circumstances. If water flux rates in an animal vary through time, errors approach +-15% in extreme situations, but are near +-3% in more typical circumstances. Errors due to fractional evaporation of tritiated water may approach -9%. This error probably varies between species. Use of an inappropriate equation for calculating water flux from isotope data can cause errors exceeding +-100%. The following sources of error are either negligible or avoidable: use of isotope dilution space as a measure of body water volume, loss of nonaqueous tritium bound to excreta, binding of tritium with nonaqueous substances in the body, radiation toxicity effects, and small analytical errors in isotope measurements. Water flux rates measured with tritiated water should be within +-10% of actual flux rates in most situations.

  6. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill

    2013-07-26

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  7. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  8. Estimation of core body temperature from skin temperature, heat flux, and heart rate using a Kalman filter.

    Science.gov (United States)

    Welles, Alexander P; Xu, Xiaojiang; Santee, William R; Looney, David P; Buller, Mark J; Potter, Adam W; Hoyt, Reed W

    2018-05-18

    Core body temperature (T C ) is a key physiological metric of thermal heat-strain yet it remains difficult to measure non-invasively in the field. This work used combinations of observations of skin temperature (T S ), heat flux (HF), and heart rate (HR) to accurately estimate T C using a Kalman Filter (KF). Data were collected from eight volunteers (age 22 ± 4 yr, height 1.75 ± 0.10 m, body mass 76.4 ± 10.7 kg, and body fat 23.4 ± 5.8%, mean ± standard deviation) while walking at two different metabolic rates (∼350 and ∼550 W) under three conditions (warm: 25 °C, 50% relative humidity (RH); hot-humid: 35 °C, 70% RH; and hot-dry: 40 °C, 20% RH). Skin temperature and HF data were collected from six locations: pectoralis, inner thigh, scapula, sternum, rib cage, and forehead. Kalman filter variables were learned via linear regression and covariance calculations between T C and T S , HF, and HR. Root mean square error (RMSE) and bias were calculated to identify the best performing models. The pectoralis (RMSE 0.18 ± 0.04 °C; bias -0.01 ± 0.09 °C), rib (RMSE 0.18 ± 0.09 °C; bias -0.03 ± 0.09 °C), and sternum (RMSE 0.20 ± 0.10 °C; bias -0.04 ± 0.13 °C) were found to have the lowest error values when using T S , HF, and HR but, using only two of these measures provided similar accuracy. Copyright © 2018. Published by Elsevier Ltd.

  9. KH 2PO4 as a novel catalyst for regioselective monobromination of aralkyl ketones using N-bromosuccinimide: a green methodology

    Directory of Open Access Journals (Sweden)

    P. Md. Khaja Mohinuddin

    2015-08-01

    Full Text Available A simple, regioselective and green method has been developed for the preparation of monobrominated ketones from various aralkyl ketones by using N-bromosuccinimide in presence of KH 2PO 4 in EtOH at reflux temperature. The present method is of short reaction time and simple with excellent isolated yields of products. The use of eco-friendly solvent, reuse of organic waste (succinimide and recyclable catalyst used for 4 times without loss of activity are advantageous. This is the first example of the use of KH 2PO 4 as a useful catalyst in organohalogen chemistry and the present method meets reduce-reuse-recycle (RRR principle towards development of green protocol.

  10. DISQUAC Characterization of the CarbonylůChlorine Interactions in Binary Mixtures of Linear Ketone with Chloroalkane

    Czech Academy of Sciences Publication Activity Database

    Dragoescu, D.; Teodorescu, M.; Barhala, A.; Wichterle, Ivan

    2003-01-01

    Roč. 68, č. 7 (2003), s. 1175-1192 ISSN 0010-0765 R&D Projects: GA ČR GA104/03/1555 Institutional research plan: CEZ:AV0Z4072921 Keywords : group contribution model * thermodynamics * chloroalkanes-linear ketones Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.041, year: 2003

  11. Flux line lattice in type II super conductors

    International Nuclear Information System (INIS)

    Manindra Kumar; Singh, Arun Kumar; Surendra Kumar

    2003-01-01

    The shear modules C 66 of the flux line lattice in type II super conductors can be obtained from a two body interaction between the flux lines even at large inductions B ∼ HC 2 . The potential is composed of a repulsive and an attractive part and has a range diverging at HC 2 . An explicit expression for the Ginzberg-Landau C 66 is given for arbitrary B and k' (G-L parameter). The graph for C 66 exhibits the expected maximum at a certain value of b. (author)

  12. Hyperglycemia (High Blood Glucose)

    Medline Plus

    Full Text Available ... for energy. When your body breaks down fats, waste products called ketones are produced. Your body cannot ... glucose) Dawn Phenomenon Checking for Ketones Tight Diabetes Control donate en -- A Future Without Diabetes - a-future- ...

  13. Kinetic Investigation of the Electrochemical Oxidation of Bis(benzene)chromium(0) in Diethyl ketone / N,N-Dimethylformamide

    Czech Academy of Sciences Publication Activity Database

    Tsierkezos, Nikos

    2008-01-01

    Roč. 37, č. 10 (2008), s. 1437-1448 ISSN 0095-9782 Institutional research plan: CEZ:AV0Z40550506 Keywords : bis(benzene)chromium(0) * cyclic voltammetry * diethyl ketone * half-wawe potential * N,N-dimethylformamide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.241, year: 2008

  14. Ion-Selective Ionic Polymer Metal Composite (IPMC) actuator based on crown ether containing sulfonated Poly(Arylene Ether Ketone)

    NARCIS (Netherlands)

    Tas, S.; Zoetebier, B.; Sukas, O.S.; Bayraktar, M.; Hempenius, M.; Vancso, G.J.; Nijmeijer, K.

    2017-01-01

    This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

  15. Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected alpha-Hydroxy Ketones

    Czech Academy of Sciences Publication Activity Database

    Jahn, Emanuela; Smrček, Jakub; Pohl, Radek; Císařová, I.; Jones, P. G.; Jahn, Ullrich

    2015-01-01

    Roč. 2015, č. 35 (2015), s. 7785-7798 ISSN 1434-193X Grant - others:COST(XE) CM1201 Institutional support: RVO:61388963 Keywords : synthetic methods * reduction * diastereoselectivity * diols * ketones Subject RIV: CC - Organic Chemistry Impact factor: 3.068, year: 2015

  16. The effect of alterations in total coenzyme A on metabolic pathways in the liver and heart

    International Nuclear Information System (INIS)

    Schlosser, C.A.S.

    1989-01-01

    The first set of experiments involved in vitro experiments using primary cultures of rat hepatocytes. A range of conditions were developed which resulted in cell cultures with variations in total CoA over a range of 1.3 to 2.9 nmol/mg protein with identical hormonal activation which simulated metabolic stress. Elevations of total CoA levels above that of controls due to preincubation with cyanamide plus pantothenate were correlated with diminished rates of total ketone body production, 3-hydroxybutyrate production and ratios of 3 hydroxybutyrate/acetoactetate with palmitate as substrate. In contrast, cells with elevated total CoA levels had higher rates of [ 14 C] CO 2 production from radioactive palmitate which implied greater flux of acetyl CoA units into the TCA cycle and less to the pathway of ketogenesis. The second set of experiments were designed to alter total CoA levels in vivo by maintaining rats on a chronic ethanol diet with or without pantothenate-supplementation. The effect of alterations of CoA on mitochondrial metabolism was evaluated by measuring substrate oxidation rates in liver and heat mitochondria as well as ketone body production with palmitoyl-1-carnitine as substrate

  17. An easy and efficient method to produce {gamma}-amino alcohols by reduction of {beta}-enamino ketones

    Energy Technology Data Exchange (ETDEWEB)

    Harris, Maria Ines N.C.; Braga, Antonio C.H. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica]. E-mail: herrera@iqm.unicamp.br

    2004-12-01

    Reduction of {beta}-enamino ketones 2 with NaBH{sub 4} in glacial acetic acid gave {gamma}-amino alcohols 1 in 70% to 98% yield with diastereomeric excesses, preferentially the syn product, from 44% to 90%. The stereochemistry of these compounds was confirmed by analysis of their tetrahydro-1,3-oxazine derivatives 3. (author)

  18. Activation of aqueous hydrogen peroxide for non-catalyzed dihydroperoxidation of ketones by azeotropic removal of water.

    Science.gov (United States)

    Starkl Renar, K; Pečar, S; Iskra, J

    2015-09-28

    Cyclic and acyclic ketones were selectively converted to gem-dihydroperoxides in 72-99% yield with 30% aq. hydrogen peroxide by azeotropic distillation of water from the reaction mixture without any catalyst. The reactions were more selective than with 100% H2O2 and due to neutral conditions also less stable products could be obtained.

  19. Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

    Directory of Open Access Journals (Sweden)

    W. J. F. Acton

    2016-06-01

    Full Text Available This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS together with the methods of virtual disjunct eddy covariance (using PTR-MS and eddy covariance (using PTR-ToF-MS. Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m−2 h−1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m−2 h−1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN isoprene emission algorithms (Guenther et al., 2006. A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC–MS to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

  20. Acute nutritional ketosis: implications for exercise performance and metabolism

    Science.gov (United States)

    2014-01-01

    Ketone bodies acetoacetate (AcAc) and D-β-hydroxybutyrate (βHB) may provide an alternative carbon source to fuel exercise when delivered acutely in nutritional form. The metabolic actions of ketone bodies are based on sound evolutionary principles to prolong survival during caloric deprivation. By harnessing the potential of these metabolic actions during exercise, athletic performance could be influenced, providing a useful model for the application of ketosis in therapeutic conditions. This article examines the energetic implications of ketone body utilisation with particular reference to exercise metabolism and substrate energetics. PMID:25379174

  1. Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

    Energy Technology Data Exchange (ETDEWEB)

    Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L., E-mail: tait@indiana.edu [Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, Indiana 47405 (United States)

    2015-03-14

    Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

  2. [Determination of nitroaromatics and cyclo ketones in sea water' by gas chromatography coupled with activated carbon fiber solid-phase micro-extraction].

    Science.gov (United States)

    Ma, Hanna; Zhu, Mengya; Wang, Yalin; Sun, Tonghua; Jia, Jinping

    2009-05-01

    A gas chromatography (GC) coupled with solid-phase micro-extraction using a special activated carbon fiber (ACF) was developed for the analysis of 6 nitroaromatics and cyclic ketones, nitrobenzene (NB), 1,3-dinitrobenzene (1,3-DNB), 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), isophorone, 1,4-naphthaquinone (1,4-NPQ), in sea water samples. The sample was extracted for 30 min under saturation of NaCl at 1,500 r/min and 60 degrees C in head space. The desorption was performance at 280 degrees C for 2 min. The linear ranges were from 0.01 to 400 microg/L. The limits of detection (LODs) were 1.4 - 3.2 ng/L. This method has been successfully applied to the determination of nitroaromatics and cyclic ketones in the sea water samples obtained from East China Sea. The concentrations of nitrobenzene, 1,3-dinitrobenzene and 2,6-dinitrotoluene in the sea water sample were 0.756, 0.944, 0.890 microg/L, respectively. The recoveries were 86.3% - 101.8% with the relative standard deviations (RSDs) of 3.7% -7.8%. The method is suitable for analyzing nitroaromatics and cyclic ketones at low concentration levels in sea water samples.

  3. Synergic extraction of europium (III) by TTA and selected carbinols or ketons in carbontetrachloride

    International Nuclear Information System (INIS)

    El-Naggar, H.A.; El-Madany, S.

    1988-01-01

    The extraction of Eu(III) by HTTA dissolved in CCl 4 has been carried from acid-perchlorate and acid-acetate solutions. Some oxygen containing solvents have been added to the chelate in extraction of the acetate complex of Eu(III). The reaction mechanisms and the equilibrium constants are calculated for the different extracted species. The data obtained are discussed in the light of the structure of carbinols and ketones used as adducts

  4. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu

    2013-05-17

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  5. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu; Zhu, Bo; Lee, Richmond; Yang, Wenguo; Tan, Davin; Yang, Caiyun; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei; Jiang, Zhiyong

    2013-01-01

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  6. Additional conformer observed in the microwave spectrum of methyl vinyl ketone

    Science.gov (United States)

    Wilcox, David S.; Shirar, Amanda J.; Williams, Owen L.; Dian, Brian C.

    2011-05-01

    A chirped-pulse Fourier transform microwave spectrometer was used to record the rotational spectrum of methyl vinyl ketone (MVK, 3-butene-2-one). Two stable conformations were identified: the previously documented antiperiplanar (ap) conformer and synperiplanar (sp), which is reported for the first time in this microwave study. Methyl torsional analysis resulted in V3 barrier heights of 433.8(1) and 376.6(2) cm-1 for ap- and sp-MVK, respectively. Heavy atom isotopic species of both conformers were detected in natural abundance allowing bond lengths and angles of the molecular frames to be calculated through Kraitchman analysis. A comparison with ab initio calculations is included.

  7. Sulfonated poly(ether ether ketone) membranes for electric double layer capacitors

    International Nuclear Information System (INIS)

    Kim, Wan Ju; Kim, Dong-Won

    2008-01-01

    Sulfonated poly(ether ether ketone) (S-PEEK) with different degree of sulfonation (DS) has been prepared and evaluated as a proton conducting membrane for electric double layer capacitor (EDLC). The polymer electrolytes prepared with S-PEEK membrane exhibited ionic conductivities about 1.2 x 10 -3 -4.5 x 10 -3 S cm -1 at room temperature, which depended on both soaking solvent and degree of sulfonation. The quasi-solid-state EDLCs consisted of activated carbon electrodes and S-PEEK membrane were assembled, and their electrochemical characteristics were studied by cyclic voltammetry and charge-discharge cycle tests. The effect of DS on the electrochemical performances of EDLCs has been investigated

  8. Near Infrared Spectroscopic Identification of Alkyl Aromatic Esters and Phenyl Ketones

    Science.gov (United States)

    Nelyubov, D. V.; Vazhenin, D. A.; Kudriavtsev, A. A.; Buzolina, A. Yu.

    2018-03-01

    Bands characterizing the content of carbon atoms in alkyl (7177-7205 cm-1) and phenyl structural fragments (9175-9192 cm-1) in organic molecules were revealed by studying the near infrared spectra of such compounds. The optical density at the maxima of these absorption bands was shown to depend strongly on the fraction of carbon atoms in the corresponding fragments. The developed models proved to be adequate for determining the fraction of carbon atoms in alkyl aromatic esters and phenyl ketones. The feasibility of modeling the molecular structure of alkyl aromatic esters using regression models was demonstrated for the product of the condensation of oleic acid and benzyl alcohol.

  9. Amin-substituierte Spiroacetale von Grundmanns Keton als neuartige Inhibitoren der humanen ∆8,7-Sterolisomerase

    OpenAIRE

    Krojer, Melanie

    2011-01-01

    Die Cholesterolbiosynthese ist ein wichtiger Ansatzpunkt für die Kontrolle und Manipulation von biochemischen Vorgängen in Wirbeltieren und damit für die Entwicklung therapeutischer Wirkstoffe. Mit der Cholesterolbiosynthese assoziierte Krankheiten sind beispielsweise Hypercholesterinämie, die Alzheimer Erkrankung oder die Creutzfeld-Jakob Krankheit. Im Rahmen dieser Arbeit konnten ausgehend von Grundmanns Keton und alpha-Tetralon verschiedene Amin-substituierte Spiroacetale dargestellt ...

  10. Ketone Body Acetoacetate Buffers Methylglyoxal via a Non-enzymatic Conversion during Diabetic and Dietary Ketosis

    DEFF Research Database (Denmark)

    Salomon, Trine; Sibbersen, Christian; Hansen, Jakob

    2017-01-01

    now demonstrate that during ketosis, another meta- bolic route is operative via direct non-enzymatic aldol reaction between methylglyoxal and the ke- tone body acetoacetate, leading to 3-hydroxyhex- ane-2,5-dione. This novel metabolite is present at a concentration of 10%–20% of the methylglyoxal...

  11. Relative measurement of the fluxes of thermal, resonant and rapid neutrons in reactor G1; Mesures relatives des flux thermique, resonnant et rapide dans le reacteur G1

    Energy Technology Data Exchange (ETDEWEB)

    Carle, R; Mazancourt, T de [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    We sought to determine the behavior of the thermal, resonant and rapid neutron fluxes in the multiplier-reflector transition region, in the two principal directions of the system. We have also measured the variation of these different fluxes in the body of the multiplier medium in a canal filled with graphite and in an empty canal. The results are given in the form of curves representing: - the variation of the ratio of the thermal flux to the rapid flux in axial and radial transitions - the behavior of the thermal and resonant fluxes and the variation of their ratio in the same regions. (author) [French] Nous avons cherche a determiner le comportement des differents flux, thermique, resonnant et rapide a la transition milieu multiplicateur-reflecteur dans les deux directions principales du reseau. Nous avons egalement mesure la variation de ces differents flux au sein du milieu multiplicateur dans un canal rempli de graphite et dans un canal vide. Les resultats sont donnes sous forme de courbe representant: - La variation du rapport du flux thermique au flux rapide aux transitions axiale et radiale - L'allure des flux thermique et resonnant et la variation de leur rapport dans les memes regions. (auteur)

  12. Dynamics of human whole body amino acid metabolism

    International Nuclear Information System (INIS)

    Young, V.R.

    1981-01-01

    The mechanism of regulation of the nitrogen metabolism in humans under various nutritional and physiological states was examined using stable isotopes. In the simultaneous continuous infusion of 1- [ 13 ] - leucine and α- [ 15 N]- lysine, their fluxed decreased when individuals received lower protein intake. The rates of oxidation and incorporation into body proteins of leucine changed in parallel with the protein intake. Such effects of diet on whole body leucine kinetics were modified by the energy state and dietary energy level. The nitrogen balance was also improved by an excess level of dietary energy. When the intake of dietary protein was lowered below the maintenance level, the whole body flux and de novo synthesis of glycine were lowered, but alanine synthesis was clearly increased. The intravenous infusion of glucose at 4 mg/kg.min, which causes increase in excess blood sugar and plasma insulin, increased the alanine flux, but had no effect on the glycine flux. The rate of albumin synthesis, determined by giving 15 N-glycine orally every 3 hr, decreased with the lowered intake of dietary protein in young men, but not in elderly men. This explains why the serum albumin synthesis increases with the increase in the intake of dietary protein in young men, but not in elderly men. The rate of whole body protein synthesis in young men receiving the L-amino acid diets providing with the required intake of specific amino acid was much lower than that in the men receiving the diets providing with generous intake of specific amino acid. Thus the control mechanism to maintain the homeostasis of body nitrogen and amino acids is related in some unknown way to the nutritional requirement of the hosts. (Kaihara, S.)

  13. Improvement in age-related cognitive functions and life expectancy by ketogenic diets

    DEFF Research Database (Denmark)

    Astrup, Arne; Hjorth, Mads Fiil

    2017-01-01

    Rodent studies have indicated that low-carbohydrate diets prevent age-related cognitive decline and extend lifespan due to increased circulating levels of ketone bodies. A possible physiological mechanism for how ketone bodies exert this effect might be by improving central nervous system insulin...

  14. Reaction Engineering of Biocatalytic Enantioselective Reduction: A Case Study for Aliphatic Ketones

    DEFF Research Database (Denmark)

    Leuchs, Susanne; Lima-Ramos, Joana; Greiner, Lasse

    2013-01-01

    , 15, 167–176.). In the present work, the process metrics of the ketone reduction were calculated. A cost analysis revealed that the enzyme costs are negligible, but the cost for nicotinamide cofactor NADP+ is dominating the overall cost of the chemical raw material followed by the ionic liquid (TEGO...... IL K5) used as solubiliser and the buffer. The overall cost of chemicals was €148/kgproduct. To assess the environmental impact of the process, the E-factor (kgwaste/kgproduct) 132 and the process mass intensity 133 (PMI, kgsubstrate/kgproduct) were calculated. A process model based on initial rate...

  15. Calorimeter probes for measuring high thermal flux. [in arc jets

    Science.gov (United States)

    Russell, L. D.

    1979-01-01

    Expendable, slug-type calorimeter probes were developed for measuring high heat-flux levels of 10-30 kW/sq cm in electric-arc jet facilities. The probes were constructed with thin tungsten caps mounted on Teflon bodies. The temperature of the back surface of the tungsten cap is measured, and its time rate of change gives the steady-state absorbed heat flux as the calorimeter probe heats to destruction when inserted into the arc jet. Design, construction, test, and performance data are presented.

  16. Microwave sintering of poly-ether-ether-ketone (PEEK) based coatings deposited on metallic substrate

    International Nuclear Information System (INIS)

    Zhang, G.; Leparoux, S.; Liao, H.; Coddet, C.

    2006-01-01

    In this paper, the feasibility of microwave (MW) sintering PEEK (poly-ether-ether-ketone) based coatings was investigated. Three coatings were studied: pure PEEK, micron-SiC and nano-SiC particles filled (wt.10%) PEEK coatings. The results indicate that, for the two composite coatings, the SiC particles distributed in the polymer matrix, as a good MW susceptor, could be heated preferentially by MW radiation. Consequently, the polymer matrix was heated by these particles

  17. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

    Science.gov (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

    2018-02-01

    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  18. Synthesis and research of derived oxazol-5-ones based on α,β – unsaturated ketones

    Directory of Open Access Journals (Sweden)

    Сергей Александрович Петров

    2015-11-01

    Full Text Available The article deals with the production of new fluorescent dyes derived oxazol-5-ones based on α, β-unsaturated ketones, as well as confirmation of the structure of the compounds obtained using NMR and IR spectroscopy. The dyes of this series are relevant because one of the important practical problems in organic chemistry and chemical technology is currently seeking new fluorescent dyes for dyeing polyester materials and polymers

  19. 210 Pb fluxes in sediment layers sampled from Northern Patagonia lakes

    International Nuclear Information System (INIS)

    Ribeiro Guevara, S.; Sanchez, R.; Arribere, M.; Rizzo, A.

    2003-01-01

    Unsupported 210 Pb fluxes were determined from sediment core inventories in lakes located in Northern Patagonia, Argentina. Total 210 Pb, 226 Ra, associated with supported 210 Pb, and 137 Cs specific activity profiles were measured by gamma-ray spectrometry. Unsupported 210 Pb fluxes showed very low values when compared to other regions, with a 12 fold variation, ranging from 4 to 48 Bq m -2 x y -1 . The linear correlation observed between the 210 Pb fluxes and 137 Cs cumulative fluxes in sediment cores sampled from water bodies within a zone with similar precipitation demonstrated that both radioisotopes behave in the same manner in these systems concerning the processes occurred from fallout to sediment deposition, and that there are no appreciable local or regional sources of unsupported 210 Pb. Positive correlation of 210 Pb fluxes with organic matter contents of the uppermost sediment core layers was also observed. (author)

  20. Asymmetric reduction of ketones and β-keto esters by (S)-1-phenylethanol dehydrogenase from denitrifying bacterium Aromatoleum aromaticum.

    Science.gov (United States)

    Dudzik, A; Snoch, W; Borowiecki, P; Opalinska-Piskorz, J; Witko, M; Heider, J; Szaleniec, M

    2015-06-01

    Enzyme-catalyzed enantioselective reductions of ketones and keto esters have become popular for the production of homochiral building blocks which are valuable synthons for the preparation of biologically active compounds at industrial scale. Among many kinds of biocatalysts, dehydrogenases/reductases from various microorganisms have been used to prepare optically pure enantiomers from carbonyl compounds. (S)-1-phenylethanol dehydrogenase (PEDH) was found in the denitrifying bacterium Aromatoleum aromaticum (strain EbN1) and belongs to the short-chain dehydrogenase/reductase family. It catalyzes the stereospecific oxidation of (S)-1-phenylethanol to acetophenone during anaerobic ethylbenzene mineralization, but also the reverse reaction, i.e., NADH-dependent enantioselective reduction of acetophenone to (S)-1-phenylethanol. In this work, we present the application of PEDH for asymmetric reduction of 42 prochiral ketones and 11 β-keto esters to enantiopure secondary alcohols. The high enantioselectivity of the reaction is explained by docking experiments and analysis of the interaction and binding energies of the theoretical enzyme-substrate complexes leading to the respective (S)- or (R)-alcohols. The conversions were carried out in a batch reactor using Escherichia coli cells with heterologously produced PEDH as whole-cell catalysts and isopropanol as reaction solvent and cosubstrate for NADH recovery. Ketones were converted to the respective secondary alcohols with excellent enantiomeric excesses and high productivities. Moreover, the progress of product formation was studied for nine para-substituted acetophenone derivatives and described by neural network models, which allow to predict reactor behavior and provides insight on enzyme reactivity. Finally, equilibrium constants for conversion of these substrates were derived from the progress curves of the reactions. The obtained values matched very well with theoretical predictions.

  1. Direct Synthesis of Renewable Dodecanol and Dodecane with Methyl Isobutyl Ketone over Dual-Bed Catalyst Systems.

    Science.gov (United States)

    Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Wang, Aiqin; Cong, Yu; Wang, Xiaodong; Zhang, Tao

    2017-03-09

    For the first time, we demonstrated two integrated processes for the direct synthesis of dodecanol or 2,4,8-trimethylnonane (a jet fuel range C 12 -branched alkane) using methyl isobutyl ketone (MIBK) that can be derived from lignocellulose. The reactions were carried out in dual-bed continuous flow reactors. In the first bed, MIBK was selectively converted to a mixture of C 12 alcohol and ketone. Over the Pd-modified magnesium- aluminium hydrotalcite (Pd-MgAl-HT) catalyst, a high total carbon yield (73.0 %) of C 12 oxygenates can be achieved under mild conditions. In the second bed, the C 12 oxygenates generated in the first bed were hydrogenated to dodecanol over a Ru/C catalyst or hydrodeoxygenated to 2,4,8-trimethylnonane over a Cu/SiO 2 catalyst. The as-obtained dodecanol can be used as feedstock in the production of sodium dodecylsulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), which are widely used as surfactants or detergents. The asobtained 2,4,8-trimethylnonane can be blended into conventional jet fuel without hydroisomerization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Relative measurement of the fluxes of thermal, resonant and rapid neutrons in reactor G1; Mesures relatives des flux thermique, resonnant et rapide dans le reacteur G1

    Energy Technology Data Exchange (ETDEWEB)

    Carle, R.; Mazancourt, T. de [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    We sought to determine the behavior of the thermal, resonant and rapid neutron fluxes in the multiplier-reflector transition region, in the two principal directions of the system. We have also measured the variation of these different fluxes in the body of the multiplier medium in a canal filled with graphite and in an empty canal. The results are given in the form of curves representing: - the variation of the ratio of the thermal flux to the rapid flux in axial and radial transitions - the behavior of the thermal and resonant fluxes and the variation of their ratio in the same regions. (author) [French] Nous avons cherche a determiner le comportement des differents flux, thermique, resonnant et rapide a la transition milieu multiplicateur-reflecteur dans les deux directions principales du reseau. Nous avons egalement mesure la variation de ces differents flux au sein du milieu multiplicateur dans un canal rempli de graphite et dans un canal vide. Les resultats sont donnes sous forme de courbe representant: - La variation du rapport du flux thermique au flux rapide aux transitions axiale et radiale - L'allure des flux thermique et resonnant et la variation de leur rapport dans les memes regions. (auteur)

  3. Organic monolith frits encased in polyether ether ketone tubing with improved durability for liquid chromatography.

    Science.gov (United States)

    Park, Sin Young; Cheong, Won Jo

    2015-09-01

    This study introduces a preparation method for polymer-encased monolith frits with improved durability for liquid chromatography columns. The inner surface of the polyether ether ketone tubing is pretreated with sulfuric acid in the presence of catalysts (vanadium oxide and sodium sulfate). The tubing was rinsed with water and acetone, flushed with nitrogen, and treated with glycidyl methacrylate. After washing, the monolith reaction mixture composed of lauryl methacrylate, ethylene glycol dimethacrylate, initiator, and porogenic solvent was filled in the tubing and subjected to in situ polymerization. The tubing was cut into thin slices and used as frits for microcolumns. To check their durability, the frit slices were placed in a vial and a heavy impact was applied on the vial by a vortex mixer for various periods. The frits made in the presence of catalysts were found to be more durable than those made without catalysts. Furthermore, when the monolith-incorporated tubing was used as a chromatography column, the column prepared in the presence of catalysts resulted in a better separation efficiency. The separation performance of the columns installed with the polyether ether ketone encased monolith frits was comparable to that of the columns installed with the commercial stainless-steel screen frits. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Strigolactone analogs derived from ketones using a working model for germination stimulants as a blueprint.

    Science.gov (United States)

    Mwakaboko, Alinanuswe S; Zwanenburg, Binne

    2011-04-01

    Strigolactones are important signaling compounds in the plant kingdom. Here we focus on their germination stimulatory effect on seeds of the parasitic weeds Striga and Orobanche spp. and more particularly on the design and synthesis of new active strigolactone analogs derived from simple cyclic ketones. New analogs derived from 1-indanone, 1-tetralone, cyclopentanone, cyclohexanone and a series of substituted cyclohexanones (including carvone and pulegone) are prepared by formylation of the ketones with ethyl formate followed by coupling with a halo butenolide. Both enantiomers of the analog derived from 1-tetralone have been prepared by employing a homochiral synthon for the coupling reaction. For three other strigolactone analogs the antipodes have been obtained by chromatography on a chiral column. All analogs have an appreciable germinating activity towards seeds of Striga hermomonthica and Orobanche crenata and O. cernua. Stereoisomers having the same configuration at the D-ring as in naturally occurring strigol have a higher stimulatory effect than the corresponding antipodes. The analogs obtained from 1-indanone and 1-tetralone have an activity comparable with that of the well known stimulant GR 24. Analogs derived from 2-phenyl-cylohexanone, carvone and pulegone also have a good germinating response. The results show that the working model for designing new bioactive strigolactones is applicable.

  5. Availability of neurotransmitter glutamate is diminished when beta-hydroxybutyrate replaces glucose in cultured neurons

    DEFF Research Database (Denmark)

    Lund, Trine Meldgaard; Risa, Øystein; Sonnewald, Ursula

    2009-01-01

    Ketone bodies serve as alternative energy substrates for the brain in cases of low glucose availability such as during starvation or in patients treated with a ketogenic diet. The ketone bodies are metabolized via a distinct pathway confined to the mitochondria. We have compared metabolism of [2...

  6. Observing Planets and Small Bodies in Sputtered High Energy Atom (SHEA) Fluxes

    Science.gov (United States)

    Milillo, A.; Orsini, S.; Hsieh, K. C.; Baragiola, R.; Fama, M.; Johnson, R.; Mura, A.; Plainaki, Ch.; Sarantos, M.; Cassidy, T. A.; hide

    2012-01-01

    The evolution of the surfaces of bodies unprotected by either strong magnetic fields or thick atmospheres in the Solar System is caused by various processes, induced by photons, energetic ions and micrometeoroids. Among these processes, the continuous bombardment of the solar wind or energetic magnetospheric ions onto the bodies may significantly affect their surfaces, with implications for their evolution. Ion precipitation produces neutral atom releases into the exosphere through ion sputtering, with velocity distribution extending well above the particle escape limits. We refer to this component of the surface ejecta as sputtered high-energy atoms (SHEA). The use of ion sputtering emission for studying the interaction of exposed bodies (EB) with ion environments is described here. Remote sensing in SHEA in the vicinity of EB can provide mapping of the bodies exposed to ion sputtering action with temporal and mass resolution. This paper speculates on the possibility of performing remote sensing of exposed bodies using SHEA The evolution of the surfaces of bodies unprotected by either strong magnetic fields or thick atmospheres in the Solar System is caused by various processes, induced by photons, energetic ions and micrometeoroids. Among these processes, the continuous bombardment of the solar wind or energetic magnetospheric ions onto the bodies may significantly affect their surfaces, with implications for their evolution. Ion precipitation produces neutral atom releases into the exosphere through ion sputtering, with velocity distribution extending well above the particle escape limits. We refer to this component of the surface ejecta as sputtered high-energy atoms (SHEA). The use of ion sputtering emission for studying the interaction of exposed bodies (EB) with ion environments is described here. Remote sensing in SHEA in the vicinity of EB can provide mapping of the bodies exposed to ion sputtering action with temporal and mass resolution. This paper

  7. Relative measurement of the fluxes of thermal, resonant and rapid neutrons in reactor G1

    International Nuclear Information System (INIS)

    Carle, R.; Mazancourt, T. de

    1957-01-01

    We sought to determine the behavior of the thermal, resonant and rapid neutron fluxes in the multiplier-reflector transition region, in the two principal directions of the system. We have also measured the variation of these different fluxes in the body of the multiplier medium in a canal filled with graphite and in an empty canal. The results are given in the form of curves representing: - the variation of the ratio of the thermal flux to the rapid flux in axial and radial transitions - the behavior of the thermal and resonant fluxes and the variation of their ratio in the same regions. (author) [fr

  8. Metabolic Effects of the Very-Low-Carbohydrate Diets: Misunderstood "Villains" of Human Metabolism

    Directory of Open Access Journals (Sweden)

    Manninen Anssi H

    2004-12-01

    Full Text Available Abstract During very low carbohydrate intake, the regulated and controlled production of ketone bodies causes a harmless physiological state known as dietary ketosis. Ketone bodies flow from the liver to extra-hepatic tissues (e.g., brain for use as a fuel; this spares glucose metabolism via a mechanism similar to the sparing of glucose by oxidation of fatty acids as an alternative fuel. In comparison with glucose, the ketone bodies are actually a very good respiratory fuel. Indeed, there is no clear requirement for dietary carbohydrates for human adults. Interestingly, the effects of ketone body metabolism suggest that mild ketosis may offer therapeutic potential in a variety of different common and rare disease states. Also, the recent landmark study showed that a very-low-carbohydrate diet resulted in a significant reduction in fat mass and a concomitant increase in lean body mass in normal-weight men. Contrary to popular belief, insulin is not needed for glucose uptake and utilization in man. Finally, both muscle fat and carbohydrate burn in an amino acid flame.

  9. Hyperketonemia and ketosis increase the risk of complications in type 1 diabetes.

    Science.gov (United States)

    Kanikarla-Marie, Preeti; Jain, Sushil K

    2016-06-01

    Diets that boost ketone production are increasingly used for treating several neurological disorders. Elevation in ketones in most cases is considered favorable, as they provide energy and are efficient in fueling the body's energy needs. Despite all the benefits from ketones, the above normal elevation in the concentration of ketones in the circulation tend to illicit various pathological complications by activating injurious pathways leading to cellular damage. Recent literature demonstrates a plausible link between elevated levels of circulating ketones and oxidative stress, linking hyperketonemia to innumerable morbid conditions. Ketone bodies are produced by the oxidation of fatty acids in the liver as a source of alternative energy that generally occurs in glucose limiting conditions. Regulation of ketogenesis and ketolysis plays an important role in dictating ketone concentrations in the blood. Hyperketonemia is a condition with elevated blood levels of acetoacetate, 3-β-hydroxybutyrate, and acetone. Several physiological and pathological triggers, such as fasting, ketogenic diet, and diabetes cause an accumulation and elevation of circulating ketones. Complications of the brain, kidney, liver, and microvasculature were found to be elevated in diabetic patients who had elevated ketones compared to those diabetics with normal ketone levels. This review summarizes the mechanisms by which hyperketonemia and ketoacidosis cause an increase in redox imbalance and thereby increase the risk of morbidity and mortality in patients. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Convenient synthesis of non-conjugated alkynyl ketones from keto aldehydes by a chemoselective one-pot nonaflation-base catalyzed elimination sequence

    Czech Academy of Sciences Publication Activity Database

    Boltukhina, Ekaterina; Sheshenev, Andrey; Lyapkalo, Ilya

    2011-01-01

    Roč. 67, č. 30 (2011), s. 5382-5388 ISSN 0040-4020 Institutional research plan: CEZ:AV0Z40550506 Keywords : nonaflation * alkynyl ketones * cross-coupling * elimination * phosphazene base Subject RIV: CC - Organic Chemistry Impact factor: 3.025, year: 2011

  11. Enhancement of magnetic flux distribution in a DC superconducting electric motor

    International Nuclear Information System (INIS)

    Hamid, N A; Ewe, L S; Chin, K M

    2013-01-01

    Most motor designs require an air gap between the rotor and stator to enable the armature to rotate freely. The interaction of magnetic flux from rotor and stator within the air gap will provide the thrust for rotational motion. Thus, the understanding of magnetic flux in the vicinity of the air gap is very important to mathematically calculate the magnetic flux generated in the area. In this work, a finite element analysis was employed to study the behavior of the magnetic flux in view of designing a synchronous DC superconducting electric motor. The analysis provides an ideal magnetic flux distribution within the components of the motor. From the flux plot analysis, it indicates that flux losses are mainly in the forms of leakage and fringe effect. The analysis also shows that the flux density is high at the area around the air gap and the rotor. The high flux density will provide a high force area that enables the rotor to rotate. In contrast, the other parts of the motor body do not show high flux density indicating low distribution of flux. Consequently, a bench top model of a DC superconducting motor was developed where by motor with a 2-pole type winding was chosen. Each field coil was designed with a racetrack-shaped double pancake wound using DI-BSCCO Bi-2223 superconducting tapes. The performance and energy efficiency of the superconducting motor was superior when compared to the conventional motor with similar capacity.

  12. Clinical utility of Abbott Precision Xceed Pro® ketone meter in diabetic patients.

    Science.gov (United States)

    Yu, Hoi-Ying Elsie; Agus, Michael; Kellogg, Mark D

    2011-11-01

    Diagnosis and management of diabetic ketoacidosis (DKA) often rely on the measurement of urine ketones along with blood glucose, anion gap, and pH. These values, however, do not reliably reflect the severity of ketoacidosis. The Abbott Precision Xceed Pro® meter is an FDA-approved device that quantitatively measures β-hydroxybutyrate (BOH) in whole blood. This study was undertaken to determine whether the ketone meter meets the analytical criteria to aid DKA diagnosis and management in the hospital. 54 heparinized venous whole blood BOH concentrations from 27 diabetic patients were measured by the Abbott meter, and compared with the plasma BOH concentrations measured with Stanbio reagent (reference method). Measurements were done in the hospital central laboratory. Of the 54 pairs of specimens analyzed, 17 pairs displayed a difference of >15% between the two methods. Nearly all discrepant points occurred when BOH >5 mmol/L (reference method). Linearity evaluation revealed that the meter is not linear from 0.0 to 8.0 mmol/L, contrary to the claim by the manufacturer. Further, we identified acetoacetate, a metabolite commonly present in DKA patients, as a potential interfering substance for the meter BOH measurement. BOH measurements by the Abbott meter up to 3 mmol/L correlate well with the reference method, but become discrepant above that point. While this characteristic may be useful in the diagnosis of DKA, it may not allow clinicians to serially follow the response to therapy in hospitalized DKA patients with BOH values greater than 5 mmol/L (reference method). © 2011 John Wiley & Sons A/S.

  13. Nitrates in Groundwater Discharges from the Azores Archipelago: Occurrence and Fluxes to Coastal Waters

    Directory of Open Access Journals (Sweden)

    J. Virgílio Cruz

    2017-02-01

    Full Text Available Groundwater discharge is an important vector of chemical fluxes to the ocean environment, and as the concentration of nutrients is often higher in discharging groundwater, the deterioration of water quality in the receiving environment can be the result. The main objective of the present paper is to estimate the total NO3 flux to coastal water bodies due to groundwater discharge in the volcanic Azores archipelago (Portugal. Therefore, 78 springs discharging from perched-water bodies have been monitored since 2003, corresponding to cold (mean = 14.9 °C and low mineralized (47.2–583 µS/cm groundwater from the sodium-bicarbonate to sodium-chloride water types. A set of 36 wells was also monitored, presenting groundwater with a higher mineralization. The nitrate content in springs range between 0.02 and 37.4 mg/L, and the most enriched samples are associated to the impact of agricultural activities. The total groundwater NO3 flux to the ocean is estimated in the range of 5.23 × 103 to 190.6 × 103 mol/km2/a (∑ = ~523 × 103 mol/km2/a, exceeding the total flux associated to surface runoff (∑ = ~281 × 103 mol/km2/a. In the majority of the islands, the estimated fluxes are higher than runoff fluxes, with the exception of Pico (47.2%, Corvo (46% and Faial (7.2%. The total N-NO3 flux estimated in the Azores (~118.9 × 103 mol/km2/a is in the lower range of estimates made in other volcanic islands.

  14. Microbial transformation of sesquitepenoid ketone, (+ Nootkatone by Macrophomia phaseolina

    Directory of Open Access Journals (Sweden)

    Vajira P. Bulugahapitiya

    2009-09-01

    Full Text Available Microbial transformation is an effective tool for the structural modification of bioactive natural and synthetic compounds leading to synthesis of more potent derivatives. Its application in asymmetric synthesis is increasing due to its versatility and ease. This article presents biotransformation of sesquiterpenoid ketone, (+-Nootkatone (1 by M. phaseolina, a plant pathogenic fungus. The transformation afforded four main compounds. They were determined to be 1:6 stereoisomeric mixture of 11,12-dihydroxy- 11,12-dihydronootkatone (2, 3, 13-hydroxynootkaone (4 and 12-hydroxy-11,12- dihydronootkatone (5 with the help of EI-MS, HR-FAB-MS(pos, HR-FAB-MS (neg, 1H-NMR, 13CNMR, COSY-450, NOESY, HMBC, HMQC spectral analyses. The compound 4 was firstchandana- amarasingha-samayawardana-avifauna-Bundala-1.1-28.07 identified as Nootkatone metabolites in this study. Further, the parental compound (1 and the transformed products 4 and 5 were found to be present significant antiprotozoal activity.

  15. Determination of acetone and methyl ethyl ketone in water

    Science.gov (United States)

    Tai, D.Y.

    1978-01-01

    Analytical procedures for the determination of acetone and methyl ethyl ketone in water samples were developed. Concentrations in the milligram-per-liter range were determined by injecting an aqueous sample into the analysis system through an injection port, trapping the organics on Tenax-GC at room temperature, and thermally desorbing the organics into a gas chromatograph with a flame ionization detector for analysis. Concentrations in the microgram-per-liter range were determined by sweeping the headspace vapors over a water sample at 50C, trapping on Tenax-GC, and thermally desorbing the organics into the gas chromatograph. The precision for two operators of the milligram-per-liter concentration procedure, expressed as the coefficient of variation, was generally less than 2 percent for concentrations ranging from 16 to 160 milligrams per liter. The precision from two operators of the microgram-per-liter concentration procedure was between 2 and 4 percent for concentrations of 20 and 60 micrograms per liter. (Woodard-USGS)

  16. N-Heterocyclic Carbene-Catalyzed Olefination of Aldehydes with Vinyliodonium Salts To Generate α,β-Unsaturated Ketones.

    Science.gov (United States)

    Rajkiewicz, Adam A; Kalek, Marcin

    2018-04-06

    An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.

  17. Solar flux incident on an orbiting surface after reflection from a planet

    Science.gov (United States)

    Modest, M. F.

    1980-01-01

    Algorithms describing the solar radiation impinging on an infinitesimal surface after reflection from a gray and diffuse planet are derived. The following conditions apply: only radiation from the sunny half of the planet is taken into account; the radiation must fall on the top of the orbiting surface, and radiation must come from that part of the planet that can be seen from the orbiting body. A simple approximate formula is presented which displays excellent accuracy for all significant situations, with an error which is always less than 5% of the maximum possible reflected flux. Attention is also given to solar albedo flux on a surface directly facing the planet, the influence of solar position on albedo flux, and to solar albedo flux as a function of the surface-planet tilt angle.

  18. FINE-SCALE STRUCTURES OF FLUX ROPES TRACKED BY ERUPTING MATERIAL

    Energy Technology Data Exchange (ETDEWEB)

    Li Ting; Zhang Jun, E-mail: liting@nao.cas.cn, E-mail: zjun@nao.cas.cn [Key Laboratory of Solar Activity, National Astronomical Observatories, Chinese Academy of Sciences, Beijing 100012 (China)

    2013-06-20

    We present Solar Dynamics Observatory observations of two flux ropes tracked out by material from a surge and a failed filament eruption on 2012 July 29 and August 4, respectively. For the first event, the interaction between the erupting surge and a loop-shaped filament in the east seems to 'peel off' the filament and add bright mass into the flux rope body. The second event is associated with a C-class flare that occurs several minutes before the filament activation. The two flux ropes are, respectively, composed of 85 {+-} 12 and 102 {+-} 15 fine-scale structures, with an average width of about 1.''6. Our observations show that two extreme ends of the flux rope are rooted in opposite polarity fields and each end is composed of multiple footpoints (FPs) of fine-scale structures. The FPs of the fine-scale structures are located at network magnetic fields, with magnetic fluxes from 5.6 Multiplication-Sign 10{sup 18} Mx to 8.6 Multiplication-Sign 10{sup 19} Mx. Moreover, almost half of the FPs show converging motion of smaller magnetic structures over 10 hr before the appearance of the flux rope. By calculating the magnetic fields of the FPs, we deduce that the two flux ropes occupy at least 4.3 Multiplication-Sign 10{sup 20} Mx and 7.6 Multiplication-Sign 10{sup 20} Mx magnetic fluxes, respectively.

  19. EFSA ; Scientific Opinion on Flavouring Group Evaluation 63, Revision 1 (FGE.63Rev1): Consideration of aliphatic secondary alcohols, ketones and related esters evaluated by JECFA (59th and 69th meetings) structurally related to saturated and unsaturated aliphatic secondary alcohols, ketones

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 19 aliphatic secondary alcohols, ketones and related esters evaluated by the JECFA at the 59th and 69th meetings in 2002 and 2008. This revision is made due to inclusion of six...

  20. Effects of lactone, ketone, and phenolic compounds on methane production and metabolic intermediates during anaerobic digestion.

    Science.gov (United States)

    Wikandari, Rachma; Sari, Noor Kartika; A'yun, Qurrotul; Millati, Ria; Cahyanto, Muhammad Nur; Niklasson, Claes; Taherzadeh, Mohammad J

    2015-02-01

    Fruit waste is a potential feedstock for biogas production. However, the presence of fruit flavors that have antimicrobial activity is a challenge for biogas production. Lactones, ketones, and phenolic compounds are among the several groups of fruit flavors that are present in many fruits. This work aimed to investigate the effects of two lactones, i.e., γ-hexalactone and γ-decalactone; two ketones, i.e., furaneol and mesifurane; and two phenolic compounds, i.e., quercetin and epicatechin on anaerobic digestion with a focus on methane production, biogas composition, and metabolic intermediates. Anaerobic digestion was performed in a batch glass digester incubated at 55 °C for 30 days. The flavor compounds were added at concentrations of 0.05, 0.5, and 5 g/L. The results show that the addition of γ-decalactone, quercetin, and epicathechin in the range of 0.5-5 g/L reduced the methane production by 50 % (MIC50). Methane content was reduced by 90 % with the addition of 5 g/L of γ-decalactone, quercetin, and epicathechin. Accumulation of acetic acid, together with an increase in carbon dioxide production, was observed. On the contrary, γ-hexalactone, furaneol, and mesifurane increased the methane production by 83-132 % at a concentration of 5 g/L.

  1. Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2010-01-01

    Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact...... angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes...

  2. Polyether ether ketone implants achieve increased bone fusion when coated with nano-sized hydroxyapatite

    DEFF Research Database (Denmark)

    Johansson, Pär; Jimbo, Ryo; Naito, Yoshihito

    2016-01-01

    Polyether ether ketone (PEEK) possesses excellent mechanical properties similar to those of human bone and is considered the best alternative material other than titanium for orthopedic spine and trauma implants. However, the deficient osteogenic properties and the bioinertness of PEEK limit its...... fields of application. The aim of this study was to limit these drawbacks by coating the surface of PEEK with nano-scaled hydroxyapatite (HA) minerals. In the study, the biological response to PEEK, with and without HA coating, was investigated. Twenty-four screw-like and apically perforated implants...

  3. Thermal Stability of Sulfonated Poly(Ether Ether Ketone) Films: on the Role of Protodesulfonation

    OpenAIRE

    Koziara, Beata; Kappert, Emiel; Ogieglo, Wojciech; Nijmeijer, Dorothea C.; Hempenius, Mark A.; Benes, Nieck Edwin

    2016-01-01

    Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material, most likely via a slight cross-linking by H-substitution. It is well-known that the sulfonate proton plays a major role in the desulfonation reactions, and exchanging the protons with other cations ...

  4. Synthesis of enantiomerically enriched drug precursors and an insect pheromone via reduction of ketones using commercially available carbonyl reductase screening kit "Chiralscreen® OH".

    Science.gov (United States)

    Nagai, Toshiya; Sakurai, Saki; Natori, Naoki; Hataoka, Manaka; Kinoshita, Takako; Inoue, Hiroyoshi; Hanaya, Kengo; Shoji, Mitsuru; Sugai, Takeshi

    2018-04-01

    Commercially available "Chiralscreen® OH" starter kit containing five types of carbonyl reductases (E001, E007, E031, E039, and E078) was used for the reduction of several aromatic and aliphatic ketones to obtain enantiomerically enriched drug precursors and an insect pheromone. Almost stereochemically pure secondary alcohols, used in the synthesis of drugs such as (R)-rasagiline mesylate, (S)-rivastigmine, (R)-chlorphenesin carbamate, and (R)-mexiletine, and the insect pheromone (4S,5R)-sitophilure, were conveniently obtained. The enzymes worked well with ketones containing at least one non-bulky substituent at the carbonyl group. The diverse stereochemical preference of the above five carbonyl reductases was clarified. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Solvent-free synthesis of C10 and C11 branched alkanes from furfural and methyl isobutyl ketone.

    Science.gov (United States)

    Yang, Jinfan; Li, Ning; Li, Guangyi; Wang, Wentao; Wang, Aiqin; Wang, Xiaodong; Cong, Yu; Zhang, Tao

    2013-07-01

    Our best results jet: C10 and C11 branched alkanes, with low freezing points, are synthesized through the aldol condensation of furfural and methyl isobutyl ketone from lignocellulose, which is then followed by hydrodeoxygenation. These jet-fuel-range alkanes are obtained in high overall yields (≈90%) under solvent-free conditions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Copper-catalyzed transformation of ketones to amides via C(CO)-C(alkyl) bond cleavage directed by picolinamide.

    Science.gov (United States)

    Ma, Haojie; Zhou, Xiaoqiang; Zhan, Zhenzhen; Wei, Daidong; Shi, Chong; Liu, Xingxing; Huang, Guosheng

    2017-09-13

    Copper catalyzed chemoselective cleavage of the C(CO)-C(alkyl) bond leading to C-N bond formation with chelation assistance of N-containing directing groups is described. Inexpensive Cu(ii)-acetate serves as a convenient catalyst for this transformation. This method highlights the emerging strategy to transform unactivated alkyl ketones into amides in organic synthesis and provides a new strategy for C-C bond cleavage.

  7. Detection of Subclinical Ketosis in Dairy Cows

    Directory of Open Access Journals (Sweden)

    Zhigang Zhang, Guowen Liu1, Hongbin Wang, Xiaobing Li1 and Zhe Wang1*

    2012-05-01

    Full Text Available Ketosis is a common metabolic disorder frequently observed in dairy cows during the early lactation period. It is characterized by increased levels of ketone bodies in the blood, urine, and milk. Subclinical ketosis (SCK in dairy cattle is an excess level of circulating ketone bodies in the absence of clinical signs of ketosis. Usually, detection of SCK is carried out by testing the ketone concentrations in blood, urine, and milk. Here, This review overview the detection methods for SCK in dairy cows, including cowside and laboratory tests.

  8. CO2 as a C1-organic building block: Enantioselective electrocarboxylation of aromatic ketones with CO2catalyzed by cinchona alkaloids under mild conditions

    International Nuclear Information System (INIS)

    Chen, Bao-Li; Tu, Zhuo-Ying; Zhu, Hong-Wei; Sun, Wen-Wen; Wang, Huan; Lu, Jia-Xing

    2014-01-01

    Highlights: •Cinchona alkaloids catalysis achieve enantioselective electrocarboxylation of racemic aromatic ketones. •The applications of CO 2 enantioselective electrochemical fixation into optically active hydroxyl carboxylic acids have been expanded. •The applications of alkaloids have been expanded. •The applications of asymmetric synthesis by electrochemical methodology have been expanded. -- Abstract: The enantioselective electrocarboxylation of pro-chiral aromatic ketones (2-acetonaphthone, 1-(6-methoxy-2-naphthyl)ethanone, 1-(4-methoxy-1-naphthyl)ethanone) with atmospheric pressure of CO 2 catalyzed by cinchona alkaloids in the presence of phenol was investigated in an undivided cell for the first time to give optically active 2-hydroxy-2-arylpropionic acid. For the model compound 2-acetonaphthone, the influence of various reaction conditions, such as cathode material, current density, catalyst type, ratio of proton to catalyst and catalyst quantity, on the enantiomeric excesses (ee) and yield has been investigated. Under the optimized conditions of 2-acetonaphthone, all the aromatic ketones examined are converted into corresponding optically active 2-hydroxy-2-arylpropionic acids in moderate yield (32.2% - 41.3%) and ee (48.1% - 48.6%). In addition, the electrochemical behavior of 2-acetonaphthone has been studied by cyclic voltammetry (CV) in the absence and presence of CO 2 . Moreover, the probable reaction pathway was proposed accordingly

  9. Acid-base and ionic fluxes in rainbow trout (Oncorhynchus mykiss) during exposure to chloramine-T

    Energy Technology Data Exchange (ETDEWEB)

    Powell, M.D.; Perry, S.F. [Department of Biology, University of Ottawa, 30 Marie Curie Ottawa, Ontario, K1N 6N5 (Canada)

    1998-09-01

    The effects of chloramine-T and its degradation products, sodium hypochlorite (NaOCl) and para-toluenesulphonamide (pTSA), on whole body acid-base and branchial and renal ion (Na{sup +}and Cl{sup -}) fluxes were examined in rainbow trout (Oncorhynchus mykiss). Exposure to chloramine-T (3.5 h, 18 mg l{sup -1}) resulted in increases in plasma total CO{sub 2} but no coincident rise in P{sub a}CO{sub 2} or reduction in blood pH. Exposure of fish to 2, 9 or 18 mg l{sup -1} chloramine-T (3.5 h duration) resulted in a reduction in net acid uptake suggesting the development of a metabolic alkalosis. Exposure to the chloramine-T breakdown product pTSA (dissolved in DMSO) resulted in increased net acid uptake (decreased acid excretion) suggesting a metabolic acidosis. Whole body ion fluxes demonstrated increases in the losses of both Na{sup +}and Cl{sup -} with chloramine-T, NaOCl and pTSA. However, the effect of DMSO alone could not be isolated. Confirmatory studies using fish in which the urinary bladder (to allow collection of urine) and dorsal aorta (to allow injection of [{sup 14}C]polyethylene glycol 4000 ([{sup 14}C]PEG), an extracellular fluid marker) were catheterised, revealed that changes in whole body ion fluxes during chloramine-T exposure could not be explained by increased renal efflux through urine flow, glomerular filtration or renal clearance. Branchial effluxes of [{sup 14}C]PEG were not significantly affected by chloramine-T exposure suggesting that the changes in whole body ionic fluxes were caused by transcellular rather than paracellular processes. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  10. Acid-base and ionic fluxes in rainbow trout (Oncorhynchus mykiss) during exposure to chloramine-T

    International Nuclear Information System (INIS)

    Powell, M.D.; Perry, S.F.

    1998-01-01

    The effects of chloramine-T and its degradation products, sodium hypochlorite (NaOCl) and para-toluenesulphonamide (pTSA), on whole body acid-base and branchial and renal ion (Na + and Cl - ) fluxes were examined in rainbow trout (Oncorhynchus mykiss). Exposure to chloramine-T (3.5 h, 18 mg l -1 ) resulted in increases in plasma total CO 2 but no coincident rise in P a CO 2 or reduction in blood pH. Exposure of fish to 2, 9 or 18 mg l -1 chloramine-T (3.5 h duration) resulted in a reduction in net acid uptake suggesting the development of a metabolic alkalosis. Exposure to the chloramine-T breakdown product pTSA (dissolved in DMSO) resulted in increased net acid uptake (decreased acid excretion) suggesting a metabolic acidosis. Whole body ion fluxes demonstrated increases in the losses of both Na + and Cl - with chloramine-T, NaOCl and pTSA. However, the effect of DMSO alone could not be isolated. Confirmatory studies using fish in which the urinary bladder (to allow collection of urine) and dorsal aorta (to allow injection of [ 14 C]polyethylene glycol 4000 ([ 14 C]PEG), an extracellular fluid marker) were catheterised, revealed that changes in whole body ion fluxes during chloramine-T exposure could not be explained by increased renal efflux through urine flow, glomerular filtration or renal clearance. Branchial effluxes of [ 14 C]PEG were not significantly affected by chloramine-T exposure suggesting that the changes in whole body ionic fluxes were caused by transcellular rather than paracellular processes. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  11. Prediction of human core body temperature using non-invasive measurement methods.

    Science.gov (United States)

    Niedermann, Reto; Wyss, Eva; Annaheim, Simon; Psikuta, Agnes; Davey, Sarah; Rossi, René Michel

    2014-01-01

    The measurement of core body temperature is an efficient method for monitoring heat stress amongst workers in hot conditions. However, invasive measurement of core body temperature (e.g. rectal, intestinal, oesophageal temperature) is impractical for such applications. Therefore, the aim of this study was to define relevant non-invasive measures to predict core body temperature under various conditions. We conducted two human subject studies with different experimental protocols, different environmental temperatures (10 °C, 30 °C) and different subjects. In both studies the same non-invasive measurement methods (skin temperature, skin heat flux, heart rate) were applied. A principle component analysis was conducted to extract independent factors, which were then used in a linear regression model. We identified six parameters (three skin temperatures, two skin heat fluxes and heart rate), which were included for the calculation of two factors. The predictive value of these factors for core body temperature was evaluated by a multiple regression analysis. The calculated root mean square deviation (rmsd) was in the range from 0.28 °C to 0.34 °C for all environmental conditions. These errors are similar to previous models using non-invasive measures to predict core body temperature. The results from this study illustrate that multiple physiological parameters (e.g. skin temperature and skin heat fluxes) are needed to predict core body temperature. In addition, the physiological measurements chosen in this study and the algorithm defined in this work are potentially applicable as real-time core body temperature monitoring to assess health risk in broad range of working conditions.

  12. The performance of a glucose-ketone meter in the diagnosis of diabetic ketoacidosis in patients with type 2 diabetes in the emergency room.

    Science.gov (United States)

    Voulgari, Christina; Tentolouris, Nicholas

    2010-07-01

    Diabetic ketoacidosis (DKA) is a serious metabolic complication. One of its precipitating causes is insulin omission. DKA requires early diagnosis and strict glucose control, which increases the use of glucose meters in the Emergency Room (ER). We aimed to determine the performance of a glucose-ketone meter in the diagnosis of DKA. From 450 type 2 diabetes mellitus insulin-treated patients attending the ER with a capillary glucose level >13.9 mmol/L, 50 patients (26 men and 24 women, mean age 60.2 +/- 8.2 years) had DKA. Capillary glucose and beta-hydroxybutyrate (beta-OHB) were measured with the Precision-Xtra device (Abbott Laboratories, Abingdon, UK). Serum glucose and biochemical parameters were measured on an automatic analyzer; serum beta-OHB was determined using an enzymatic end-point spectrophotometric method. Urine ketones were determined using a semiquantitative assay (Ketodiastix, Bayer Diagnostics, Stoke Poges, Slough, UK). Serum and capillary beta-OHB values were highly correlated (r = 0.99, P 3.0 mmol/L) had the highest performance (sensitivity 99.87%, specificity 92.89%, positive predictive value 92.89%) for the diagnosis of DKA compared with serum ketonemia (sensitivity 90.45%, specificity 88.65%, positive predictive value 87.76%) or ketonuria (sensitivity 89.89%, specificity 52.73%, positive predictive value 41.87%). Implementation of measures such as home glucose and ketone monitoring can possibly decrease the number of hospital admissions due to DKA.

  13. Craniofacial reconstruction using patient-specific implants polyether ether ketone with computer-assisted planning.

    Science.gov (United States)

    Manrique, Oscar J; Lalezarzadeh, Frank; Dayan, Erez; Shin, Joseph; Buchbinder, Daniel; Smith, Mark

    2015-05-01

    Reconstruction of bony craniofacial defects requires precise understanding of the anatomic relationships. The ideal reconstructive technique should be fast as well as economical, with minimal donor-site morbidity, and provide a lasting and aesthetically pleasing result. There are some circumstances in which a patient's own tissue is not sufficient to reconstruct defects. The development of sophisticated software has facilitated the manufacturing of patient-specific implants (PSIs). The aim of this study was to analyze the utility of polyether ether ketone (PEEK) PSIs for craniofacial reconstruction. We performed a retrospective chart review from July 2009 to July 2013 in patients who underwent craniofacial reconstruction using PEEK-PSIs using a virtual process based on computer-aided design and computer-aided manufacturing. A total of 6 patients were identified. The mean age was 46 years (16-68 y). Operative indications included cancer (n = 4), congenital deformities (n = 1), and infection (n = 1). The mean surgical time was 3.7 hours and the mean hospital stay was 1.5 days. The mean surface area of the defect was 93.4 ± 43.26 cm(2), the mean implant cost was $8493 ± $837.95, and the mean time required to manufacture the implants was 2 weeks. No major or minor complications were seen during the 4-year follow-up. We found PEEK implants to be useful in the reconstruction of complex calvarial defects, demonstrating a low complication rate, good outcomes, and high patient satisfaction in this small series of patients. Polyether ether ketone implants show promising potential and warrant further study to better establish the role of this technology in cranial reconstruction.

  14. Combination of Scanning Probe Microscopy and Coordination Chemistry: Structural and Electronic Study of Bis(methylbenzimidazolyl)ketone and Its Iron Complex

    NARCIS (Netherlands)

    Folkertsma, Emma; Van Der Lit, Joost; Di Cicco, Francesca; Lutz, Martin; Klein Gebbink, Robertus J. M.; Swart, Ingmar; Moret, Marc-etienne

    2017-01-01

    Here, we report the bulk synthesis of [FeII(BMBIK)Cl2] bearing the redox noninnocent bis(methylbenzimidazolyl)ketone (BMBIK) ligand and the synthesis of the similar complex [FeI(BMBIK)]+ on a Au(111) surface using lateral manipulation at the atomic level. Cyclic voltammetry and scanning tunneling

  15. Bias voltage dependence of molecular orientation of dialkyl ketone and fatty acid alkyl ester at the liquid–graphite interface

    Energy Technology Data Exchange (ETDEWEB)

    Hibino, Masahiro, E-mail: hibino@mmm.muroran-it.ac.jp [Department of Applied Sciences, Muroran Institute of Technology, 27-1 Mizumoto-cho, Muroran 050-8585 (Japan); Tsuchiya, Hiroshi [Department of Applied Physics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601 (Japan)

    2014-10-30

    Graphical abstract: - Highlights: • Self-assembled monolayers (SAMs) of 18-pentatriacontanone (as ketone) and stearyl stearate (as ester) were formed on a graphite surface at the liquid–solid interface. • Orientations of the molecules in SAMs on the substrate were studied by scanning tunneling microscopy. • A perpendicular carbon skeleton-plane orientation with the CO pointing up on the surface is favorable for a substrate with negative charge and vice versa. - Abstract: Molecular orientations of self-assembled 18-pentatriacontanone (as ketone) and stearyl stearate (as ester) monolayers adsorbed on a graphite surface were studied by scanning tunneling microscopy (STM) at the liquid–solid interface. At a positive sample bias, the central areas of the dialkyl ketone and fatty acid alkyl ester molecules in the STM images appeared as two bright regions on both sides of a dim spot and a bright region on one side of a dim spot, whereas at a negative sample bias, the areas appeared dim. This contrast variation indicates that a perpendicular carbon skeleton-plane orientation with the CO pointing down on the surface is favorable for a substrate with positive charge and vice versa because of the greater electronegativity of the oxygen atom. Upon the bias voltage reversal, the delay time for the STM image contrast change in the region was observed on a time scale of minutes. The difference between the delay time lengths for the direction of bias polarity change indicates that the perpendicular configuration with CO pointing up is more stable than that with CO pointing down. These results indicate that the use of an electric field along a direction vertical to the monolayer on the substrate provides control over the orientations of the molecules between two stable states at the liquid–solid interface.

  16. Highly Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram.

    Science.gov (United States)

    Huang, Linwei; Zhu, Jinbin; Jiao, Guangjun; Wang, Zheng; Yu, Xingxin; Deng, Wei-Ping; Tang, Wenjun

    2016-03-24

    Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)-WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. From elementary flux modes to elementary flux vectors: Metabolic pathway analysis with arbitrary linear flux constraints

    Science.gov (United States)

    Klamt, Steffen; Gerstl, Matthias P.; Jungreuthmayer, Christian; Mahadevan, Radhakrishnan; Müller, Stefan

    2017-01-01

    Elementary flux modes (EFMs) emerged as a formal concept to describe metabolic pathways and have become an established tool for constraint-based modeling and metabolic network analysis. EFMs are characteristic (support-minimal) vectors of the flux cone that contains all feasible steady-state flux vectors of a given metabolic network. EFMs account for (homogeneous) linear constraints arising from reaction irreversibilities and the assumption of steady state; however, other (inhomogeneous) linear constraints, such as minimal and maximal reaction rates frequently used by other constraint-based techniques (such as flux balance analysis [FBA]), cannot be directly integrated. These additional constraints further restrict the space of feasible flux vectors and turn the flux cone into a general flux polyhedron in which the concept of EFMs is not directly applicable anymore. For this reason, there has been a conceptual gap between EFM-based (pathway) analysis methods and linear optimization (FBA) techniques, as they operate on different geometric objects. One approach to overcome these limitations was proposed ten years ago and is based on the concept of elementary flux vectors (EFVs). Only recently has the community started to recognize the potential of EFVs for metabolic network analysis. In fact, EFVs exactly represent the conceptual development required to generalize the idea of EFMs from flux cones to flux polyhedra. This work aims to present a concise theoretical and practical introduction to EFVs that is accessible to a broad audience. We highlight the close relationship between EFMs and EFVs and demonstrate that almost all applications of EFMs (in flux cones) are possible for EFVs (in flux polyhedra) as well. In fact, certain properties can only be studied with EFVs. Thus, we conclude that EFVs provide a powerful and unifying framework for constraint-based modeling of metabolic networks. PMID:28406903

  18. EFSA Scientific Opinion on Flavouring Group Evaluation 87 Revision 1 (FGE.87Rev1): Consideration of bicyclic secondary alcohols, ketones and related esters evaluated by JECFA (63rd meeting) structurally related to bicyclic secondary alcohols, ketones and related esters evaluated by EFSA in FGE.47

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 17 bicyclic secondary alcohols, ketones and related esters evaluated by the JECFA at the 63rd meeting in 2004. This revision of FGE.87 is made due to consideration of two additional...

  19. Bioimpedance measurement of body water correlates with measured volume balance in injured patients.

    Science.gov (United States)

    Rosemurgy, A S; Rodriguez, E; Hart, M B; Kurto, H Z; Albrink, M H

    1993-06-01

    Bioimpedance technology is being used increasingly to determine drug volume of distribution, body water status, and nutrition repletion. Its accuracy in patients experiencing large volume flux is not established. To address this, we undertook this prospective study in 54 consecutive seriously injured adults who had emergency celiotomy soon after arrival in the emergency department. Bioimpedance measurements were obtained in the emergency department before the patient was transported to the operating room, on completion of celiotomy, and 24 hours and 48 hours after celiotomy. Bioimpedance measurements of body water were compared with measured fluid balance. If insensible losses are subtracted from measured fluid balance, the percentage of body weight, which is body water determined by bioimpedance, closely follows fluid flux. This study supports the use of bioimpedance measurements in determining total body water even during periods of surgery, blood loss, and vigorous resuscitation.

  20. The Influence of Operation Temperature of the Characteristic of Sulfonated Polyether-Ether Ketone Electrolyte Membrane

    International Nuclear Information System (INIS)

    Sri Handayani; Eniya Listiani Dewi

    2008-01-01

    Recently, high temperature Direct Methanol Fuel Cell (DMFC) has been receiving great attention, because provide faster reaction kinetic, the enhance electrode kinetics, reduced size and reduce Pt-based catalyst poisoning by CO. But at high temperature, it will decrease the membrane performance i.e. low proton conductivity affected by humidification and high methanol crossover as happening to Nafion-117 membrane (commercial membrane). To solve this problems, sulfonated polyether-ether ketone and composite (silica additive) as electrolyte membrane at high temperature DMFC was tried to use. In this research, sPEEK with sulfonation degree (SD) 47 % and 68 % and addition silica 3 wt % were used as electrolyte membranes. Proton conductivity and methanol permeability of these membranes were measured at various temperatures (25, 50, 90 and 140 C ). Proton conductivity of membranes were measured by standard bridge impedance spectroscopy (LCR-meter, HIOKI 3522-50) and it was found about 0.01-0.04 S/cm. Methanol permeability of membranes were investigated by diffusion cell and gave the result about 10 - 6 - 10 - 7cm 2 /s. The best sPEEK membrane was sPEEK membrane with SD 68 % and the addition of silica 3 wt%, signed by highest selectivity value (ratio proton conductivity to methanol permeability). Therefore, electrolyte membrane based sulfonated polyether-ether ketone (SD 68 %) with silica could be used at high temperature which give promising as solid electrolyte membrane in application high temperature DMFC. (author)

  1. FluxVisualizer, a Software to Visualize Fluxes through Metabolic Networks

    Directory of Open Access Journals (Sweden)

    Tim Daniel Rose

    2018-04-01

    Full Text Available FluxVisualizer (Version 1.0, 2017, freely available at https://fluxvisualizer.ibgc.cnrs.fr is a software to visualize fluxes values on a scalable vector graphic (SVG representation of a metabolic network by colouring or increasing the width of reaction arrows of the SVG file. FluxVisualizer does not aim to draw metabolic networks but to use a customer’s SVG file allowing him to exploit his representation standards with a minimum of constraints. FluxVisualizer is especially suitable for small to medium size metabolic networks, where a visual representation of the fluxes makes sense. The flux distribution can either be an elementary flux mode (EFM, a flux balance analysis (FBA result or any other flux distribution. It allows the automatic visualization of a series of pathways of the same network as is needed for a set of EFMs. The software is coded in python3 and provides a graphical user interface (GUI and an application programming interface (API. All functionalities of the program can be used from the API and the GUI and allows advanced users to add their own functionalities. The software is able to work with various formats of flux distributions (Metatool, CellNetAnalyzer, COPASI and FAME export files as well as with Excel files. This simple software can save a lot of time when evaluating fluxes simulations on a metabolic network.

  2. Density, viscosity, isothermal (vapour + liquid) equilibrium, excess molar volume, viscosity deviation, and their correlations for chloroform + methyl isobutyl ketone binary system

    International Nuclear Information System (INIS)

    Clara, Rene A.; Gomez Marigliano, Ana C.; Solimo, Horacio N.

    2007-01-01

    Density and viscosity measurements for pure chloroform and methyl isobutyl ketone at T = (283.15, 293.15, 303.15, and 313.15) K as well as for the binary system {x 1 chloroform + (1 - x 1 ) methyl isobutyl ketone} at the same temperatures were made over the whole concentration range. The experimental results were fitted to empirical equations, which permit the calculation of these properties over the whole concentration and temperature ranges studied. Data of the binary mixture were further used to calculate the excess molar volume and viscosity deviation. The (vapour + liquid) equilibrium (VLE) at T = 303.15 K for this binary system was also measured in order to calculate the activity coefficients and the excess molar Gibbs energy. This binary system shows no azeotrope and negative deviations from ideal behaviour. The excess or deviation properties were fitted to the Redlich-Kister polynomial relation to obtain their coefficients and standard deviations

  3. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    International Nuclear Information System (INIS)

    Tewatia, Arya; Hendrix, Justin; Dong, Zhizhong; Taghon, Meredith; Tse, Stephen; Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas; Lynch, Jennifer

    2017-01-01

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

  4. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

    2017-02-15

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

  5. The truth is out there: measured, calculated and modelled benthic fluxes.

    Science.gov (United States)

    Pakhomova, Svetlana; Protsenko, Elizaveta

    2016-04-01

    In a modern Earth science there is a great importance of understanding the processes, forming the benthic fluxes as one of element sources or sinks to or from the water body, which affects the elements balance in the water system. There are several ways to assess benthic fluxes and here we try to compare the results obtained by chamber experiments, calculated from porewater distributions and simulated with model. Benthic fluxes of dissolved elements (oxygen, nitrogen species, phosphate, silicate, alkalinity, iron and manganese species) were studied in the Baltic and Black Seas from 2000 to 2005. Fluxes were measured in situ using chamber incubations (Jch) and at the same time sediment cores were collected to assess the porewater distribution at different depths to calculate diffusive fluxes (Jpw). Model study was carried out with benthic-pelagic biogeochemical model BROM (O-N-P-Si-C-S-Mn-Fe redox model). It was applied to simulate biogeochemical structure of the water column and upper sediment and to assess the vertical fluxes (Jmd). By the behaviour at the water-sediment interface all studied elements can be divided into three groups: (1) elements which benthic fluxes are determined by the concentrations gradient only (Si, Mn), (2) elements which fluxes depend on redox conditions in the bottom water (Fe, PO4, NH4), and (3) elements which fluxes are strongly connected with organic matter fate (O2, Alk, NH4). For the first group it was found that measured fluxes are always higher than calculated diffusive fluxes (1.5disadvantages and the main facing us question is - which value should be taken for calculation the balance? This research is funded by VISTA - a basic research program and collaborative partnership between the Norwegian Academy of Science and Letters and Statoil.

  6. Human body capacitance: static or dynamic concept? [ESD

    DEFF Research Database (Denmark)

    Jonassen, Niels M

    1998-01-01

    A standing human body insulated from ground by footwear and/or floor covering is in principle an insulated conductor and has, as such, a capacitance, i.e. the ability to store a charge and possibly discharge the stored energy in a spark discharge. In the human body, the human body capacitance (HBC...... when a substantial part of the flux extends itself through badly defined stray fields. Since the concept of human body capacitance is normally used in a static (electric) context, it is suggested that the HBC be determined by a static method. No theoretical explanation of the observed differences...

  7. A model to assess the feasibility of shifting reaction equilibrium by acetone removal in the transamination of ketones using 2‐propylamine

    DEFF Research Database (Denmark)

    Tufvesson, Pär; Bach, Christian; Woodley, John

    2014-01-01

    also shows the value of a modeling approach in conceptual process design prior to entering a biocatalyst screening or engineering program to assess the feasibility of a particular process strategy for a given target product. Biotechnol. Bioeng. 2014;111: 309–319. © 2013 Wiley Periodicals, Inc....... strategy. To avoid excessive laboratory work a model was used to assess the process feasibility. The results from the current study show that a simple model of the acetone removal dependence on temperature and sparging gas flowrate can be developed and fits the experimental data well. The model for acetone...... removal was then coupled to a simple model for biocatalyst kinetics and also for loss of substrate ketone by evaporation. The three models were used to simulate the effects of varying the critical process parameters and reaction equilibrium constants (K eq) as well as different substrate ketone...

  8. Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones

    KAUST Repository

    Shylesh, Sankaranarayanapillai

    2016-09-22

    The effects of chemical composition and pretreatment on Mg–Al hydrotalcites and alumina-supported MgO were evaluated for the gas-phase, self-condensation reaction of C3–C5 biomass-derived methyl ketones. We show that the selectivity toward the acyclic dimer enone and the cyclic enone trimer can be tuned by controlling the temperature of hydrotalcite calcination. Methyl ketone cyclization is promoted by Lewis acidic sites present on the hydrotalcite catalysts. XRD and thermal decomposition analysis reveal that the formation of periclase MgO starts above 623 K accompanied by complete disappearance of the hydrotalcite structure and is accompanied by an increase in hydroxyl condensation as the formation of well-crystallized periclase. 27Al MQMAS and 25Mg MAS NMR show that at progressively higher temperatures, Al3+ cations diffuses out of the octahedral brucite layers and incorporate into the tetrahedral and octahedral sites of the MgO matrix thereby creating defects to compensate the excess positive charge generated. The oxygen anions adjacent to the Mg2+/Al3+ defects become coordinatively unsaturated, leading to the formation of new basic sites. A kinetic isotope effect, kH/kD = 0.96, is observed at 473 K for the reaction of (CH3)2CO versus (CD3)2CO, which suggests that carbon–carbon bond formation leading to the dimer aldol product is the rate-determining step in the condensation reaction of methyl ketones. We also show that acid–base catalysts having similar reactivity and higher hydrothermal stability to that of calcined hydrotalcites can be achieved by creating defects in MgO crystallites supported alumina as a consequence of the diffusion of Al3+ cations into MgO. The physical properties of these materials are shown to be very similar to those of hydrotalcite calcined at 823 K.

  9. Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones

    KAUST Repository

    Shylesh, Sankaranarayanapillai; Kim, Daeyoup; Gokhale, Amit A.; Canlas, Christian; Struppe, Jochem O.; Ho, Christopher R.; Jadhav, Deepak; Yeh, Alice; Bell, Alexis T.

    2016-01-01

    The effects of chemical composition and pretreatment on Mg–Al hydrotalcites and alumina-supported MgO were evaluated for the gas-phase, self-condensation reaction of C3–C5 biomass-derived methyl ketones. We show that the selectivity toward the acyclic dimer enone and the cyclic enone trimer can be tuned by controlling the temperature of hydrotalcite calcination. Methyl ketone cyclization is promoted by Lewis acidic sites present on the hydrotalcite catalysts. XRD and thermal decomposition analysis reveal that the formation of periclase MgO starts above 623 K accompanied by complete disappearance of the hydrotalcite structure and is accompanied by an increase in hydroxyl condensation as the formation of well-crystallized periclase. 27Al MQMAS and 25Mg MAS NMR show that at progressively higher temperatures, Al3+ cations diffuses out of the octahedral brucite layers and incorporate into the tetrahedral and octahedral sites of the MgO matrix thereby creating defects to compensate the excess positive charge generated. The oxygen anions adjacent to the Mg2+/Al3+ defects become coordinatively unsaturated, leading to the formation of new basic sites. A kinetic isotope effect, kH/kD = 0.96, is observed at 473 K for the reaction of (CH3)2CO versus (CD3)2CO, which suggests that carbon–carbon bond formation leading to the dimer aldol product is the rate-determining step in the condensation reaction of methyl ketones. We also show that acid–base catalysts having similar reactivity and higher hydrothermal stability to that of calcined hydrotalcites can be achieved by creating defects in MgO crystallites supported alumina as a consequence of the diffusion of Al3+ cations into MgO. The physical properties of these materials are shown to be very similar to those of hydrotalcite calcined at 823 K.

  10. Theoretical assessment of whole body counting performances using numerical phantoms of different gender and sizes.

    Science.gov (United States)

    Marzocchi, O; Breustedt, B; Mostacci, D; Zankl, M; Urban, M

    2011-03-01

    A goal of whole body counting (WBC) is the estimation of the total body burden of radionuclides disregarding the actual position within the body. To achieve the goal, the detectors need to be placed in regions where the photon flux is as independent as possible from the distribution of the source. At the same time, the detectors need high photon fluxes in order to achieve better efficiency and lower minimum detectable activities. This work presents a method able to define the layout of new WBC systems and to study the behaviour of existing ones using both detection efficiency and its dependence on the position of the source within the body of computational phantoms.

  11. Theoretical assessment of whole body counting performances using numerical phantoms of different gender and sizes

    International Nuclear Information System (INIS)

    Marzocchi, O.; Breustedt, B.; Mostacci, D.; Zankl, M.; Urban, M.

    2011-01-01

    A goal of whole body counting (WBC) is the estimation of the total body burden of radionuclides disregarding the actual position within the body. To achieve the goal, the detectors need to be placed in regions where the photon flux is as independent as possible from the distribution of the source. At the same time, the detectors need high photon fluxes in order to achieve better efficiency and lower minimum detectable activities. This work presents a method able to define the layout of new WBC systems and to study the behaviour of existing ones using both detection efficiency and its dependence on the position of the source within the body of computational phantoms. (authors)

  12. Elastic energy of the flux lines in the matter. The interaction energy

    International Nuclear Information System (INIS)

    Dolocan, Voicu

    1999-01-01

    A theoretical treatment of the interaction between the bodies, by using the elastic coupling through the flux lines, is presented. We show that the elastic coupling through the flux lines gives an interaction energy between two superconductor or magnetic pieces, which is inversely proportional to the distance between the two bodies. We extend this concept to the gravitational and electrical interaction. For the electrical interaction one obtains that the statics interaction energy is inversely proportional to the distance between the charges, as in the Coulomb's law, while the oscillatory interaction is inversely proportional to the third power of the distance between the charged particles. This means that at shorter distance an attraction between the two charged particles of the same sign, may appear if the oscillatory energy of interaction is larger than the statics energy of interaction. In addition, the oscillatory interaction appears only as a virtual process. We apply these results to the deuteron and to the electron pairs in superconductors. Also, for the gravitation one obtains that the interaction energy is inversely proportional to the distance between the centers of the two bodies as in Newton's law. (author)

  13. Tree Species with Photosynthetic Stems Have Greater Nighttime Sap Flux

    Directory of Open Access Journals (Sweden)

    Xia Chen

    2018-01-01

    Full Text Available An increasing body of evidence has shown that nighttime sap flux occurs in most plants, but the physiological implications and regulatory mechanism are poorly known. The significance of corticular photosynthesis has received much attention during the last decade, however, the knowledge of the relationship between corticular photosynthesis and nocturnal stem sap flow is limited at present. In this study, we divided seven tree species into two groups according to different photosynthetic capabilities: trees of species with (Castanopsis hystrix, Michelia macclurei, Eucalyptus citriodora, and Eucalyptus grandis × urophylla and without (Castanopsis fissa, Schima superba, and Acacia auriculiformis photosynthetic stems, and the sap flux (Js and chlorophyll fluorescence parameters for these species were measured. One-way ANOVA analysis showed that the Fv/Fm (Maximum photochemical quantum yield of PSII and ΦPSII (effective photochemical quantum yield of PSII values were lower in non-photosynthetic stem species compared to photosynthetic stem species. The linear regression analysis showed that Js,d (daytime sap flux and Js,n (nighttime sap flux of non-photosynthetic stem species was 87.7 and 60.9% of the stem photosynthetic species. Furthermore, for a given daytime transpiration water loss, total nighttime sap flux was higher in species with photosynthetic stems (SlopeSMA = 2.680 than in non-photosynthetic stems species (SlopeSMA = 1.943. These results mean that stem corticular photosynthesis has a possible effect on the nighttime water flow, highlighting the important eco-physiological relationship between nighttime sap flux and corticular photosynthesis.

  14. Tree Species with Photosynthetic Stems Have Greater Nighttime Sap Flux

    Science.gov (United States)

    Chen, Xia; Gao, Jianguo; Zhao, Ping; McCarthy, Heather R.; Zhu, Liwei; Ni, Guangyan; Ouyang, Lei

    2018-01-01

    An increasing body of evidence has shown that nighttime sap flux occurs in most plants, but the physiological implications and regulatory mechanism are poorly known. The significance of corticular photosynthesis has received much attention during the last decade, however, the knowledge of the relationship between corticular photosynthesis and nocturnal stem sap flow is limited at present. In this study, we divided seven tree species into two groups according to different photosynthetic capabilities: trees of species with (Castanopsis hystrix, Michelia macclurei, Eucalyptus citriodora, and Eucalyptus grandis × urophylla) and without (Castanopsis fissa, Schima superba, and Acacia auriculiformis) photosynthetic stems, and the sap flux (Js) and chlorophyll fluorescence parameters for these species were measured. One-way ANOVA analysis showed that the Fv/Fm (Maximum photochemical quantum yield of PSII) and ΦPSII (effective photochemical quantum yield of PSII) values were lower in non-photosynthetic stem species compared to photosynthetic stem species. The linear regression analysis showed that Js,d (daytime sap flux) and Js,n (nighttime sap flux) of non-photosynthetic stem species was 87.7 and 60.9% of the stem photosynthetic species. Furthermore, for a given daytime transpiration water loss, total nighttime sap flux was higher in species with photosynthetic stems (SlopeSMA = 2.680) than in non-photosynthetic stems species (SlopeSMA = 1.943). These results mean that stem corticular photosynthesis has a possible effect on the nighttime water flow, highlighting the important eco-physiological relationship between nighttime sap flux and corticular photosynthesis. PMID:29416547

  15. A nonintrusive temperature measuring system for estimating deep body temperature in bed.

    Science.gov (United States)

    Sim, S Y; Lee, W K; Baek, H J; Park, K S

    2012-01-01

    Deep body temperature is an important indicator that reflects human being's overall physiological states. Existing deep body temperature monitoring systems are too invasive to apply to awake patients for a long time. Therefore, we proposed a nonintrusive deep body temperature measuring system. To estimate deep body temperature nonintrusively, a dual-heat-flux probe and double-sensor probes were embedded in a neck pillow. When a patient uses the neck pillow to rest, the deep body temperature can be assessed using one of the thermometer probes embedded in the neck pillow. We could estimate deep body temperature in 3 different sleep positions. Also, to reduce the initial response time of dual-heat-flux thermometer which measures body temperature in supine position, we employed the curve-fitting method to one subject. And thereby, we could obtain the deep body temperature in a minute. This result shows the possibility that the system can be used as practical temperature monitoring system with appropriate curve-fitting model. In the next study, we would try to establish a general fitting model that can be applied to all of the subjects. In addition, we are planning to extract meaningful health information such as sleep structure analysis from deep body temperature data which are acquired from this system.

  16. Contribution to the study of the structure and reactivity of ketones using deuterium substitution of the {alpha} - ketone hydrogens; Contribution a l'etude de la structure et de la reactivite des cetones, par utilisation de la substitution deuteriee des hydrogenes {alpha}-cetoniques

    Energy Technology Data Exchange (ETDEWEB)

    Frejaville, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1966-02-01

    This work is an attempt to obtain more knowledge about the structure and the reactivity of ketones; it is also a contribution to conformational analysis based on infrared signals associated with the C-D vibration in mono-deuterated compounds. In the first chapter the various dosage and synthetic methods used in this work are described. In the second chapter the infrared spectra in the 2100-2200 cm{sup -1} region for mono-deuterated ketones are interpreted on the basis of a simple model. This model is then studied in detail, and also critically and precisely, in the case of the mono deuterated acetone molecule. In the third chapter is studied the mechanism of the Favorskii reaction and the reactivity of all the {alpha}-ketonic hydrogens of 2 chloro-cyclohexanone are classified. In a technical appendix is described a counter-current exchange method for obtaining a great variety of solvents and deuterated pure raw materials under advantageous conditions. (author) [French] Ce travail est un effort vers une meilleure connaissance de la structure et de la reactivite des cetones; c'est egalement une contribution a l'analyse conformationnelle d'apres l'etude des signaux infrarouges associes a la vibration C-D dans les composes monodeuteries. Dans le premier chapitre sont decrites les differentes methodes de dosage et de synthese qui ont ete utilisees dans ce travail. Dans le deuxieme chapitre, les spectres infrarouges dans la region 2100-2200 cm{sup -1} de cetones monodeuteriees sont interpretes sur la base d'un modele simple. Ce modele est ensuite etudie de facon detaillee, critique et precise sur la molecule d'acetone monodeuteriee. Dans le troisieme chapitre on etudie le mecanisme de la reaction de FAWORSKII et l'on classe la reactivite de tous les hydrogenes {alpha}-cetoniques de la chloro-2-cyclohexanone. Dons l'appendice technique on decrit la mise en oeuvre d'un appareil d'echange a contre-courant qui permet d'obtenir dans des conditions tres interessantes une

  17. Reactions of enolisable ketones with dichloroisocyanuric acid in absence and presence of added chloride ions – a kinetic study

    Directory of Open Access Journals (Sweden)

    Y. L. Kumar

    2015-01-01

    Full Text Available Kinetics of reactions of enolisable ketones (S = acetone/2-butanone with dichloroisocyanuric acid (DCICA were studied in aqueous acetic acid and perchloric acid media in absence and presence of added chloride ions. The reactions were found to be pseudo zero order and pseudo first order on [DCICA] in absence and presence of chloride ions respectively. Both in presence and absence of chloride ions, first order and fractional order in substrate and perchloric acid were observed respectively. An increase in the rate of reaction was observed with an increase in chloride ion concentration as well as acetic acid composition. The results were interpreted in terms of probable mechanisms involving (i rate-determining enol formation from the conjugate acid of the ketone (SH+ in the absence of added chloride ions and (ii rate-determining interaction of SH+ with the most effective molecular chlorine species produced by the hydrolysis of DCICA (rather than a rate-determining interaction of enol with chlorine in the presence of added chloride ions, prior to the rapid steps of product formation. DOI: http://dx.doi.org/10.4314/bcse.v29i1.12

  18. Mechanical Properties Optimization of Poly-Ether-Ether-Ketone via Fused Deposition Modeling.

    Science.gov (United States)

    Deng, Xiaohu; Zeng, Zhi; Peng, Bei; Yan, Shuo; Ke, Wenchao

    2018-01-30

    Compared to the common selective laser sintering (SLS) manufacturing method, fused deposition modeling (FDM) seems to be an economical and efficient three-dimensional (3D) printing method for high temperature polymer materials in medical applications. In this work, a customized FDM system was developed for polyether-ether-ketone (PEEK) materials printing. The effects of printing speed, layer thickness, printing temperature and filling ratio on tensile properties were analyzed by the orthogonal test of four factors and three levels. Optimal tensile properties of the PEEK specimens were observed at a printing speed of 60 mm/s, layer thickness of 0.2 mm, temperature of 370 °C and filling ratio of 40%. Furthermore, the impact and bending tests were conducted under optimized conditions and the results demonstrated that the printed PEEK specimens have appropriate mechanical properties.

  19. Synthesis of Polycyclic Ring Systems Using Transition Metal Catalyzed Cyclizations of Diazo Alkynyl Ketones

    Directory of Open Access Journals (Sweden)

    Albert Padwa

    2000-12-01

    Full Text Available The rhodium(II-catalyzed reaction of α-diazo ketones bearing tethered alkyne units represents a new and useful method for the construction of a variety of substituted cyclopentenones. The process proceeds by addition of the rhodium-stabilized carbenoid onto the acetylenic π-bond to give a vinyl carbenoid intermediate. The resulting rhodium complex undergoes a wide assortment of reactions including cyclopropanation, 1,2-hydrogen migration, CH-insertion, addition to tethered alkynes and ylide formation. When 2-alkynyl-2-diazo-3-oxobutanoates were treated with a Rh(II-catalyst, furo[3,4-c]furans were formed in excellent yield.

  20. Laboratory studies of Aedes aegypti (L.) attraction to ketones, sulfides and primary chloroalkanes tested alone and in combination with l-lactic acid

    Science.gov (United States)

    The attraction of female Aedes aegypti to single compounds and binary compositions comprised of L-lactic acid and an additional saturated compound from a set of ketones, sulfides, and chloroalkanes was studied using a triple-cage dual-port olfactometer. These chemical classes were studied because o...

  1. A shock tube and laser absorption study of ignition delay times and OH reaction rates of ketones: 2-Butanone and 3-buten-2-one

    KAUST Repository

    Badra, Jihad; Elwardani, Ahmed Elsaid; Khaled, Fathi; Vasu, Subith S.; Farooq, Aamir

    2014-01-01

    Ketones are potential biofuel candidates and are also formed as intermediate products during the oxidation of large hydrocarbons or oxygenated fuels, such as alcohols and esters. This paper presents shock tube ignition delay times and OH reaction

  2. Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

    International Nuclear Information System (INIS)

    Silva, V.S.; Ruffmann, B.; Vetter, S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M.; Nunes, S.P.

    2006-01-01

    Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion[reg] 112 was used as reference material. DMFC tests were also performed at 50 deg. C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion[reg] 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion[reg] 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%

  3. Implant Failure After Motec Wrist Joint Prosthesis Due to Failure of Ball and Socket-Type Articulation-Two Patients With Adverse Reaction to Metal Debris and Polyether Ether Ketone.

    Science.gov (United States)

    Karjalainen, Teemu; Pamilo, Konsta; Reito, Aleksi

    2018-04-21

    We describe 2 cases of articulation-related failures resulting in revision surgery after a Motec total wrist arthroplasty: one with an adverse reaction to metal debris and the other with an adverse reaction to polyether ether ketone. In the first patient, blood cobalt and chrome levels were elevated and magnetic resonance imaging showed clear signs of a pseudotumor. The other patient had an extensive release of polyether ether ketone particles into the surrounding synovia due to adverse wear conditions in the cup, leading to the formation of a fluid-filled cyst sac with a black lining and diffuse lymphocyte-dominated inflammation in the synovia. We recommend regular follow-up including x-rays, monitoring of cobalt and chrome ion levels, and a low threshold for cross-sectional imaging in patients who have undergone total wrist arthroplasty with a Motec joint prosthesis. Wear-related problems can also develop in implants in which polyether ether ketone is the bulk material. Copyright © 2018 American Society for Surgery of the Hand. Published by Elsevier Inc. All rights reserved.

  4. Gas-chromatographic resolution of enantiomeric secondary alcohols. Stereoselective reductive metabolism of ketones in rabbit-liver cytosol.

    Science.gov (United States)

    Gal, J; DeVito, D; Harper, T W

    1981-01-01

    Chiral secondary alcohols were treated with (S)-(-)-1-phenylethyl isocyanate. For each racemic alcohol, the resulting diastereomeric urethane derivatives were resolved on flexible fused-silica capillary GLC columns with retention times of 15 min or less. Derivatization of individual enantiomers showed that the urethane derivatives of (R)-(-)-2-octanol, (R)-(+)-1-phenylethyl alcohol, and (S)-(+)-2,2,2-trifluoro-1-phenylethanol are eluted before the corresponding diastereomers. The procedure is simple and rapid, and is suitable for the determination of the enantiomeric composition of chiral alcohols extracted from biological media. A series of aliphatic alcohols, aryl alkyl carbinols, and arylalkyl alkyl carbinols were resolved with the procedure, and the degree of resolution varied from good to excellent. Eight achiral ketones were incubated, individually, with rabbit-liver 90,000 g supernatant fractions, and the enantiomeric composition of the alcohol metabolites was determined with the GLC procedure. The reductions proceeded with high stereoselectivity to give alcohol products of 90% or greater enantiomeric purity. The reduction of 2-octanone and acetophenone gave predominant alcohols of (S)-configuration, in agreement with the Baumann-Prelog rule. The configuration of the predominant alcohols arising in the reduction of the remainder of the ketones could not be firmly established, but the evidence suggests that they are also of the (S)-configuration. Fluorine or methyl substitution in the ortho position of acetophenone produced an increase in the stereoselectivity, and the alcohol produced from ortho-methylacetophenone was enantiomerically greater than 99% pure.

  5. CHROMOSPHERIC AND CORONAL WAVE GENERATION IN A MAGNETIC FLUX SHEATH

    International Nuclear Information System (INIS)

    Kato, Yoshiaki; Hansteen, Viggo; Gudiksen, Boris; Wedemeyer, Sven; Carlsson, Mats; Steiner, Oskar

    2016-01-01

    Using radiation magnetohydrodynamic simulations of the solar atmospheric layers from the upper convection zone to the lower corona, we investigate the self-consistent excitation of slow magneto-acoustic body waves (slow modes) in a magnetic flux concentration. We find that the convective downdrafts in the close surroundings of a two-dimensional flux slab “pump” the plasma inside it in the downward direction. This action produces a downflow inside the flux slab, which encompasses ever higher layers, causing an upwardly propagating rarefaction wave. The slow mode, excited by the adiabatic compression of the downflow near the optical surface, travels along the magnetic field in the upward direction at the tube speed. It develops into a shock wave at chromospheric heights, where it dissipates, lifts the transition region, and produces an offspring in the form of a compressive wave that propagates further into the corona. In the wake of downflows and propagating shock waves, the atmosphere inside the flux slab in the chromosphere and higher tends to oscillate with a period of ν ≈ 4 mHz. We conclude that this process of “magnetic pumping” is a most plausible mechanism for the direct generation of longitudinal chromospheric and coronal compressive waves within magnetic flux concentrations, and it may provide an important heat source in the chromosphere. It may also be responsible for certain types of dynamic fibrils.

  6. CHROMOSPHERIC AND CORONAL WAVE GENERATION IN A MAGNETIC FLUX SHEATH

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Yoshiaki; Hansteen, Viggo; Gudiksen, Boris; Wedemeyer, Sven; Carlsson, Mats [Institute of Theoretical Astrophysics, University of Oslo, P.O. Box 1029 Blindern, NO-0315 Oslo (Norway); Steiner, Oskar, E-mail: yoshiaki.kato@astro.uio.no [Kiepenheuer-Institut für Sonnenphysik, Schöneckstrasse 6, D-79104 Freiburg (Germany)

    2016-08-10

    Using radiation magnetohydrodynamic simulations of the solar atmospheric layers from the upper convection zone to the lower corona, we investigate the self-consistent excitation of slow magneto-acoustic body waves (slow modes) in a magnetic flux concentration. We find that the convective downdrafts in the close surroundings of a two-dimensional flux slab “pump” the plasma inside it in the downward direction. This action produces a downflow inside the flux slab, which encompasses ever higher layers, causing an upwardly propagating rarefaction wave. The slow mode, excited by the adiabatic compression of the downflow near the optical surface, travels along the magnetic field in the upward direction at the tube speed. It develops into a shock wave at chromospheric heights, where it dissipates, lifts the transition region, and produces an offspring in the form of a compressive wave that propagates further into the corona. In the wake of downflows and propagating shock waves, the atmosphere inside the flux slab in the chromosphere and higher tends to oscillate with a period of ν ≈ 4 mHz. We conclude that this process of “magnetic pumping” is a most plausible mechanism for the direct generation of longitudinal chromospheric and coronal compressive waves within magnetic flux concentrations, and it may provide an important heat source in the chromosphere. It may also be responsible for certain types of dynamic fibrils.

  7. Local deformation behavior of surface porous polyether-ether-ketone.

    Science.gov (United States)

    Evans, Nathan T; Torstrick, F Brennan; Safranski, David L; Guldberg, Robert E; Gall, Ken

    2017-01-01

    Surface porous polyether-ether-ketone has the ability to maintain the tensile monotonic and cyclic strength necessary for many load bearing orthopedic applications while providing a surface that facilitates bone ingrowth; however, the relevant deformation behavior of the pore architecture in response to various loading conditions is not yet fully characterized or understood. The focus of this study was to examine the compressive and wear behavior of the surface porous architecture using micro Computed Tomography (micro CT). Pore architectures of various depths (~0.5-2.5mm) and pore sizes (212-508µm) were manufactured using a melt extrusion and porogen leaching process. Compression testing revealed that the pore architecture deforms in the typical three staged linear elastic, plastic, and densification stages characteristic of porous materials. The experimental moduli and yield strengths decreased as the porosity increased but there was no difference in properties between pore sizes. The porous architecture maintained a high degree of porosity available for bone-ingrowth at all strains. Surface porous samples showed no increase in wear rate compared to injection molded samples, with slight pore densification accompanying wear. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Thermotolerant cyclamen with reduced acrolein and methyl vinyl ketone.

    Science.gov (United States)

    Kai, Hiroomi; Hirashima, Keita; Matsuda, Osamu; Ikegami, Hidetoshi; Winkelmann, Traud; Nakahara, Takao; Iba, Koh

    2012-06-01

    Reduced levels of trienoic fatty acids (TAs) in chloroplast membranes induce thermotolerance in several plant species, but the underlying mechanisms remain unclear. TA peroxidation in plant cell membranes generates cytotoxic, TA-derived compounds containing α,β-unsaturated carbonyl groups. The relationship between low TA levels and the amounts of cytotoxic TA-derived compounds was examined using thermotolerant transgenic cyclamen (Cyclamen persicum Mill.) with low TA contents. Changes in the levels of the cytotoxic TA-derived acrolein (ACR), methyl vinyl ketone (MVK), (E)-2-hexenal, 4-hydroxy-2-nonenal, and malondialdehyde were analysed in the leaf tissues of wild-type (WT) and thermotolerant transgenic cyclamen under heat stress. Levels of ACR and MVK in the WT increased in parallel with the occurrence of heat-induced tissue damage, whereas no such changes were observed in the thermotolerant transgenic lines. Furthermore, exogenous ACR and MVK infiltrated into leaves to concentrations similar to those observed in heat-stressed WT leaves caused similar disease symptoms. These results suggest that thermotolerance in transgenic cyclamen depends on reduced production rates of ACR and MVK under heat stress, due to the low level of TAs in these plants.

  9. Design of a flux buffer based on the flux shuttle

    International Nuclear Information System (INIS)

    Gershenson, M.

    1991-01-01

    This paper discusses the design considerations for a flux buffer based on the flux-shuttle concept. Particular attention is given to the issues of flux popping, stability of operation and saturation levels for a large input. Modulation techniques used in order to minimize 1/f noise, in addition to offsets are also analyzed. Advantages over conventional approaches using a SQUID for a flux buffer are discussed. Results of computer simulations are presented

  10. Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

    Energy Technology Data Exchange (ETDEWEB)

    Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

    2011-01-01

    Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

  11. Analysis of electron-irradiated poly-ether ether ketone by X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Oyabu, Matashige; Kobayashi, Yoshinori; Seguchi, Tadao; Sasuga, Tsuneo; Kudoh, Hisaaki.

    1995-01-01

    Organic polymers used in atomic power plants or space are damaged by ionizing irradiation. Radicals produced by irradiation cause oxidation, chain scission and crosslinking, all of which lead to degradation of the material. In this paper, the surface of electron-irradiated poly-ether ether ketone (PEEK) was studied by X-ray photoelectron spectroscopy (XPS). The irradiation in air was found to oxidize the PEEK surface producing carboxyl groups, the content of which dependant on the dose. Carboxyl groups were not produced in helium gas. Quantitative spectral analysis indicated that the aromatic structure might be decomposed. Some comparison was made between the semicrystalline and amorphous samples. The oxygen content resulting from irradiation, of semicrystalline PEEK increased more than that of amorphous PEEK. (author)

  12. Field trial on progesterone cycles, metabolic profiles, body condition score and their relation to fertility in Estonian Holstein dairy cows.

    Science.gov (United States)

    Samarütel, J; Ling, K; Waldmann, A; Jaakson, H; Kaart, T; Leesmäe, A

    2008-08-01

    Resumption of luteal activity postpartum and fertility were investigated in an Estonian Holstein high milk production and good fertility dairy herd. Body condition was scored after every 10 days in 54 multiparous dairy cows (71 lactations) calving inside from December to March during 4-year period. Blood samples were taken 1-14 days before calving and 1-14, 28-42 and 63-77 days after calving: analytes estimated were serum aspartate aminotransferase (AST), glucose, ketone bodies, total cholesterol, non-esterified fatty acids and triglycerides. The general linear mixed model was used to compare the data for cows with different characteristics in luteal activity postpartum based on their milk progesterone profiles. Forty-five per cent of cases had abnormal profiles; delayed resumption of ovarian cyclicity postpartum (DC) was the most prevalent abnormality. There was no difference in body condition scores between the groups. The DC and prolonged luteal phase groups had higher serum AST activity (p fertility.

  13. Fluctuations of radiative heat exchange between two bodies

    Science.gov (United States)

    Biehs, S.-A.; Ben-Abdallah, P.

    2018-05-01

    We present a theory to describe the fluctuations of nonequilibrium radiative heat transfer between two bodies both in the far- and near-field regimes. As predicted by the blackbody theory, in the far field, we show that the variance of radiative heat flux is of the same order of magnitude as its mean value. However, in the near-field regime, we demonstrate that the presence of surface polaritons makes this variance more than one order of magnitude larger than the mean flux. We further show that the correlation time of heat flux in this regime is comparable to the relaxation time of heat carriers in each medium. This theory could open the way to an experimental investigation of heat exchanges far from the thermal equilibrium condition.

  14. Magnetic-flux pump

    Science.gov (United States)

    Hildebrandt, A. F.; Elleman, D. D.; Whitmore, F. C. (Inventor)

    1966-01-01

    A magnetic flux pump is described for increasing the intensity of a magnetic field by transferring flux from one location to the magnetic field. The device includes a pair of communicating cavities formed in a block of superconducting material, and a piston for displacing the trapped magnetic flux into the secondary cavity producing a field having an intense flux density.

  15. Tree Species with Photosynthetic Stems Have Greater Nighttime Sap Flux.

    Science.gov (United States)

    Chen, Xia; Gao, Jianguo; Zhao, Ping; McCarthy, Heather R; Zhu, Liwei; Ni, Guangyan; Ouyang, Lei

    2018-01-01

    An increasing body of evidence has shown that nighttime sap flux occurs in most plants, but the physiological implications and regulatory mechanism are poorly known. The significance of corticular photosynthesis has received much attention during the last decade, however, the knowledge of the relationship between corticular photosynthesis and nocturnal stem sap flow is limited at present. In this study, we divided seven tree species into two groups according to different photosynthetic capabilities: trees of species with ( Castanopsis hystrix, Michelia macclurei, Eucalyptus citriodora , and Eucalyptus grandis × urophylla ) and without ( Castanopsis fissa, Schima superba , and Acacia auriculiformis ) photosynthetic stems, and the sap flux ( J s ) and chlorophyll fluorescence parameters for these species were measured. One-way ANOVA analysis showed that the F v / F m (Maximum photochemical quantum yield of PSII) and Φ PSII (effective photochemical quantum yield of PSII) values were lower in non-photosynthetic stem species compared to photosynthetic stem species. The linear regression analysis showed that J s,d (daytime sap flux) and J s,n (nighttime sap flux) of non-photosynthetic stem species was 87.7 and 60.9% of the stem photosynthetic species. Furthermore, for a given daytime transpiration water loss, total nighttime sap flux was higher in species with photosynthetic stems (Slope SMA = 2.680) than in non-photosynthetic stems species (Slope SMA = 1.943). These results mean that stem corticular photosynthesis has a possible effect on the nighttime water flow, highlighting the important eco-physiological relationship between nighttime sap flux and corticular photosynthesis.

  16. Mechanical Properties Optimization of Poly-Ether-Ether-Ketone via Fused Deposition Modeling

    Directory of Open Access Journals (Sweden)

    Xiaohu Deng

    2018-01-01

    Full Text Available Compared to the common selective laser sintering (SLS manufacturing method, fused deposition modeling (FDM seems to be an economical and efficient three-dimensional (3D printing method for high temperature polymer materials in medical applications. In this work, a customized FDM system was developed for polyether-ether-ketone (PEEK materials printing. The effects of printing speed, layer thickness, printing temperature and filling ratio on tensile properties were analyzed by the orthogonal test of four factors and three levels. Optimal tensile properties of the PEEK specimens were observed at a printing speed of 60 mm/s, layer thickness of 0.2 mm, temperature of 370 °C and filling ratio of 40%. Furthermore, the impact and bending tests were conducted under optimized conditions and the results demonstrated that the printed PEEK specimens have appropriate mechanical properties.

  17. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    International Nuclear Information System (INIS)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

    2014-01-01

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  18. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    Energy Technology Data Exchange (ETDEWEB)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang, E-mail: wolfgang.bacsa@cemes.fr [CEMES-CNRS and University of Toulouse, 29 Jeanne Marvig, 31055 Toulouse (France); Boyer, François; Olivier, Philippe [Université de Toulouse, Institut Clément Ader, I.U.T. Université Paul Sabatier - 133C Avenue de Rangueil - B.P. 67701, 31077 Toulouse CEDEX 4 (France); Sapelkin, Andrei [School of Physics and Astronomy, Queen Mary, University of London, Mile End Road, E1 4NS London (United Kingdom); King, Stephen; Heenan, Richard [ISIS Facility, Rutherford Appleton Laboratory, Chilton, OX11 0QX Didcot (United Kingdom); Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri [AIRBUS FRANCE (B.E. M and P Toulouse), 316 Route de Bayonne, 31060 Toulouse (France)

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  19. Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones.

    Science.gov (United States)

    Liang, Guanfeng; Wang, Aiqin; Li, Lin; Xu, Gang; Yan, Ning; Zhang, Tao

    2017-03-06

    Transformation of biomass into valuable nitrogen-containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO 2 , which could catalyze the reductive amination of a variety of biomass-derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two-step approach for production of ethanolamine, a large-market nitrogen-containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO 2 -containing multivalence Ru association species worked as a bifunctional catalyst, with RuO 2 as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Low-temperature direct heterogeneous bonding of polyether ether ketone and platinum.

    Science.gov (United States)

    Fu, Weixin; Shigetou, Akitsu; Shoji, Shuichi; Mizuno, Jun

    2017-10-01

    Direct heterogeneous bonding between polyether ether ketone (PEEK) and Pt was realized at the temperatures lower than 150°C. In order to create sufficient bondability to diverse materials, the surface was modified by vacuum ultraviolet (VUV) irradiation, which formed hydrate bridges. For comparison, direct bonding between surfaces atomically cleaned via Ar fast atom bombardment (FAB) was conducted in a vacuum. The VUV irradiation was found to be effective for creating an ultrathin hydrate bridge layer from the residual water molecules in the chamber. Tight bonds were formed through dehydration of the hydrate bridges by heating at 150°C, which also contributed to enhancing interdiffusion across the interface. The VUV-modified surfaces showed bondability as good as that of the FAB-treated surfaces, and the VUV-modified samples had shear strengths at the same level as those of FAB-treated surfaces. This technology will be of practical use in the packaging of lightweight, flexible biomedical devices. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Dielectric and conformational studies of hydrogen bonded 2-ethoxyethanol and ethyl methyl ketone system

    Science.gov (United States)

    Pattebahadur, Kanchan. L.; Deshmukh, S. D.; Mohod, A. G.; Undre, P. B.; Patil, S. S.; Khirade, P. W.

    2018-05-01

    The Dielectric constant, density and refractive index of binary mixture of 2-ethoxy ethanol (2-EE) with ethyl methyl ketone (EMK) including those of the pure liquids were measured for 11 concentrations at 25°C temperature. The experimental data is used to calculate the Excess molar volume, Excess dielectric constant, Kirkwood correlation factor and Bruggemann factor. The excess parameters results were fitted to the Redlich-Kister type polynomial equation to derive its fitting coefficient. The Kirkwood correlation factor of the mixture has been discussed to yield information about solute solvent interaction. The Bruggeman plot shows a deviation from linearity. The FT-IR spectra of pure and their binary mixtures are also studied.

  2. OpenFLUX: efficient modelling software for 13C-based metabolic flux analysis

    Directory of Open Access Journals (Sweden)

    Nielsen Lars K

    2009-05-01

    Full Text Available Abstract Background The quantitative analysis of metabolic fluxes, i.e., in vivo activities of intracellular enzymes and pathways, provides key information on biological systems in systems biology and metabolic engineering. It is based on a comprehensive approach combining (i tracer cultivation on 13C substrates, (ii 13C labelling analysis by mass spectrometry and (iii mathematical modelling for experimental design, data processing, flux calculation and statistics. Whereas the cultivation and the analytical part is fairly advanced, a lack of appropriate modelling software solutions for all modelling aspects in flux studies is limiting the application of metabolic flux analysis. Results We have developed OpenFLUX as a user friendly, yet flexible software application for small and large scale 13C metabolic flux analysis. The application is based on the new Elementary Metabolite Unit (EMU framework, significantly enhancing computation speed for flux calculation. From simple notation of metabolic reaction networks defined in a spreadsheet, the OpenFLUX parser automatically generates MATLAB-readable metabolite and isotopomer balances, thus strongly facilitating model creation. The model can be used to perform experimental design, parameter estimation and sensitivity analysis either using the built-in gradient-based search or Monte Carlo algorithms or in user-defined algorithms. Exemplified for a microbial flux study with 71 reactions, 8 free flux parameters and mass isotopomer distribution of 10 metabolites, OpenFLUX allowed to automatically compile the EMU-based model from an Excel file containing metabolic reactions and carbon transfer mechanisms, showing it's user-friendliness. It reliably reproduced the published data and optimum flux distributions for the network under study were found quickly ( Conclusion We have developed a fast, accurate application to perform steady-state 13C metabolic flux analysis. OpenFLUX will strongly facilitate and

  3. Sulphur and oxygen sequestration of n-C 37 and n-C 38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

    Science.gov (United States)

    Koopmans, Martin P.; Schaeffer-Reiss, Christine; de Leeuw, Jan W.; Lewan, Michael D.; Maxwell, James R.; Schaeffer, Philippe; Sinninghe Damsté, Jaap S.

    1997-06-01

    Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330°C for 72 h to study the diagenetic fate of n-C 37 and n-C 38 di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260°C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C 37 and n-C 38 skeletons, saturated n-C 37 and n-C38 methyl, ethyl, and mid-chain ketones, C 37 and C 38 mid-chain 2,5-di- n-alkylthiophenes, C 37 and C 38 1,2-di- n-alkylbenzenes, and C 37 and C 38n-alkanes. With increasing thermal maturation, three forms of the n-C 37 and n-C 38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di- n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C 37 and n-C 38 skeleton can be expected as well as the corresponding hydrocarbons.

  4. Sulphur and oxygen sequestration of n-C37 and n-C38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

    Science.gov (United States)

    Koopmans, M.P.; Schaeffer-Reiss, C.; De Leeuw, J. W.; Lewan, M.D.; Maxwell, J.R.; Schaeffer, P.; Sinninghe, Damste J.S.

    1997-01-01

    Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330??C for 72 h to study the diagenetic fate of n-C37 and n-C38 di-and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260??C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S-and O-bound n-C37 and n-C38 skeletons, saturated n-C37 and n-C38 methyl, ethyl, and mid-chain ketones, C37 and C38 mid-chain 2,5-di-n-alkylthiophenes, C37 and C38 1,2-di-n-alkylbenzenes, and C37 and C38 n-alkanes. With increasing thermal maturation, three forms of the n-C37 and n-C38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S-and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C37 and n-C38 skeleton can be expected as well as the corresponding hydrocarbons. Copyright ?? 1997 Elsevier Science Ltd.

  5. Communication: On the calculation of time-dependent electron flux within the Born-Oppenheimer approximation: A flux-flux reflection principle

    Science.gov (United States)

    Albert, Julian; Hader, Kilian; Engel, Volker

    2017-12-01

    It is commonly assumed that the time-dependent electron flux calculated within the Born-Oppenheimer (BO) approximation vanishes. This is not necessarily true if the flux is directly determined from the continuity equation obeyed by the electron density. This finding is illustrated for a one-dimensional model of coupled electronic-nuclear dynamics. There, the BO flux is in perfect agreement with the one calculated from a solution of the time-dependent Schrödinger equation for the coupled motion. A reflection principle is derived where the nuclear BO flux is mapped onto the electronic flux.

  6. SGLT2 Inhibitors May Predispose to Ketoacidosis.

    Science.gov (United States)

    Taylor, Simeon I; Blau, Jenny E; Rother, Kristina I

    2015-08-01

    Sodium glucose cotransporter 2 (SGLT2) inhibitors are antidiabetic drugs that increase urinary excretion of glucose, thereby improving glycemic control and promoting weight loss. Since approval of the first-in-class drug in 2013, data have emerged suggesting that these drugs increase the risk of diabetic ketoacidosis. In May 2015, the Food and Drug Administration issued a warning that SGLT2 inhibitors may lead to ketoacidosis. Using PubMed and Google, we conducted Boolean searches including terms related to ketone bodies or ketoacidosis with terms for SGLT2 inhibitors or phlorizin. Priority was assigned to publications that shed light on molecular mechanisms whereby SGLT2 inhibitors could affect ketone body metabolism. SGLT2 inhibitors trigger multiple mechanisms that could predispose to diabetic ketoacidosis. When SGLT2 inhibitors are combined with insulin, it is often necessary to decrease the insulin dose to avoid hypoglycemia. The lower dose of insulin may be insufficient to suppress lipolysis and ketogenesis. Furthermore, SGLT2 is expressed in pancreatic α-cells, and SGLT2 inhibitors promote glucagon secretion. Finally, phlorizin, a nonselective inhibitor of SGLT family transporters decreases urinary excretion of ketone bodies. A decrease in the renal clearance of ketone bodies could also increase the plasma ketone body levels. Based on the physiology of SGLT2 and the pharmacology of SGLT2 inhibitors, there are several biologically plausible mechanisms whereby this class of drugs has the potential to increase the risk of developing diabetic ketoacidosis. Future research should be directed toward identifying which patients are at greatest risk for this side effect and also to optimizing pharmacotherapy to minimize the risk to patients.

  7. The metabolic impact of β-hydroxybutyrate on neurotransmission: Reduced glycolysis mediates changes in calcium responses and KATP channel receptor sensitivity.

    Science.gov (United States)

    Lund, Trine M; Ploug, Kenneth B; Iversen, Anne; Jensen, Anders A; Jansen-Olesen, Inger

    2015-03-01

    Glucose is the main energy substrate for neurons, and ketone bodies are known to be alternative substrates. However, the capacity of ketone bodies to support different neuronal functions is still unknown. Thus, a change in energy substrate from glucose alone to a combination of glucose and β-hydroxybutyrate might change neuronal function as there is a known coupling between metabolism and neurotransmission. The purpose of this study was to shed light on the effects of the ketone body β-hydroxybutyrate on glycolysis and neurotransmission in cultured murine glutamatergic neurons. Previous studies have shown an effect of β-hydroxybutyrate on glucose metabolism, and the present study further specified this by showing attenuation of glycolysis when β-hydroxybutyrate was present in these neurons. In addition, the NMDA receptor-induced calcium responses in the neurons were diminished in the presence of β-hydroxybutyrate, whereas a direct effect of the ketone body on transmitter release was absent. However, the presence of β-hydroxybutyrate augmented transmitter release induced by the KATP channel blocker glibenclamide, thus giving an indirect indication of the involvement of KATP channels in the effects of ketone bodies on transmitter release. Energy metabolism and neurotransmission are linked and involve ATP-sensitive potassium (KATP ) channels. However, it is still unclear how and to what degree available energy substrate affects this link. We investigated the effect of changing energy substrate from only glucose to a combination of glucose and R-β-hydroxybutyrate in cultured neurons. Using the latter combination, glycolysis was diminished, NMDA receptor-induced calcium responses were lower, and the KATP channel blocker glibenclamide caused a higher transmitter release. © 2014 International Society for Neurochemistry.

  8. Effect of Polyether Ether Ketone on Therapeutic Radiation to the Spine: A Pilot Study.

    Science.gov (United States)

    Jackson, J Benjamin; Crimaldi, Anthony J; Peindl, Richard; Norton, H James; Anderson, William E; Patt, Joshua C

    2017-01-01

    Cadaveric model. To compare the effect of PEEK versus conventional implants on scatter radiation to a simulated tumor bed in the spine SUMMARY OF BACKGROUND DATA.: Given the highly vasculature nature of the spine, it is the most common place for bony metastases. After surgical treatment of a spinal metastasis, adjuvant radiation therapy is typically administered. Radiation dosing is primarily limited by toxicity to the spinal cord. The scatter effect caused by metallic implants decreases the accuracy of dosing and can unintentionally increase the effective dose seen by the spinal cord. This represents a dose-limiting factor for therapeutic radiation postoperatively. A cadaveric thorax specimen was utilized as a metastatic tumor model with two separate three-level spine constructs (one upper thoracic and one lower thoracic). Each construct was examined independently. All four groups compared included identical posterior instrumentation. The anterior constructs consisted of either: an anterior polyether ether ketone (PEEK) cage, an anterior titanium cage, an anterior bone cement cage (polymethyl methacrylate), or a control group with posterior instrumentation alone. Each construct had six thermoluminescent detectors to measure the radiation dose. The mean dose was similar across all constructs and locations. There was more variability in the upper thoracic spine irrespective of the construct type. The PEEK construct had a more uniform dose distribution with a standard deviation of 9.76. The standard deviation of the others constructs was 14.26 for the control group, 19.31 for the titanium cage, and 21.57 for the cement (polymethyl methacrylate) construct. The PEEK inter-body cage resulted in a significantly more uniform distribution of therapeutic radiation in the spine when compared with the other constructs. This may allow for the application of higher effective dosing to the tumor bed for spinal metastases without increasing spinal cord toxicity with either

  9. Fast Flux Test Facility

    International Nuclear Information System (INIS)

    Munn, W.I.

    1981-01-01

    The Fast Flux Test Facility (FFTF), located on the Hanford site a few miles north of Richland, Washington, is a major link in the chain of development required to sustain and advance Liquid Metal Fast Breeder Reactor (LMFBR) technology in the United States. This 400 MWt sodium cooled reactor is a three loop design, is operated by Westinghouse Hanford Company for the US Department of Energy, and is the largest research reactor of its kind in the world. The purpose of the facility is three-fold: (1) to provide a test bed for components, materials, and breeder reactor fuels which can significantly extend resource reserves; (2) to produce a complete body of base data for the use of liquid sodium in heat transfer systens; and (3) to demonstrate inherent safety characteristics of LMFBR designs

  10. Postprandial changes in plasma acylcarnitine concentrations as markers of fatty acid flux in overweight and obesity.

    Science.gov (United States)

    Ramos-Roman, Maria A; Sweetman, Lawrence; Valdez, Maressa J; Parks, Elizabeth J

    2012-02-01

    This study determined whether reductions in postprandial plasma nonesterified fatty acid (FFA) flux would lead to reductions in plasma acylcarnitine (AC) concentrations. Plasma AC was measured by liquid chromatography with tandem mass spectrometry in the fasting state and over 6 hours after a high-fat (50% energy) meal was fed to 16 overweight and obese subjects with a wide range of insulin sensitivities. Body composition was measured by dual-energy x-ray absorptiometry; insulin sensitivity by insulin-modified, frequently sampled intravenous glucose tolerance test; substrate oxidation by indirect calorimetry; blood metabolite and hormone concentrations biochemically; and fatty acid flux by using stable isotope tracers. Lean body mass and fasting fat oxidation correlated positively (r > 0.522, P 0.515, P Conditions that impact fatty acid flux contribute to the control of postprandial plasma AC concentrations. These data underscore the need for a better understanding of postprandial fatty acid oxidation and dietary fat delivery in the setting of adipose insulin resistance to determine how postprandial lipemia contributes to chronic disease risk. Copyright © 2012 Elsevier Inc. All rights reserved.

  11. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    International Nuclear Information System (INIS)

    Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

    1983-01-01

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH 4 CN, CH 3 CN, and C 2 H 4 CN, that had received multikilogray doses of 60 Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

  12. BAD-Dependent Regulation of Fuel Metabolism and KATP Channel Activity Confers Resistance to Epileptic Seizures

    OpenAIRE

    Giménez-Cassina, Alfredo; Martínez-François, Juan Ramón; Fisher, Jill K.; Szlyk, Benjamin; Polak, Klaudia; Wiwczar, Jessica; Tanner, Geoffrey R.; Lutas, Andrew; Yellen, Gary; Danial, Nika N.

    2012-01-01

    Neuronal excitation can be substantially modulated by alterations in metabolism, as evident from the anticonvulsant effect of diets that reduce glucose utilization and promote ketone body metabolism. We provide genetic evidence that BAD, a protein with dual functions in apoptosis and glucose metabolism, imparts reciprocal effects on metabolism of glucose and ketone bodies in brain cells. These effects involve phospho-regulation of BAD and are independent of its apoptotic function. BAD modific...

  13. Development of an improved wearable device for core body temperature monitoring based on the dual heat flux principle.

    Science.gov (United States)

    Feng, Jingjie; Zhou, Congcong; He, Cheng; Li, Yuan; Ye, Xuesong

    2017-04-01

    In this paper, a miniaturized wearable core body temperature (CBT) monitoring system based on the dual heat flux (DHF) principle was developed. By interspersing calcium carbonate powder in PolyDimethylsiloxane (PDMS), a reformative heat transfer medium was produced to reduce the thermal equilibrium time. Besides, a least mean square (LMS) algorithm based active noise cancellation (ANC) method was adopted to diminish the impact of ambient temperature fluctuations. Theoretical analyses, finite element simulation, experiments on a hot plate and human volunteers were performed. The results showed that the proposed system had the advantages of small size, reduced initial time (~23.5 min), and good immunity to fluctuations of the air temperature. For the range of 37-41 °C on the hot plate, the error compared with a Fluke high accuracy thermometer was 0.08  ±  0.20 °C. In the human experiments, the measured temperature in the rest trial (34 subjects) had a difference of 0.13  ±  0.22 °C compared with sublingual temperature, while a significant increase of 1.36  ±  0.44 °C from rest to jogging was found in the exercise trial (30 subjects). This system has the potential for reliable continuous CBT measurement in rest and can reflect CBT variations during exercise.

  14. Flux flow and flux creep in thick films of YBCO. [Y-Ba-Cu-O

    Energy Technology Data Exchange (ETDEWEB)

    Rickets, J.; Vinen, W.F.; Abell, J.S.; Shields, T.C. (Superconductivity Research Group, Univ. of Birmingham (United Kingdom))

    1991-12-01

    The results are described of new experiments designed to study flux creep and flux flow along a single flux percolation path in thick films of YBCO. The flux flow regime is studied by a four-point resistive technique using pulsed currents, and the flux creep regime by observing the rate at which flux enters a superconducting loop in parallel with the resistance that is associated with the flux percolation path. (orig.).

  15. Fatigue data for polyether ether ketone (PEEK) under fully-reversed cyclic loading.

    Science.gov (United States)

    Shrestha, Rakish; Simsiriwong, Jutima; Shamsaei, Nima

    2016-03-01

    In this article, the data obtained from the uniaxial fully-reversed fatigue experiments conducted on polyether ether ketone (PEEK), a semi-crystalline thermoplastic, are presented. The tests were performed in either strain-controlled or load-controlled mode under various levels of loading. The data are categorized into four subsets according to the type of tests, including (1) strain-controlled fatigue tests with adjusted frequency to obtain the nominal temperature rise of the specimen surface, (2) strain-controlled fatigue tests with various frequencies, (3) load-controlled fatigue tests without step loadings, and (4) load-controlled fatigue tests with step loadings. Accompanied data for each test include the fatigue life, the maximum (peak) and minimum (valley) stress-strain responses for each cycle, and the hysteresis stress-strain responses for each collected cycle in a logarithmic increment. A brief description of the experimental method is also given.

  16. Accuracy of the tritium water dilution method for determining water flux in reindeer (Rangifer tarandus)

    Energy Technology Data Exchange (ETDEWEB)

    Cameron, R D; White, R G; Luick, J R

    1976-06-01

    The accuracy of the tritium water dilution method in estimating water flux was evaluated in reindeer under various conditions of temperature and diet. Two non-pregnant female reindeer were restrained in metabolism stalls, within controlled-environment chambers, at temperatures of +10, -5, and -20/sup 0/C; varying amounts of a commercial pelleted ration (crude protein, 13 percent) or mixed lichens (crude protein, 3 percent) were offered, and water was provided ad libitum either as snow or in liquid form. Total body water volume and water turnover were estimated using tritiated water, and the daily outputs of feces and urine were measured for each of 12 different combinations of diet and temperature. Statistical analysis of the data showed that the tritium water dilution technique gives accurate determinations of total body water flux over a wide range of environmental and nutritional conditions.

  17. Continuous-flow hydration–condensation reaction: Synthesis of α,β-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2011-12-01

    Full Text Available A simple, practical and efficient continuous-flow hydration–condensation protocol was developed for the synthesis of α,β-unsaturated ketones starting from alkynes and aldehydes by employing a heterogeneous catalyst in a flow microwave. The procedure presents a straightforward and convenient access to valuable differently substituted chalcones and can be applied on multigram scale.

  18. Development of monograph titled "augmented chemistry aldehida & keton" with 3 dimensional (3D) illustration as a supplement book on chemistry learning

    Science.gov (United States)

    Damayanti, Latifah Adelina; Ikhsan, Jaslin

    2017-05-01

    Integration of information technology in education more rapidly performed in a medium of learning. Three-dimensional (3D) molecular modeling was performed in Augmented Reality as a tangible manifestation of increasingly modern technology utilization. Based on augmented reality, three-dimensional virtual object is projected in real time and the exact environment. This paper reviewed the uses of chemical learning supplement book of aldehydes and ketones which are equipped with three-dimensional molecular modeling by which students can inspect molecules from various viewpoints. To plays the 3D illustration printed on the book, smartphones with the open-source software of the technology based integrated Augmented Reality can be used. The aims of this research were to develop the monograph of aldehydes and ketones with 3 dimensional (3D) illustrations, to determine the specification of the monograph, and to determine the quality of the monograph. The quality of the monograph is evaluated by experiencing chemistry teachers on the five aspects of contents/materials, presentations, language and images, graphs, and software engineering, resulted in the result that the book has a very good quality to be used as a chemistry learning supplement book.

  19. Non-Toxic Metabolic Management of Metastatic Cancer in VM Mice: Novel Combination of Ketogenic Diet, Ketone Supplementation, and Hyperbaric Oxygen Therapy.

    Directory of Open Access Journals (Sweden)

    A M Poff

    Full Text Available The Warburg effect and tumor hypoxia underlie a unique cancer metabolic phenotype characterized by glucose dependency and aerobic fermentation. We previously showed that two non-toxic metabolic therapies - the ketogenic diet with concurrent hyperbaric oxygen (KD+HBOT and dietary ketone supplementation - could increase survival time in the VM-M3 mouse model of metastatic cancer. We hypothesized that combining these therapies could provide an even greater therapeutic benefit in this model. Mice receiving the combination therapy demonstrated a marked reduction in tumor growth rate and metastatic spread, and lived twice as long as control animals. To further understand the effects of these metabolic therapies, we characterized the effects of high glucose (control, low glucose (LG, ketone supplementation (βHB, hyperbaric oxygen (HBOT, or combination therapy (LG+βHB+HBOT on VM-M3 cells. Individually and combined, these metabolic therapies significantly decreased VM-M3 cell proliferation and viability. HBOT, alone or in combination with LG and βHB, increased ROS production in VM-M3 cells. This study strongly supports further investigation into this metabolic therapy as a potential non-toxic treatment for late-stage metastatic cancers.

  20. Enhanced Hydrothermal Stability and Catalytic Activity of La x Zr y O z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Ruiz, Juan A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Cooper, Alan R. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Li, Guosheng [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Albrecht, Karl O. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States

    2017-08-24

    Common ketonization catalysts such as ZrO2, CeO2, CexZryOz, and TiO2-based catalysts have been reported to lose surface area, undergo phase-transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized and tested a series of LaxZryOz mixed metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with enhanced ketonization activities 360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniques suggest that the formation of a hydrothermally stable catalyst which is isomorphic with tetragonal-ZrO2 under hydrothermal reaction conditions.

  1. Fast modeling of flux trapping cascaded explosively driven magnetic flux compression generators.

    Science.gov (United States)

    Wang, Yuwei; Zhang, Jiande; Chen, Dongqun; Cao, Shengguang; Li, Da; Liu, Chebo

    2013-01-01

    To predict the performance of flux trapping cascaded flux compression generators, a calculation model based on an equivalent circuit is investigated. The system circuit is analyzed according to its operation characteristics in different steps. Flux conservation coefficients are added to the driving terms of circuit differential equations to account for intrinsic flux losses. To calculate the currents in the circuit by solving the circuit equations, a simple zero-dimensional model is used to calculate the time-varying inductance and dc resistance of the generator. Then a fast computer code is programmed based on this calculation model. As an example, a two-staged flux trapping generator is simulated by using this computer code. Good agreements are achieved by comparing the simulation results with the measurements. Furthermore, it is obvious that this fast calculation model can be easily applied to predict performances of other flux trapping cascaded flux compression generators with complex structures such as conical stator or conical armature sections and so on for design purpose.

  2. Fast Flux Watch: A mechanism for online detection of fast flux networks

    Directory of Open Access Journals (Sweden)

    Basheer N. Al-Duwairi

    2014-07-01

    Full Text Available Fast flux networks represent a special type of botnets that are used to provide highly available web services to a backend server, which usually hosts malicious content. Detection of fast flux networks continues to be a challenging issue because of the similar behavior between these networks and other legitimate infrastructures, such as CDNs and server farms. This paper proposes Fast Flux Watch (FF-Watch, a mechanism for online detection of fast flux agents. FF-Watch is envisioned to exist as a software agent at leaf routers that connect stub networks to the Internet. The core mechanism of FF-Watch is based on the inherent feature of fast flux networks: flux agents within stub networks take the role of relaying client requests to point-of-sale websites of spam campaigns. The main idea of FF-Watch is to correlate incoming TCP connection requests to flux agents within a stub network with outgoing TCP connection requests from the same agents to the point-of-sale website. Theoretical and traffic trace driven analysis shows that the proposed mechanism can be utilized to efficiently detect fast flux agents within a stub network.

  3. A Facial Protocol for the Synthesis of Benzofuran Derivatives by the Reaction of o-Hydroxy Aryl Ketone, Amine and Chloroacetyl Chloride

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Shuai; Wang, Xiuhua; Liu, Jiqiang; Liu, Chang; Chen, Jianbin; Zuo, Hua [Southwest Univ., Chongqing (China); Xie, Yongsheng; Dong, Wenliang; Shin, Dongsoo [Changwon National Univ., Changwon (Korea, Republic of)

    2014-06-15

    A facile and effective method has been developed for the synthesis of a novel series of benzofuran derivatives via N-acylation, O-alkylation and intramolecular condensation reactions, starting from readily available substituted o-hydroxy aryl ketone, and chloroacetyl arylamides. This metal-free transition process is characterized by mild reaction conditions, atom economy, short reaction time and a high yield with a decreased amount of by-products.

  4. More power and less loads in wind farms. 'Heat and flux'

    Energy Technology Data Exchange (ETDEWEB)

    Corten, G.P.; Schaak, P. [ECN Wind Energy, Petten (Netherlands)

    2004-11-01

    We consider a farm as a single energy extracting body instead of a superposition of individual energy extractors, i.e. wind turbines. As a result we found two new hypotheses called Heat and Flux. Both hypotheses reveal that the classical operation of turbines in a wind farm at the Lanchester-Betz optimum does not lead to maximum farm output. However, when the turbines at the windward side of the farm are operated below their optimum, then the power of the turbines under the lee increases in such a way that the net farm production increases slightly. Next to this production advantage of Heat and Flux operation there is also a loading advantage. The average axial loading of the upwind turbines of a farm is reduced in a 'Heat and Flux'-farm. As a result those turbines generate less turbines so that the fatigue loads of the downwind turbines reduce too. The results were confirmed by in a boundary layer tunnel by means of differential measurements between a 'Heat and Flux'-farm and a classical farm.

  5. Flux flow and flux dynamics in high-Tc superconductors

    International Nuclear Information System (INIS)

    Bennett, L.H.; Turchinskaya, M.; Swartzendruber, L.J.; Roitburd, A.; Lundy, D.; Ritter, J.; Kaiser, D.L.

    1991-01-01

    Because high temperature superconductors, including BYCO and BSSCO, are type 2 superconductors with relatively low H(sub c 1) values and high H(sub c 2) values, they will be in a critical state for many of their applications. In the critical state, with the applied field between H(sub c 1) and H(sub c 2), flux lines have penetrated the material and can form a flux lattice and can be pinned by structural defects, chemical inhomogeneities, and impurities. A detailed knowledge of how flux penetrates the material and its behavior under the influence of applied fields and current flow, and the effect of material processing on these properties, is required in order to apply, and to improve the properties of these superconductors. When the applied field is changed rapidly, the time dependence of flux change can be divided into three regions, an initial region which occurs very rapidly, a second region in which the magnetization has a 1n(t) behavior, and a saturation region at very long times. A critical field is defined for depinning, H(sub c,p) as that field at which the hysteresis loop changes from irreversible to reversible. As a function of temperature, it is found that H(sub c,p) is well described by a power law with an exponent between 1.5 and 2.5. The behavior of H(sub c,p) for various materials and its relationship to flux flow and flux dynamics are discussed

  6. Study of sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups as ion conductive binder in lithium-ion batteries

    Science.gov (United States)

    Wei, Zengbin; Xue, Lixin; Nie, Feng; Sheng, Jianfang; Shi, Qianru; Zhao, Xiulan

    2014-06-01

    In an attempt to reduce the Li+ concentration polarization and electrolyte depletion from the electrode porous space, sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups (SPEEK-FSA-Li) is prepared and attempted as ionic conductivity binder. Sulfonated aromatic poly(ether ether ketone) exhibits strong adhesion and chemical stability, and lithiated fluorinated sulfonic side chains help to enhance the ionic conductivity and Li+ ion diffusion due to the charge delocalization over the sulfonic chain. The performances are evaluated by cyclic voltammetry, electrochemical impedance spectroscopy, charge-discharge cycle testing, 180° peel testing, and compared with the cathode prepared with polyvinylidene fluoride binder. The electrode prepared with SPEEK-FSA-Li binder forms the relatively smaller resistances of both the SEI and the charge transfer of lithium ion transport. This is beneficial to lithium ion intercalation and de-intercalation of the cathode during discharging-charging, therefore the cell prepared with SPEEK-FSA-Li shows lower charge plateau potential and higher discharge plateau potential. Compared with PVDF, the electrode with ionic binder shows smaller decrease in capacity with the increasing of cycle rate. Meanwhile, adhesion strength of electrode prepared with SPEEK-FSA-Li is more than five times greater than that with PVDF.

  7. Neutron flux monitor

    International Nuclear Information System (INIS)

    Oda, Naotaka.

    1993-01-01

    The device of the present invention greatly saves an analog processing section such as an analog filter and an analog processing circuit. That is, the device of the present invention comprises (1) a neutron flux detection means for detecting neutron fluxed in the reactor, (2) a digital filter means for dividing signals corresponding to the detected neutron fluxes into predetermined frequency band regions, (3) a calculation processing means for applying a calculation processing corresponding to the frequency band regions to the neutron flux detection signals divided by the digital filter means. With such a constitution, since the neutron detection signals are processed by the digital filter means, the accuracy is improved and the change for the property of the filter is facilitated. Further, when a neutron flux level is obtained, a calculation processing corresponding to the frequency band region can be conducted without the analog processing circuit. Accordingly, maintenance and accuracy are improved by greatly decreasing the number of parts. Further, since problems inherent to the analog circuit are solved, neutron fluxes are monitored at high reliability. (I.S.)

  8. 1,5-Asymmetric induction in the boron-mediated aldol reaction of β-oxygenated methyl ketones

    International Nuclear Information System (INIS)

    Dias, Luiz C.

    2007-01-01

    High levels of substrate-based 1,5-stereo induction are obtained in the boron-mediated aldol reactions of β-oxygenated methyl ketones with achiral and chiral aldehydes. Remote induction from the boron enolates gives the 1,5-anti adducts, with the enolate pi-facial selectivity critically dependent upon the nature of the beta-alkoxy protecting group. This 1,5-anti aldol methodology has been strategically employed in the total synthesis of several natural products. At present, the origin of the high level of 1,5-anti induction obtained with the boron enolates is unclear, although a model based on a hydrogen bonding between the alkoxy oxygen and the formyl hydrogen has been recently proposed. (author)

  9. Preliminary Investigation of Poly-Ether-Ether-Ketone Based on Fused Deposition Modeling for Medical Applications

    Directory of Open Access Journals (Sweden)

    Feng Zhao

    2018-02-01

    Full Text Available Poly-ether-ether-ketone (PEEK fabricated by fused deposition modeling for medical applications was evaluated in terms of mechanical strength and in vitro cytotoxicity in this study. Orthogonal experiments were firstly designed to investigate the significant factors on tensile strength. Nozzle temperature, platform temperature, and the filament diameter were tightly controlled for improved mechanical strength performance. These sensitive parameters affected the interlayer bonding and solid condition in the samples. Fourier transform infrared (FTIR spectrometry analysis was secondly conducted to compare the functional groups in PEEK granules, filaments, and printed parts. In vitro cytotoxicity test was carried out at last, and no toxic substances were introduced during the printing process.

  10. Repairing a Facial Cleft by Polyether-Ether-Ketone Implant Combined With Titanium Mesh.

    Science.gov (United States)

    Deng, Yuan; Tang, Weiwei; Li, Zhengkang

    2018-05-15

    The Tessier Number 4 cleft is one of the rarest, most complex craniofacial anomalies that presents difficulties in surgical treatment. In this article, we report a case of simultaneous facial depression, eye displacement, and medial canthus deformity. In this case, the maxillary bony defect was reconstructed using computer-assisted design computer-assisted manufacturing (CAD-CAM) polyether-ether-ketone (PEEK) material, and the orbital floor defect was repaired with AO prefabricated titanium mesh. Additionally, the medial canthus was modified with canthopexy and a single Z-plasty flap. Owing to its relative rarity and varied clinical presentations, no definitive operative methods have been accepted for Tessier No. 4 facial cleft. This study presents the combination of CAD-CAM manufactured PEEK material and titanium mesh as an alternative approach for reconstructing the bony defect of Tessier No. 4 facial clefts.

  11. Anthropogenic perturbation of the carbon fluxes from land to ocean

    KAUST Repository

    Regnier, Pierre

    2013-06-09

    A substantial amount of the atmospheric carbon taken up on land through photosynthesis and chemical weathering is transported laterally along the aquatic continuum from upland terrestrial ecosystems to the ocean. So far, global carbon budget estimates have implicitly assumed that the transformation and lateral transport of carbon along this aquatic continuum has remained unchanged since pre-industrial times. A synthesis of published work reveals the magnitude of present-day lateral carbon fluxes from land to ocean, and the extent to which human activities have altered these fluxes. We show that anthropogenic perturbation may have increased the flux of carbon to inland waters by as much as 1.0 Pg C yr -1 since pre-industrial times, mainly owing to enhanced carbon export from soils. Most of this additional carbon input to upstream rivers is either emitted back to the atmosphere as carbon dioxide (∼0.4 Pg C yr -1) or sequestered in sediments (∼0.5 Pg C yr -1) along the continuum of freshwater bodies, estuaries and coastal waters, leaving only a perturbation carbon input of ∼0.1 Pg C yr -1 to the open ocean. According to our analysis, terrestrial ecosystems store ∼0.9 Pg C yr -1 at present, which is in agreement with results from forest inventories but significantly differs from the figure of 1.5 Pg C yr -1 previously estimated when ignoring changes in lateral carbon fluxes. We suggest that carbon fluxes along the land-ocean aquatic continuum need to be included in global carbon dioxide budgets.

  12. Reaction of 11 C-benzoyl chlorides with metalloid reagents: 11 C-labeling of benzyl alcohols, benzaldehydes, and phenyl ketones from [11 C]CO.

    Science.gov (United States)

    Roslin, Sara; Dahl, Kenneth; Nordeman, Patrik

    2018-01-26

    In this article, we describe the carbon-11 ( 11 C, t 1/2  = 20.4 minutes) labeling of benzyl alcohols, benzaldehydes, and ketones using an efficient 2-step synthesis in which 11 C-carbon monoxide is used in an initial palladium-mediated reaction to produce 11 C-benzoyl chloride as a key intermediate. In the second step, the obtained 11 C-benzoyl chloride is further treated with a metalloid reagent to furnish the final 11 C-labeled product. Benzyl alcohols were obtained in moderated to high non-isolated radiochemical yields (RCY, 35%-90%) with lithium aluminum hydride or lithium aluminum deuteride as metalloid reagent. Changing the metalloid reagent to either tributyltin hydride or sodium borohydride, allowed for the reliable syntheses of 11 C-benzaldehydes in RCYs ranging from 58% to 95%. Finally, sodium tetraphenylborate were utilized to obtain 11 C-phenyl ketones in high RCYs (77%-95%). The developed method provides a new and efficient route to 3 different classes of compounds starting from aryl iodides or aryl bromides. Copyright © 2018 John Wiley & Sons, Ltd.

  13. Partial molar volumes of organic solutes in water. XXIII. Cyclic ketones at T = (298 to 573) K and pressures up to 30 MPa

    International Nuclear Information System (INIS)

    Cibulka, Ivan; Simurka, Lukas; Hnedkovsky, Lubomir; Bolotov, Alexander

    2011-01-01

    Research highlights: → In this study we examine standard molar volumes of aqueous cyclic ketones. → State parameters of measurements were (298 to 573) K and pressures up to 30 MPa. → Differences in behavior of monoketones and cyclohexane-1,4-dione were observed. → Group contribution method was designed and examined. - Abstract: Density data for dilute aqueous solutions of four cyclic ketones (cyclopentanone, cyclohexanone, cycloheptanone, and cyclohexane-1,4-dione) are presented together with standard molar volumes (partial molar volumes at infinite dilution) calculated from the experimental data. The measurements were performed at temperatures from T = 298 K up to T = 573 K. Experimental pressures were close to the saturated vapor pressure of water, and (15 and 30) MPa. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter. Experimental standard molar volumes were correlated as a function of temperature and pressure using an empirical polynomial function. Contributions of the molecular structural segments (methylene and carbonyl groups) to the standard molar volume were also evaluated and analyzed.

  14. TRANSHEX, 2-D Thermal Neutron Flux Distribution from Epithermal Flux in Hexagonal Geometry

    International Nuclear Information System (INIS)

    Patrakka, E.

    1994-01-01

    1 - Description of program or function: TRANSHEX is a multigroup integral transport program that determines the thermal scalar flux distribution arising from a known epithermal flux in two- dimensional hexagonal geometry. 2 - Method of solution: The program solves the isotropic collision probability equations for a region-averaged scalar flux by an iterative method. Either a successive over-relaxation or an inner-outer iteration technique is applied. Flat flux collision probabilities between trigonal space regions with white boundary condition are utilized. The effect of epithermal flux is taken into consideration as a slowing-down source that is calculated for a given spatial distribution and 1/E energy dependence of the epithermal flux

  15. Mechanical properties of orthodontic wires covered with a polyether ether ketone tube.

    Science.gov (United States)

    Shirakawa, Nobukazu; Iwata, Toshio; Miyake, Shinjiro; Otuka, Takero; Koizumi, So; Kawata, Toshitugu

    2018-03-21

    To evaluate the esthetics and frictional force of an orthodontic wire passed through a newly designed tube made of a polyether ether ketone (PEEK) resin. Two types of standard PEEK tubes were prepared at 0.5 × 0.6ф and 0.8 × 0.9ф, and different archwires were passed through the tubes. Color values were determined according to brightness and hues. Friction was assessed with different bracket-wire combinations, and surface roughness was determined by stereomicroscopy before and after the application of friction. The PEEK tube showed a color difference that was almost identical to that of coated wires conventionally used in clinical practice, indicating a sufficient esthetic property. The result of the friction test showed that the frictional force was greatly reduced by passing the archwire through the PEEK tube in almost all of the archwires tested. Use of the new PEEK tube demonstrated a good combination of esthetic and functional properties for use in orthodontic appliances.

  16. Theoretical study of the Wittig reaction of cyclic ketones with phosphorus ylide.

    Science.gov (United States)

    Jarwal, Nisha; Thankachan, Pompozhi Protasis

    2015-04-01

    The Wittig reaction of cyclopropanone, cyclobutanone and cyclopentanone with phosphorus ylide (Me3P = CH2) in gas phase was investigated computationally at B3LYP/6-31G** level of theory. In the Wittig reaction of cyclic ketones, two transition states (TS1 and TS2), corresponding to formation and decomposition of oxaphosphetane (OP) were located and investigated. Two loosely bound intermediates, a reactant complex (RC) and a product complex (PC) were also found. In the reaction of cyclopropanone, cyclobutanone and cyclopentanone, two oxaphosphetanes (OP1 and OP2) were predicted. OP1 initially formed was converted into OP2 by pseudorotation. In contrast to the reactions with cyclobutanone and cyclopentanone, an early TS1 was found in the reaction of cyclopropanone. The order of first activation energy barrier relative to reactant total energy was found to be cyclopropanone (-4.97 kcal mol(-1)) < cyclobutanone (0.30 kcal mol(-1)) < cyclopentanone (3.60 kcal mol(-1)).

  17. Radon flux measurement methodologies

    International Nuclear Information System (INIS)

    Nielson, K.K.; Rogers, V.C.

    1984-01-01

    Five methods for measuring radon fluxes are evaluated: the accumulator can, a small charcoal sampler, a large-area charcoal sampler, the ''Big Louie'' charcoal sampler, and the charcoal tent sampler. An experimental comparison of the five flux measurement techniques was also conducted. Excellent agreement was obtained between the measured radon fluxes and fluxes predicted from radium and emanation measurements

  18. Estimates the Effects of Benthic Fluxes on the Water Quality of the Reservoir

    Science.gov (United States)

    Lee, H.; Huh, I. A.; Park, S.; Choi, J. H.

    2014-12-01

    Reservoirs located in highly populated and industrialized regions receive discharges of nutrients and pollutants from the watershed that have great potential to impair water quality and threaten aquatic life. The Euiam reservoir is a multiple-purpose water body used for tourism, fishery, and water supply and has been reported as eutrophic since 1990s. The external nutrients loading is considered to be the main cause of eutrophication of water bodies, and control strategies therefore focus on its reduction. However, algae blooms often continue even after external nutrients loading has been controlled, being benthic nutrient loading the main source of nutrients in the water column. Attempts to quantify benthic nutrients fluxes and their role as a source of nutrients to the water column have produced ambiguous results. Benthic flux is dependent on the upward flow of pore water caused by hydrostatic pressure, molecular diffusion, and mixing of sediment and water. In addition, it is controlled by dissolved oxygen (DO) levels, pH values and temperature in the overlying water. Therefore, linking a benthic flux to a water quality model should give us more insight on the effects of benthic fluxes to better quantify nutrient concentration within an entire reservoir system where physical, chemical, biological properties are variable. To represent temporal and spatial variations in the nutrient concentrations of the reservoir, a three-dimensional time variable model, Generalized Longitudinal-Lateral-Vertical Hydrodynamic and Transport (GLLVHT) was selected. The GLLVHT model is imbedded within the Generalized Environmental Modeling System for Surface waters (GEMSS). The computational grid of the three-dimensional model was developed using the GIS. The horizontal grid is composed of 580 active cells at the surface layer with spacing varies from 54.2 m to 69.8 m. There are 15 vertical layers with uniform thickness of 1.9 m resolution. To calibrate the model, model prediction for

  19. EFSA Panel on Food Contact Material, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 51, Revision 1: Consideration of alicyclic ketones and secondary alcohols and related esters evaluated by the JECFA (59th meeting) structurally related to alicyclic, ketones secondary alcohols and related esters in FGE.09Rev3 (2011)

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 20 alicyclic ketones and secondary alcohols and related esters evaluated by JECFA (59th meeting) in 2002. This revision is made due to inclusion of seven additional substances...

  20. Flux pinning and flux flow studies in superconductors using flux flow noise techniques. Progress report, April 1, 1976--December 17, 1976

    International Nuclear Information System (INIS)

    Joiner, W.C.H.

    1976-12-01

    Measurements of flux flow noise power spectra have been combined with critical current measurements and measurements of current-voltage characteristics to study flux flow and local pinning interactions effective during flux flow. A model of flux flow noise generation in the presence of local pinning interactions is developed and applied to situations where pinning is dominated by: (1) grain boundaries, (2) normal metal precipitates in a superconducting matrix, (3) gross deformation producing a critical current peak effect, and (4) surface grooves imposed on a sample surface. In the case of pinning caused by normal metal precipitates in a superconducting matrix, unusual training and hysterisis effects are observed in the flux flow characteristics. The greater sensitivity of noise spectra, as compared with bulk critical current measurements, in obtaining a detailed picture of flux flow is emphasized

  1. Breaking the Dogma of Aldolase Specificity: Simple Aliphatic Ketones and Aldehydes are Nucleophiles for Fructose-6-phosphate Aldolase.

    Science.gov (United States)

    Roldán, Raquel; Sanchez-Moreno, Israel; Scheidt, Thomas; Hélaine, Virgil; Lemaire, Marielle; Parella, Teodor; Clapés, Pere; Fessner, Wolf-Dieter; Guérard-Hélaine, Christine

    2017-04-11

    d-Fructose-6-phosphate aldolase (FSA) was probed for extended nucleophile promiscuity by using a series of fluorogenic substrates to reveal retro-aldol activity. Four nucleophiles ethanal, propanone, butanone, and cyclopentanone were subsequently confirmed to be non-natural substrates in the synthesis direction using the wild-type enzyme and its D6H variant. This exceptional widening of the nucleophile substrate scope offers a rapid entry, in good yields and high stereoselectivity, to less oxygenated alkyl ketones and aldehydes, which was hitherto impossible. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Base-promoted isomerization of CF3-containing allylic alcohols to the corresponding saturated ketones under metal-free conditions

    Directory of Open Access Journals (Sweden)

    Yoko Hamada

    2017-08-01

    Full Text Available Following to the computational expectation, our previously reported intriguing 1,3-proton shift of 4,4,4-trifluorobut-2-yn-1-ols was successfully extended to the 4,4,4-trifluorobut-2-en-1-ol system under metal-free conditions to afford the corresponding saturated ketones in high to excellent chemical yields using such a convenient and easy-to-handle base as DBU at the toluene refluxing temperature, and utilization of the corresponding optically active substrates unambiguously demonstrated that this transformation proceeded in a highly stereoselective fashion.

  3. Flux cutting in superconductors

    International Nuclear Information System (INIS)

    Campbell, A M

    2011-01-01

    This paper describes experiments and theories of flux cutting in superconductors. The use of the flux line picture in free space is discussed. In superconductors cutting can either be by means of flux at an angle to other layers of flux, as in longitudinal current experiments, or due to shearing of the vortex lattice as in grain boundaries in YBCO. Experiments on longitudinal currents can be interpreted in terms of flux rings penetrating axial lines. More physical models of flux cutting are discussed but all predict much larger flux cutting forces than are observed. Also, cutting is occurring at angles between vortices of about one millidegree which is hard to explain. The double critical state model and its developments are discussed in relation to experiments on crossed and rotating fields. A new experiment suggested by Clem gives more direct information. It shows that an elliptical yield surface of the critical state works well, but none of the theoretical proposals for determining the direction of E are universally applicable. It appears that, as soon as any flux flow takes place, cutting also occurs. The conclusion is that new theories are required. (perspective)

  4. Solubility and solvation of alkali metal perchlorates, tetramethyl and tetraethylammonium in aqua-ketone solvents

    International Nuclear Information System (INIS)

    Kireev, A.A.; Pak, T.G.; Bezuglyj, V.D.

    1998-01-01

    The KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 H 5 ) 4 NClO 4 solubility in water and water-acetone, water-methylethylketone mixtures is determined through the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metals perchlorates in acetone and its 90% mixtures (by volume) are determined conductometrically. Solubility products and standard energies of the Gibbs transfer of the studied electrolytes from water into water-acetone and water-methylethylketone solvents. It is established that the Gibbs standard energies of Na + , K + , Rb + and Cs + cations transfer from water to water-ketone solvents are close to each other. It is shown that the effect of acetone and methylethylketone on solvation of the studied electrolytes is practically similar

  5. Are Polar Field Magnetic Flux Concentrations Responsible for Missing Interplanetary Flux?

    Science.gov (United States)

    Linker, Jon A.; Downs, C.; Mikic, Z.; Riley, P.; Henney, C. J.; Arge, C. N.

    2012-05-01

    Magnetohydrodynamic (MHD) simulations are now routinely used to produce models of the solar corona and inner heliosphere for specific time periods. These models typically use magnetic maps of the photospheric magnetic field built up over a solar rotation, available from a number of ground-based and space-based solar observatories. The line-of-sight field at the Sun's poles is poorly observed, and the polar fields in these maps are filled with a variety of interpolation/extrapolation techniques. These models have been found to frequently underestimate the interplanetary magnetic flux (Riley et al., 2012, in press, Stevens et al., 2012, in press) near the minimum part of the cycle unless mitigating correction factors are applied. Hinode SOT observations indicate that strong concentrations of magnetic flux may be present at the poles (Tsuneta et al. 2008). The ADAPT flux evolution model (Arge et al. 2010) also predicts the appearance of such concentrations. In this paper, we explore the possibility that these flux concentrations may account for a significant amount of magnetic flux and alleviate discrepancies in interplanetary magnetic flux predictions. Research supported by AFOSR, NASA, and NSF.

  6. The influence of the ketogenic diet on the elemental and biochemical compositions of the hippocampal formation.

    Science.gov (United States)

    Chwiej, Joanna; Skoczen, Agnieszka; Matusiak, Katarzyna; Janeczko, Krzysztof; Patulska, Agnieszka; Sandt, Christophe; Simon, Rolf; Ciarach, Malgorzata; Setkowicz, Zuzanna

    2015-08-01

    A growing body of evidence demonstrates that dietary therapies, mainly the ketogenic diet, may be highly effective in the reduction of epileptic seizures. All of them share the common characteristic of restricting carbohydrate intake to shift the predominant caloric source of the diet to fat. Catabolism of fats results in the production of ketone bodies which become alternate energy substrates to glucose. Although many mechanisms by which ketone bodies yield its anticonvulsant effect are proposed, the relationships between the brain metabolism of the ketone bodies and their neuroprotective and antiepileptogenic action still remain to be discerned. In the study, X-ray fluorescence microscopy and FTIR microspectroscopy were used to follow ketogenic diet-induced changes in the elemental and biochemical compositions of rat hippocampal formation tissue. The use of synchrotron sources of X-rays and infrared allowed us to examine changes in the accumulation and distribution of selected elements (P, S, K, Ca, Fe, Cu, Zn, and Se) and biomolecules (proteins, lipids, ketone bodies, etc.) with the micrometer spatial resolution. The comparison of rats fed with the ketogenic diet and rats fed with the standard laboratory diet showed changes in the hippocampal accumulation of P, K, Ca, and Zn. The relations obtained for Ca (increased level in CA3, DG, and its internal area) and Zn (decreased areal density in CA3 and DG) were analogous to those that we previously observed for rats in the acute phase of pilocarpine-induced seizures. Biochemical analysis of tissues taken from ketogenic diet-fed rats demonstrated increased intensity of absorption band occurring at 1740 cm(-1), which was probably the result of elevated accumulation of ketone bodies. Moreover, higher absolute and relative (3012 cm(-1)/2924 cm(-1), 3012 cm(-1)/lipid massif, and 3012 cm(-1)/amide I) intensity of the 3012-cm(-1) band resulting from increased unsaturated fatty acids content was found after the treatment

  7. Sulphur and oxygen sequestration of n-C{sub 37} and n-C{sub 38} unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

    Energy Technology Data Exchange (ETDEWEB)

    Koopmans, M.P.; De Leeuw, J.W.; Damste, J.S.S. [Netherlands Institute for Sea Research (NIOZ), Den Burg (Netherlands)] [and others

    1997-06-01

    Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (R{sub o} = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330{degrees}C for 72 h to study the diagenetic fate of n-C{sub 37} and n-C{sub 38} di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260{degrees}C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C{sub 37} and n-C{sub 38} skeletons, saturated n-C{sub 37} and n-C{sub 38} methyl, ethyl, and mid-chain ketones, C{sub 37} and C{sub 38} mid-chain 2,5-di-n-alkylthiophenes, C{sub 37} and C{sub 38} 1,2-di-n-alkylbenzenes, and C{sub 37} and C{sub 38} n-alkanes. With increasing thermal maturation, three forms of the n-C{sub 37} and n-C{sub 38} skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C{sub 37} and n-C{sub 38} skeleton can be expected as well as the corresponding hydrocarbons. 58 refs., 8 figs., 2 tabs.

  8. Mechanistic Insight into Ketone α-Alkylation with Unactivated Olefins via C-H Activation Promoted by Metal-Organic Cooperative Catalysis (MOCC): Enriching the MOCC Chemistry.

    Science.gov (United States)

    Dang, Yanfeng; Qu, Shuanglin; Tao, Yuan; Deng, Xi; Wang, Zhi-Xiang

    2015-05-20

    Metal-organic cooperative catalysis (MOCC) has been successfully applied for hydroacylation of olefins with aldehydes via directed C(sp(2))-H functionalization. Most recently, it was reported that an elaborated MOCC system, containing Rh(I) catalyst and 7-azaindoline (L1) cocatalyst, could even catalyze ketone α-alkylation with unactivated olefins via C(sp(3))-H activation. Herein we present a density functional theory study to understand the mechanism of the challenging ketone α-alkylation. The transformation uses IMesRh(I)Cl(L1)(CH2═CH2) as an active catalyst and proceeds via sequential seven steps, including ketone condensation with L1, giving enamine 1b; 1b coordination to Rh(I) active catalyst, generating Rh(I)-1b intermediate; C(sp(2))-H oxidative addition, leading to a Rh(III)-H hydride; olefin migratory insertion into Rh(III)-H bond; reductive elimination, generating Rh(I)-1c(alkylated 1b) intermediate; decoordination of 1c, liberating 1c and regenerating Rh(I) active catalyst; and hydrolysis of 1c, furnishing the final α-alkylation product 1d and regenerating L1. Among the seven steps, reductive elimination is the rate-determining step. The C-H bond preactivation via agostic interaction is crucial for the bond activation. The mechanism rationalizes the experimental puzzles: why only L1 among several candidates performed perfectly, whereas others failed, and why Wilkinson's catalyst commonly used in MOCC systems performed poorly. Based on the established mechanism and stimulated by other relevant experimental reactions, we attempted to enrich MOCC chemistry computationally, exemplifying how to develop new organic catalysts and proposing L7 to be an alternative for L1 and demonstrating the great potential of expanding the hitherto exclusive use of Rh(I)/Rh(III) manifold to Co(0)/Co(II) redox cycling in developing MOCC systems.

  9. Detection of Metabolic Fluxes of O and H Atoms into Intracellular Water in Mammalian Cells

    Science.gov (United States)

    Kreuzer, Helen W.; Quaroni, Luca; Podlesak, David W.; Zlateva, Theodora; Bollinger, Nikki; McAllister, Aaron; Lott, Michael J.; Hegg, Eric L.

    2012-01-01

    Metabolic processes result in the release and exchange of H and O atoms from organic material as well as some inorganic salts and gases. These fluxes of H and O atoms into intracellular water result in an isotopic gradient that can be measured experimentally. Using isotope ratio mass spectroscopy, we revealed that slightly over 50% of the H and O atoms in the intracellular water of exponentially-growing cultured Rat-1 fibroblasts were isotopically distinct from growth medium water. We then employed infrared spectromicroscopy to detect in real time the flux of H atoms in these same cells. Importantly, both of these techniques indicate that the H and O fluxes are dependent on metabolic processes; cells that are in lag phase or are quiescent exhibit a much smaller flux. In addition, water extracted from the muscle tissue of rats contained a population of H and O atoms that were isotopically distinct from body water, consistent with the results obtained using the cultured Rat-1 fibroblasts. Together these data demonstrate that metabolic processes produce fluxes of H and O atoms into intracellular water, and that these fluxes can be detected and measured in both cultured mammalian cells and in mammalian tissue. PMID:22848359

  10. Fractional flux excitations and flux creep in a superconducting film

    International Nuclear Information System (INIS)

    Lyuksyutov, I.F.

    1995-01-01

    We consider the transport properties of a modulated superconducting film in a magnetic field parallel to the film. Modulation can be either intrinsic, due to the layered structure of the high-T c superconductors, or artificial, e.g. due to thickness modulation. This system has an infinite set ( >) of pinned phases. In the pinned phase the excitation of flux loops with a fractional number of flux quanta by the applied current j results in flux creep with a generated voltage V ∝ exp[-jo/j[. (orig.)

  11. Integrated passive flux measurement in groundwater: design and performance of iFLUX samplers

    Science.gov (United States)

    Verreydt, Goedele; Razaei, Meisam; Meire, Patrick; Van Keer, Ilse; Bronders, Jan; Seuntjens, Piet

    2017-04-01

    The monitoring and management of soil and groundwater is a challenge. Current methods for the determination of movement or flux of pollution in groundwater use no direct measurements but only simulations based on concentration measurements and Darcy velocity estimations. This entails large uncertainties which cause remediation failures and higher costs for contaminated site owners. On top of that, the lack of useful data makes it difficult to get approval for a risk-based management approach which completely avoids costly remedial actions. The iFLUX technology is a key development of Dr. Goedele Verreydt at the University of Antwerp and VITO. It is supported by the passive flux measurement technology as invented by Prof. Mike Annable and his team at the University of Florida. The iFLUX technology includes an in situ measurement device for capturing dynamic groundwater quality and quantity, the iFLUX sampler, and an associated interpretation and visualization method. The iFLUX sampler is a modular passive sampler that provides simultaneous in situ point determinations of a time-averaged target compound mass flux and water flux. The sampler is typically installed in a monitoring well where it intercepts the groundwater flow and captures the compounds of interest. The sampler consists of permeable cartridges which are each packed with a specific sorbent matrix. The sorbent matrix of the water flux cartridge is impregnated with known amounts of water soluble resident tracers. These tracers are leached from the matrix at rates proportional to the groundwater flux. The measurements of the contaminants and the remaining resident tracer are used to determine groundwater and target compound fluxes. Exposure times range from 1 week to 6 months, depending on the expected concentration and groundwater flow velocity. The iFLUX sampler technology has been validated and tested at several field projects. Currently, 4 cartridges are tested and available: 1 waterflux cartridge to

  12. A flux footprint analysis to understand ecosystem fluxes in an intensively managed landscape

    Science.gov (United States)

    Hernandez Rodriguez, L. C.; Goodwell, A. E.; Kumar, P.

    2017-12-01

    Flux tower studies in agricultural sites have mainly been done at plot scale, where the footprint of the instruments is small such that the data reveals the behaviour of the nearby crop on which the study is focused. In the Midwestern United States, the agricultural ecosystem and its associated drainage, evapotranspiration, and nutrient dynamics are dominant influences on interactions between the soil, land, and atmosphere. In this study, we address large-scale ecohydrologic fluxes and states in an intensively managed landscape based on data from a 25m high eddy covariance flux tower. We show the calculated upwind distance and flux footprint for a flux tower located in Central Illinois as part of the Intensively Managed Landscapes Critical Zone Observatory (IMLCZO). In addition, we calculate the daily energy balance during the summer of 2016 from the flux tower measurements and compare with the modelled energy balance from a representative corn crop located in the flux tower footprint using the Multi-Layer Canopy model, MLCan. The changes in flux footprint over the course of hours, days, and the growing season have significant implications for the measured fluxes of carbon and energy at the flux tower. We use MLCan to simulate these fluxes under land covers of corn and soybeans. Our results demonstrate how the instrument heights impact the footprint of the captured eddy covariance fluxes, and we explore the implication for hydrological analysis. The convective turbulent atmosphere during the daytime shows a wide footprint of more than 10 km2, which reaches 3km length for the 90% contribution, where buoyancy is the dominant mechanism driving turbulence. In contrast, the stable atmosphere during the night-time shows a narrower footprint that goes beyond 8km2 and grows in the direction of the prevalent wind, which exceeds 4 km in length. This study improves our understanding of agricultural ecosystem behaviour in terms of the magnitude and variability of fluxes and

  13. Automated flux chamber for investigating gas flux at water-air interfaces.

    Science.gov (United States)

    Duc, Nguyen Thanh; Silverstein, Samuel; Lundmark, Lars; Reyier, Henrik; Crill, Patrick; Bastviken, David

    2013-01-15

    Aquatic ecosystems are major sources of greenhouse gases (GHG). Representative measurements of GHG fluxes from aquatic ecosystems to the atmosphere are vital for quantitative understanding of relationships between biogeochemistry and climate. Fluxes occur at high temporal variability at diel or longer scales, which are not captured by traditional short-term deployments (often in the order of 30 min) of floating flux chambers. High temporal frequency measurements are necessary but also extremely labor intensive if manual flux chamber based methods are used. Therefore, we designed an inexpensive and easily mobile automated flux chamber (AFC) for extended deployments. The AFC was designed to measure in situ accumulation of gas in the chamber and also to collect gas samples in an array of sample bottles for subsequent analysis in the laboratory, providing two independent ways of CH(4) concentration measurements. We here present the AFC design and function together with data from initial laboratory tests and from a field deployment.

  14. Synthesis of All-Z-1,6,9,12,15-Octadecapenten-3-one, A Vinyl Ketone Polyunsaturated Marine Natural Product Isolated from Callysponga sp.

    Directory of Open Access Journals (Sweden)

    Anne Marie Langseter

    2014-03-01

    Full Text Available The synthesis of the marine natural product 1,6Z,9Z,12Z,15Z-octadecapentaen-3-one (1 has been achieved by two different routes starting from the ethyl esters of eicosapentaenoic acid (EPA and docosahexaenoic acid (DHA, respectively. Using EPA ethyl ester as starting material the polyunsaturated vinyl ketone lipid 1 was obtained in 17% overall yield.

  15. Simultaneous and multi-point measurement of ammonia emanating from human skin surface for the estimation of whole body dermal emission rate.

    Science.gov (United States)

    Furukawa, Shota; Sekine, Yoshika; Kimura, Keita; Umezawa, Kazuo; Asai, Satomi; Miyachi, Hayato

    2017-05-15

    Ammonia is one of the members of odor gases and a possible source of odor in indoor environment. However, little has been known on the actual emission rate of ammonia from the human skin surface. Then, this study aimed to estimate the whole-body dermal emission rate of ammonia by simultaneous and multi-point measurement of emission fluxes of ammonia employing a passive flux sampler - ion chromatography system. Firstly, the emission fluxes of ammonia were non-invasively measured for ten volunteers at 13 sampling positions set in 13 anatomical regions classified by Kurazumi et al. The measured emission fluxes were then converted to partial emission rates using the surface body areas estimated by weights and heights of volunteers and partial rates of 13 body regions. Subsequent summation of the partial emission rates provided the whole body dermal emission rate of ammonia. The results ranged from 2.9 to 12mgh -1 with an average of 5.9±3.2mgh -1 per person for the ten healthy young volunteers. The values were much greater than those from human breath, and thus the dermal emission of ammonia was found more significant odor source than the breath exhalation in indoor environment. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. A cut-off in ocular chemesthesis from vapors of homologous alkylbenzenes and 2-ketones as revealed by concentration-detection functions

    International Nuclear Information System (INIS)

    Cometto-Muniz, J. Enrique; Abraham, Michael H.

    2008-01-01

    Studies of homologous series of environmental vapors have shown that their chemesthetic (i.e., sensory irritation) potency increases with carbon chain length (that is, their detection thresholds decrease) until they reach a homolog that fails to be detected, even at vapor saturation. All ensuing homologs cannot be detected either. In this investigation, we measured concentration-detection (i.e., psychometric) functions for ocular chemesthesis from homologous alkylbenzenes (pentyl, hexyl, and heptyl benzene) and 2-ketones (undecanone, dodecanone, and tridecanone). Using a three-alternative forced-choice procedure against air blanks, we tested a total of 18 to 24 subjects, about half of them females, average age 31 years, ranging from 18 to 56 years. Stimuli were generated and presented by a computer-controlled, vapor delivery device whose output was quantified by gas chromatography. Exposure time was 6 s and delivery flow 2.5 L/min. Within the context of present and previous findings, the outcome indicated that the functions for heptylbenzene and 2-tridecanone reached a plateau where further increases in concentration did not enhance detection. We conclude that: a) a cut-off point in ocular chemesthetic detection is reached along homologous alkylbenzenes and 2-ketones at the level of heptylbenzene and 2-tridecanone, respectively, and b) the observed effect rests on the homologs exceeding a critical molecular size (or dimension) rather than on them failing to achieve a high enough vapor concentration

  17. Comprehensive in Vitro Analysis of Acyltransferase Domain Exchanges in Modular Polyketide Synthases and Its Application for Short-Chain Ketone Production

    Energy Technology Data Exchange (ETDEWEB)

    Yuzawa, Satoshi [Univ. of California, Berkeley, CA (United States); Deng, Kai [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Wang, George [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Baidoo, Edward E. K. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Northen, Trent R. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Adams, Paul D. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Katz, Leonard [Univ. of California, Berkeley, CA (United States); Synthetic Biology Research Center, Emeryville, CA (United States); Keasling, Jay D. [Univ. of California, Berkeley, CA (United States); Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Synthetic Biology Research Center, Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-08-22

    Type I modular polyketide synthases (PKSs) are polymerases that utilize acyl-CoAs as substrates. Each polyketide elongation reaction is catalyzed by a set of protein domains called a module. Each module usually contains an acyltransferase (AT) domain, which determines the specific acyl-CoA incorporated into each condensation reaction. Although a successful exchange of individual AT domains can lead to the biosynthesis of a large variety of novel compounds, hybrid PKS modules often show significantly decreased activities. Using monomodular PKSs as models, we have systematically analyzed in this paper the segments of AT domains and associated linkers in AT exchanges in vitro and have identified the boundaries within a module that can be used to exchange AT domains while maintaining protein stability and enzyme activity. Importantly, the optimized domain boundary is highly conserved, which facilitates AT domain replacements in most type I PKS modules. To further demonstrate the utility of the optimized AT domain boundary, we have constructed hybrid PKSs to produce industrially important short-chain ketones. Our in vitro and in vivo analysis demonstrated production of predicted ketones without significant loss of activities of the hybrid enzymes. Finally, these results greatly enhance the mechanistic understanding of PKS modules and prove the benefit of using engineered PKSs as a synthetic biology tool for chemical production.

  18. Cortical substrate oxidation during hyperketonemia in the fasted anesthetized rat in vivo

    OpenAIRE

    Jiang, Lihong; Mason, Graeme F; Rothman, Douglas L; de Graaf, Robin A; Behar, Kevin L

    2011-01-01

    Ketone bodies are important alternate brain fuels, but their capacity to replace glucose and support neural function is unclear. In this study, the contributions of ketone bodies and glucose to cerebral cortical metabolism were measured in vivo in halothane-anesthetized rats fasted for 36 hours (n=6) and receiving intravenous [2,4-13C2]--β-hydroxybutyrate (BHB). Time courses of 13C-enriched brain amino acids (glutamate-C4, glutamine-C4, and glutamate and glutamine-C3) were measured at 9.4 Tes...

  19. Targeting energy metabolism in brain cancer with calorically restricted ketogenic diets.

    Science.gov (United States)

    Seyfried, Thomas N; Kiebish, Michael; Mukherjee, Purna; Marsh, Jeremy

    2008-11-01

    Information is presented on the calorically restricted ketogenic diet (CRKD) as an alternative therapy for brain cancer. In contrast to normal neurons and glia, which evolved to metabolize ketone bodies as an alternative fuel to glucose under energy-restricted conditions, brain tumor cells are largely glycolytic due to mitochondrial defects and have a reduced ability to metabolize ketone bodies. The CRKD is effective in managing brain tumor growth in animal models and in patients, and appears to act through antiangiogenic, anti-inflammatory, and proapoptotic mechanisms.

  20. Physics of magnetic flux ropes

    Science.gov (United States)

    Russell, C. T.; Priest, E. R.; Lee, L. C.

    The present work encompasses papers on the structure, waves, and instabilities of magnetic flux ropes (MFRs), photospheric flux tubes (PFTs), the structure and heating of coronal loops, solar prominences, coronal mass ejections and magnetic clouds, flux ropes in planetary ionospheres, the magnetopause, magnetospheric field-aligned currents and flux tubes, and the magnetotail. Attention is given to the equilibrium of MFRs, resistive instability, magnetic reconnection and turbulence in current sheets, dynamical effects and energy transport in intense flux tubes, waves in solar PFTs, twisted flux ropes in the solar corona, an electrodynamical model of solar flares, filament cooling and condensation in a sheared magnetic field, the magnetopause, the generation of twisted MFRs during magnetic reconnection, ionospheric flux ropes above the South Pole, substorms and MFR structures, evidence for flux ropes in the earth magnetotail, and MFRs in 3D MHD simulations.

  1. Meromorphic flux compactification

    Energy Technology Data Exchange (ETDEWEB)

    Damian, Cesar [Departamento de Ingeniería Mecánica, Universidad de Guanajuato,Carretera Salamanca-Valle de Santiago Km 3.5+1.8 Comunidad de Palo Blanco,Salamanca (Mexico); Loaiza-Brito, Oscar [Departamento de Física, Universidad de Guanajuato,Loma del Bosque No. 103 Col. Lomas del Campestre C.P 37150 León, Guanajuato (Mexico)

    2017-04-26

    We present exact solutions of four-dimensional Einstein’s equations related to Minkoswki vacuum constructed from Type IIB string theory with non-trivial fluxes. Following https://www.doi.org/10.1007/JHEP02(2015)187; https://www.doi.org/10.1007/JHEP02(2015)188 we study a non-trivial flux compactification on a fibered product by a four-dimensional torus and a two-dimensional sphere punctured by 5- and 7-branes. By considering only 3-form fluxes and the dilaton, as functions on the internal sphere coordinates, we show that these solutions correspond to a family of supersymmetric solutions constructed by the use of G-theory. Meromorphicity on functions constructed in terms of fluxes and warping factors guarantees that flux and 5-brane contributions to the scalar curvature vanish while fulfilling stringent constraints as tadpole cancelation and Bianchi identities. Different Einstein’s solutions are shown to be related by U-dualities. We present three supersymmetric non-trivial Minkowski vacuum solutions and compute the corresponding soft terms. We also construct a non-supersymmetric solution and study its stability.

  2. Meromorphic flux compactification

    International Nuclear Information System (INIS)

    Damian, Cesar; Loaiza-Brito, Oscar

    2017-01-01

    We present exact solutions of four-dimensional Einstein’s equations related to Minkoswki vacuum constructed from Type IIB string theory with non-trivial fluxes. Following https://www.doi.org/10.1007/JHEP02(2015)187; https://www.doi.org/10.1007/JHEP02(2015)188 we study a non-trivial flux compactification on a fibered product by a four-dimensional torus and a two-dimensional sphere punctured by 5- and 7-branes. By considering only 3-form fluxes and the dilaton, as functions on the internal sphere coordinates, we show that these solutions correspond to a family of supersymmetric solutions constructed by the use of G-theory. Meromorphicity on functions constructed in terms of fluxes and warping factors guarantees that flux and 5-brane contributions to the scalar curvature vanish while fulfilling stringent constraints as tadpole cancelation and Bianchi identities. Different Einstein’s solutions are shown to be related by U-dualities. We present three supersymmetric non-trivial Minkowski vacuum solutions and compute the corresponding soft terms. We also construct a non-supersymmetric solution and study its stability.

  3. Pd-catalyzed aerobic oxidative annulation of cyclohexanones and 2-aminophenyl ketones: A direct approach to acridines

    Science.gov (United States)

    Mu, Wanlu; Li, Xiaowei; Wang, Longfei; Chen, Yong; Wu, Yanchao

    2017-08-01

    An efficient aerobic oxidative annulation of cyclohexanones and 2-aminophenyl ketones approach to substituted acridines, a structural motif for a large number of pharmaceuticals and functional materials is described. The key feature of this method is the use of oxygen as the sole oxidant and Pd catalyst, which resulting in the high regioselectivity with unsymmetrical meta-substituted cyclohexanones. The electron gap of the global redox condensation process is filled and the reaction efficiency is significantly promoted by O2 as a redox moderator. This protocol possesses many advantages such as using O2 as a cheap and nonhazardous oxidant, high regioselectivity and water as the only by-product, which meet the principle of green chemistry.

  4. Enhanced response of microbial fuel cell using sulfonated poly ether ether ketone membrane as a biochemical oxygen demand sensor

    Energy Technology Data Exchange (ETDEWEB)

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha, E-mail: sangeetha@annauniv.edu

    2014-03-01

    Graphical abstract: - Highlights: • Sulfonated poly ether ether ketone (SPEEK) membrane in SCMFC used to determine the BOD. • The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm. • This sensing range was 62.5% higher than that of Nafion{sup ®}. • SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}. • Nafion{sup ®} shows high anodic internal resistance (67 Ω) than the SPEEK (39 Ω). - Abstract: The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion{sup ®}. The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}, resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria.

  5. Evaluation of NASA's Carbon Monitoring System (CMS) Flux Pilot: Terrestrial CO2 Fluxes

    Science.gov (United States)

    Fisher, J. B.; Polhamus, A.; Bowman, K. W.; Collatz, G. J.; Potter, C. S.; Lee, M.; Liu, J.; Jung, M.; Reichstein, M.

    2011-12-01

    NASA's Carbon Monitoring System (CMS) flux pilot project combines NASA's Earth System models in land, ocean and atmosphere to track surface CO2 fluxes. The system is constrained by atmospheric measurements of XCO2 from the Japanese GOSAT satellite, giving a "big picture" view of total CO2 in Earth's atmosphere. Combining two land models (CASA-Ames and CASA-GFED), two ocean models (ECCO2 and NOBM) and two atmospheric chemistry and inversion models (GEOS-5 and GEOS-Chem), the system brings together the stand-alone component models of the Earth System, all of which are run diagnostically constrained by a multitude of other remotely sensed data. Here, we evaluate the biospheric land surface CO2 fluxes (i.e., net ecosystem exchange, NEE) as estimated from the atmospheric flux inversion. We compare against the prior bottom-up estimates (e.g., the CASA models) as well. Our evaluation dataset is the independently derived global wall-to-wall MPI-BGC product, which uses a machine learning algorithm and model tree ensemble to "scale-up" a network of in situ CO2 flux measurements from 253 globally-distributed sites in the FLUXNET network. The measurements are based on the eddy covariance method, which uses observations of co-varying fluxes of CO2 (and water and energy) from instruments on towers extending above ecosystem canopies; the towers integrate fluxes over large spatial areas (~1 km2). We present global maps of CO2 fluxes and differences between products, summaries of fluxes by TRANSCOM region, country, latitude, and biome type, and assess the time series, including timing of minimum and maximum fluxes. This evaluation shows both where the CMS is performing well, and where improvements should be directed in further work.

  6. Leaching of Oil from Tuna Fish Liver by Using Solvent of Methyl-Ethyl Ketone

    Directory of Open Access Journals (Sweden)

    Mirna Rahmah Lubis

    2013-12-01

    Full Text Available Research of oil leaching from Tuna Fish Liver has been carried out by extracting of tuna fish liver in soxhlet by using methyl-ethyl ketone as solvent. Liver of fresh tuna fish is blended, put into soxhlet, and extracted at temperatures of 60oC, 65oC, 70oC, 75oC, and 80oC. After obtaining the oil, separation between solvent and oil is carried out by distillation. Oil obtained is analyzed by testing the yield, acid number, Iodine value, viscosity, and its impurities content. Yield obtained is influenced by temperature and time of leaching. Both variables indicates that the higher the variables, the more fish liver oil obtained. Maximum yield obtained is 25.552% at operating condition of leaching temperature 80oC, and leaching duration of 5 hours.

  7. Comparison of nonflare solar soft x ray flux with 10.7-cm radio flux

    International Nuclear Information System (INIS)

    Donnelly, R.F.

    1982-01-01

    The similarities and differences of the nonflare solar 1- to 8-A X ray flux and the daily 10.7-cm Ottawa solar radio flux are examined. The radio flux is shown to be much less sensitive than the soft X ray flux on the average to the coronal emission of active regions located near or beyond the solar chromospheric limb relative to regions near the center of the solar disk. This is caused by the solar soft X ray emission's being optically thin while much of the 10.7-cm active region emission is from optical depths of tauapprox.1. The radio flux includes a large quiet sun flux which is emitted mostly from the tenuous chromosphere-corona transition region (Tapprox.10 4 --10 6 0 K) and partly from the cooler portions of the quiet corona Tapprox.1.5 x 10 6 0 K. Conversely, the solar soft X ray flux has a very small quiet sun component

  8. Response of actinides to flux changes in high-flux systems

    International Nuclear Information System (INIS)

    Sailor, W.C.

    1993-01-01

    When discussing the transmutation of actinides in accelerator-based transmutation of waste (ATW) systems, there has been some concern about the dynamics of the actinides under high transient fluxes. For a pure neptunium feed, it has been estimated that the 238 Np/ 237 Np ratio increase due to an increasing flux may lead to an unstable, positive reactivity growth. In this analysis, a perturbation method is used to calculate the response of the entire set of actinides in a general way that allows for more species than just neptunium. The time response of the system can be calculated; i.e., a plot of fuel composition and reactivity versus time after a change in flux can be made. The effects of fission products can also be included. The procedure is extremely accurate on short time scales (∼ 1000 s) for the flux levels we contemplate. Calculational results indicate that the reactivity insertions are always smaller than previously estimated

  9. About Merging Threshold and Critical Flux Concepts into a Single One: The Boundary Flux

    Directory of Open Access Journals (Sweden)

    Marco Stoller

    2014-01-01

    Full Text Available In the last decades much effort was put in understanding fouling phenomena on membranes. One successful approach to describe fouling issues on membranes is the critical flux theory. The possibility to measure a maximum value of the permeate flux for a given system without incurring in fouling issues was a breakthrough in membrane process design. However, in many cases critical fluxes were found to be very low, lower than the economic feasibility of the process. The knowledge of the critical flux value must be therefore considered as a good starting point for process design. In the last years, a new concept was introduced, the threshold flux, which defines the maximum permeate flow rate characterized by a low constant fouling rate regime. This concept, more than the critical flux, is a new practical tool for membrane process designers. In this paper a brief review on critical and threshold flux will be reported and analyzed. And since the concepts share many common aspects, merged into a new concept, called the boundary flux, the validation will occur by the analysis of previously collected data by the authors, during the treatment of olive vegetation wastewater by ultrafiltration and nanofiltration membranes.

  10. Conversion of no-carrier-added [11C]carbon dioxide to [11C]carbon monoxide on molybdenum for the synthesis of 11C-labelled aromatic ketones

    International Nuclear Information System (INIS)

    Zeisler, S.K.; Nader, M.; Theobald, A.; Oberdorfer, F.

    1997-01-01

    A new method for the efficient conversion of no-carrier-added [ 11 C]carbon dioxide into [ 11 C]carbon monoxide is described. [ 11 C]Carbon dioxide produced by proton bombardment of ultra high purity nitrogen is pre-concentrated in a cryo trap and then passed through a quartz tube filled with a mesh of thin molybdenum wire heated to 850 o C. [ 11 C]Carbon dioxide readily reacts with molybdenum to form [ 11 C]carbon monoxide and molybdenum(IV) oxide. The latter also reduces carbon dioxide to carbon monoxide and helps improve the performance of the converter. [ 11 C]Carbon monoxide is purified from remaining [ 11 C]carbon dioxide and collected in a small silica trap from which it is eluted into a reaction mixture for the palladium-mediated synthesis of a 11 C-labelled aromatic ketone. Radiochemical yields of up to 81% (decay-corrected) for [ 11 C]carbon monoxide were obtained. Radiochemical purity and specific radioactivity of both [ 11 C]carbon monoxide and the 11 C-labelled ketone are sufficient for nuclear medical studies with PET. (Author)

  11. One-Pot Synthesis of 2-Acylindole-3-acetylketones via Domino Aza-alkylation/Michael Reaction Using o-Aminophenyl α,β-Unsaturated Ketones Followed by Desulfonative Dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, A Reum; Yu, Mi Rim; Sim, Jong Tack; Kim, Sung Gon [Kyonggi Univ., Suwon (Korea, Republic of)

    2016-09-15

    The development of novel and practical synthetic methods with a minimum number of operations for the construction of bioactive structurally complex compounds is a major challenge in synthetic organic chemistry. Recently, we reported an efficient method for the stereoselective synthesis of 2,3-disubstituted indoline derivatives; cis-2,3-disubstituted indolines were obtained by the aza-alkylation/Michael cascade reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones in good yields and with excellent diastereoselectivities (Scheme 2, Eq. (1)). Among the available synthetic strategies, domino or cascade reactions have received wide acceptance as highly efficient and powerful methods for the synthesis of molecules with a high structural complexity. An efficient synthesis of 2,3-disubstituted indoles was developed by the domino aza-alkylation/intramolecular Michael reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones, followed by desulfonative dehydrogenation with DBU. The reaction afforded structurally diverse and highly functionalized 2,3-disubstituted indoles in moderate to excellent yields (up to 99%). The synthesis of 2,3-disubstituted indoles without desulfonation through DDQ-induced oxidative dehydrogenation was also achieved.

  12. An efficient synthesis of β-amino ketone compounds through one-pot three-component Mannich-type reactions using bismuth nitrate as catalyst

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2015-07-01

    Full Text Available Three components one-pot Mannich reaction of aromatic ketone, aromatic aldehyde and aromatic amines has been efficiently catalyzed by recyclable bismuth nitrate (Bi(NO33, BN at ambient temperature to give various β-amino carbonyl compounds in high yields. This method has advantages of mild condition, no environmental pollution, and simple work-up procedures. Most importantly, β-amino carbonyl compounds with ortho-substituted aromatic amines are obtained in acceptable to moderate yields by this methodology.

  13. Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

    2017-03-03

    Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

  14. Filament Activation in Response to Magnetic Flux Emergence and Cancellation in Filament Channels

    Science.gov (United States)

    Li, Ting; Zhang, Jun; Ji, Haisheng

    2015-06-01

    We conducted a comparative analysis of two filaments that showed a quite different activation in response to the flux emergence within the filament channels. The observations from the Solar Dynamics Observatory (SDO) and Global Oscillation Network Group (GONG) were made to analyze the two filaments on 2013 August 17 - 20 (SOL2013-08-17) and September 29 (SOL2013-09-29). The first event showed that the main body of the filament was separated into two parts when an active region (AR) emerged with a maximum magnetic flux of about 6.4×1021 Mx underlying the filament. The close neighborhood and common direction of the bright threads in the filament and the open AR fan loops suggest a similar magnetic connectivity of these two flux systems. The equilibrium of the filament was not destroyed three days after the start of the emergence of the AR. To our knowledge, similar observations have never been reported before. In the second event, the emerging flux occurred nearby a barb of the filament with a maximum magnetic flux of 4.2×1020 Mx, about one order of magnitude lower than that of the first event. Two patches of parasitic polarity in the vicinity of the barb merged, then cancelled with nearby network fields. About 20 hours after the onset of the emergence, the filament erupted. Our findings imply that the location of emerging flux within the filament channel is probably crucial to filament evolution. If the flux emergence appears nearby the barbs, it is highly likely that the emerging flux and the filament magnetic fields will cancel, which may lead to the eruption of the filament. The comparison of the two events shows that the emergence of a small AR may still not be enough to disrupt the stability of a filament system, and the actual eruption only occurs after the flux cancellation sets in.

  15. ß-Hydroxybutyrate is the preferred substrate for GABA and glutamate synthesis while glucose is indispensable during depolarization in cultured GABAergic neurons

    DEFF Research Database (Denmark)

    Lund, Trine Meldgaard; Obel, Linea F; Risa, Øystein

    2011-01-01

    The ketogenic diet has multiple beneficial effects not only in treatment of epilepsy, but also in that of glucose transporter 1 deficiency, cancer, Parkinson's disease, obesity and pain. Thus, there is an increasing interest in understanding the mechanism behind this metabolic therapy. Patients...... on a ketogenic diet reach high plasma levels of ketone bodies, which are used by the brain as energy substrates. The interaction between glucose and ketone bodies is complex and there is still controversy as to what extent it affects the homeostasis of the neurotransmitters glutamate, aspartate and GABA...

  16. Heat flux microsensor measurements

    Science.gov (United States)

    Terrell, J. P.; Hager, J. M.; Onishi, S.; Diller, T. E.

    1992-01-01

    A thin-film heat flux sensor has been fabricated on a stainless steel substrate. The thermocouple elements of the heat flux sensor were nickel and nichrome, and the temperature resistance sensor was platinum. The completed heat flux microsensor was calibrated at the AEDC radiation facility. The gage output was linear with heat flux with no apparent temperature effect on sensitivity. The gage was used for heat flux measurements at the NASA Langley Vitiated Air Test Facility. Vitiated air was expanded to Mach 3.0 and hydrogen fuel was injected. Measurements were made on the wall of a diverging duct downstream of the injector during all stages of the hydrogen combustion tests. Because the wall and the gage were not actively cooled, the wall temperature reached over 1000 C (1900 F) during the most severe test.

  17. A portable infrared laser spectrometer for flux measurements of trace gases at the geosphere–atmosphere interface

    International Nuclear Information System (INIS)

    Guimbaud, C; Catoire, V; Robert, C; Chartier, M; Pomathiod, L; Gogo, S; Laggoun-Défarge, F; Albéric, P; Grossel, A; Nicoullaud, B; Richard, G

    2011-01-01

    A portable infrared laser absorption spectrometer named SPIRIT (SPectromètre Infra-Rouge In situ Troposphérique) has been set up for the simultaneous flux measurements of trace gases at the geosphere–atmosphere interface. It uses a continuous wave distributed feedback room temperature quantum cascade laser and a patented new optical multi-pass cell. The aim of SPIRIT field studies is to get a better understanding of land and water bodies to atmosphere exchange mechanisms of greenhouse gases (GHG). The analytical procedures to derive concentrations and fluxes are described, as well as the performances of the instrument under field conditions. The ability of SPIRIT to assess space and time dependence emissions of two GHG—nitrous oxide (N 2 O) and methane (CH 4 )—for different types of ecosystems is demonstrated through in situ measurements on peatland, on fertilized soil, and on water body systems. The objectives of these investigations and preliminary significant results are reported

  18. Evolution of the magnetic helicity flux during the formation and eruption of flux ropes

    Energy Technology Data Exchange (ETDEWEB)

    Romano, P. [INAF—Osservatorio Astrofisico di Catania, Via S. Sofia 78, I-95123 Catania (Italy); Zuccarello, F. P. [Centre for Mathematical Plasma-Astrophysics, KU Leuven, Celestijnenlaan 200B, B-3001 Leuven (Belgium); Guglielmino, S. L.; Zuccarello, F., E-mail: paolo.romano@oact.inaf.it [Dipartimento di Fisica e Astronomia—Sezione Astrofisica, Università di Catania, Via S. Sofia 78, I-95123 Catania (Italy)

    2014-10-20

    We describe the evolution and the magnetic helicity flux for two active regions (ARs) since their appearance on the solar disk: NOAA 11318 and NOAA 11675. Both ARs hosted the formation and destabilization of magnetic flux ropes. In the former AR, the formation of the flux rope culminated in a flare of C2.3 GOES class and a coronal mass ejection (CME) observed by Large Angle and Spectrometric Coronagraph Experiment. In the latter AR, the region hosting the flux rope was involved in several flares, but only a partial eruption with signatures of a minor plasma outflow was observed. We found a different behavior in the accumulation of the magnetic helicity flux in the corona, depending on the magnetic configuration and on the location of the flux ropes in the ARs. Our results suggest that the complexity and strength of the photospheric magnetic field is only a partial indicator of the real likelihood of an AR producing the eruption of a flux rope and a subsequent CME.

  19. Monte Carlo simulated dose to the human body due to neutrons emitted in laser-fusion

    International Nuclear Information System (INIS)

    Gileadi, A.E.; Cohen, M.O.

    1977-01-01

    Considering a point neutron source located at a given distance from the human body, modeled by a 'standard reference man' phantom, neutron doses to the whole body, as well as to selected organs thereof, are determined, using the SAM-CE system, a Monte Carlo computer code, written in Fortran and designed to solve time, space and energy dependent neutron and gamma ray transport equations in complex three-dimensional geometrice. Collision density, energy deposition and dose are treated in the SAM-CE system as flux functionals. A special feature of SAM-CE is its use of the 'Combinatorial Geometry' technique which affords the user geometric capabilities exceeding those available with other commonly used geometric packages. All neutron and gamma ray cross section data, as well as gamma ray production data, are derived from the ENDF libraries. Both resolved and unresolved resonance parameters from ENDF neutron data files are treated automatically and extremely precise and detailed descriptions of cross section behavior is permitted. Such treatment avoids the ambiguities usually associated with multi-group codes, which use flux-averaged cross sections based on assumed flux distributions which may or may not be appropriate. The 'standard reference man', a heterogeneous phantom, uses simple geometric forms to approximate the shape and dimensions of the human body. Materials composition of each subregion representing a certain 'organ' is given. Typical values of neutron doses to the whole body and to selected 'organs' of interest are presented

  20. Characteristics of heat flux and particle flux to the divertor in H-mode of JT-60U

    International Nuclear Information System (INIS)

    Itami, K.; Hosogane, N.; Asakura, N.; Kubo, H.; Tsuji, S.; Shimada, M.

    1995-01-01

    Heat flux and particle flux behavior in H-mode is studied in a comparative manner. It was confirmed that the multiple peak structure of heat flux during ELM activity has a role in reducing the average value of a peak heat flux at the divertor. In order to characterize heat and particle flux during ELM activity, the ELM part and the steady state part of heat flux and particle flux were determined and statistically analyzed. A large in-out asymmetry of peak ELM heat flux density was found. The asymmetry is almost unaffected by the ion grad-B drift direction. In-out asymmetry of both ELM and steady-state parts of the particle flux were found to be similar. ((orig.))