Multi-dimensional roles of ketone bodies in fuel metabolism, signaling, and therapeutics

PubMed Central

Puchalska, Patrycja; Crawford, Peter A.

2017-01-01

Ketone body metabolism is a central node in physiological homeostasis. In this review, we discuss how ketones serve discrete fine-tuning metabolic roles that optimize organ and organism performance in varying nutrient states, and protect from inflammation and injury in multiple organ systems. Traditionally viewed as metabolic substrates enlisted only in carbohydrate restriction, recent observations underscore the importance of ketone bodies as vital metabolic and signaling mediators when carbohydrates are abundant. Complementing a repertoire of known therapeutic options for diseases of the nervous system, prospective roles for ketone bodies in cancer have arisen, as have intriguing protective roles in heart and liver, opening therapeutic options in obesity-related and cardiovascular disease. Controversies in ketone metabolism and signaling are discussed to reconcile classical dogma with contemporary observations. PMID:28178565

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

PubMed Central

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

The interconversion and disposal of ketone bodies in untreated and injured post-absorptive rats

PubMed Central

Barton, Roger N.

1973-01-01

[3-14C]Acetoacetate and β-hydroxy[3-14C]butyrate were used to investigate the kinetics of ketone body metabolism in rats 3h after bilateral hind-limb ischaemia and in controls, both groups being in the post-absorptive state and in a 20°C environment. Calculations were carried out as described by Heath & Barton (1973) and the following conclusions were reached. 1. In both injured and control rats, the rates of irreversible disposal (extrahepatic utilization) of β-hydroxybutyrate and acetoacetate were proportional within experimental error to their blood concentrations up to at least 0.4mm (the maximum found in these rats), implying that they were determined, via these concentrations, by the rates of production by the liver. 2. Conversion of blood β-hydroxybutyrate into blood acetoacetate took place mainly in the liver, but the reverse process occurred mainly in extrahepatic tissues. 3. The `metabolic clearance rate' (the volume of blood which, if completely cleared of substrate in unit time, would give a disposal rate equal to that in the whole animal) was calculated for β-hydroxybutyrate and acetoacetate. Comparison with the cardiac output showed that in control rats the proportion of circulating β-hydroxybutyrate extracted was lower than that of acetoacetate, clearance of which appeared almost complete. After injury both metabolic clearance rates decreased, probably because of the lower cardiac output. 4. After injury, because the average blood concentrations of ketone bodies, especially acetoacetate, were higher, the mean total rate of disposal also increased. Assuming complete oxidation, the mean contribution of ketone bodies to the whole body O2 consumption rose from 7 to 15%. PMID:4798577

The interconversion and disposal of ketone bodies in untreated and injured post-absorptive rats.

PubMed

Barton, R N

1973-11-01

[3-(14)C]Acetoacetate and beta-hydroxy[3-(14)C]butyrate were used to investigate the kinetics of ketone body metabolism in rats 3h after bilateral hind-limb ischaemia and in controls, both groups being in the post-absorptive state and in a 20 degrees C environment. Calculations were carried out as described by Heath & Barton (1973) and the following conclusions were reached. 1. In both injured and control rats, the rates of irreversible disposal (extrahepatic utilization) of beta-hydroxybutyrate and acetoacetate were proportional within experimental error to their blood concentrations up to at least 0.4mm (the maximum found in these rats), implying that they were determined, via these concentrations, by the rates of production by the liver. 2. Conversion of blood beta-hydroxybutyrate into blood acetoacetate took place mainly in the liver, but the reverse process occurred mainly in extrahepatic tissues. 3. The ;metabolic clearance rate' (the volume of blood which, if completely cleared of substrate in unit time, would give a disposal rate equal to that in the whole animal) was calculated for beta-hydroxybutyrate and acetoacetate. Comparison with the cardiac output showed that in control rats the proportion of circulating beta-hydroxybutyrate extracted was lower than that of acetoacetate, clearance of which appeared almost complete. After injury both metabolic clearance rates decreased, probably because of the lower cardiac output. 4. After injury, because the average blood concentrations of ketone bodies, especially acetoacetate, were higher, the mean total rate of disposal also increased. Assuming complete oxidation, the mean contribution of ketone bodies to the whole body O(2) consumption rose from 7 to 15%.

Ketone bodies and brain glutamate and GABA metabolism.

PubMed

Daikhin, Y; Yudkoff, M

1998-01-01

The effects of ketone bodies on brain metabolism of glutamate and GABA were studied in three different systems: synaptosomes, cultured astrocytes and the whole animal. In synaptosomes the addition of either acetoacetate or 3-OH-butyrate was associated with diminished consumption of glutamate via transamination to aspartate and increased formation of labelled GABA from either L-[2H5-2,3,3,4, 4]glutamine or L-[15N]glutamine. There was no effect of ketone bodies on synaptosomal GABA transamination. An increase of total forebrain GABA and a diminution of aspartate was noted when mice were injected intraperitoneally with 3-OH-butyrate. In cultured astrocytes the addition of acetoacetate to the medium was associated with a significantly enhanced rate of citrate production and with a diminution in the rate of conversion of [15N]glutamate to [15N]aspartate. These data are consistent with the hypothesis that the metabolism of ketone bodies to acetyl-CoA results in a diminution of the pool of brain oxaloacetate, which is consumed in the citrate synthetase reaction (oxaloacetate + acetyl-CoA --> citrate). As less oxaloacetate is available to the aspartate aminotransferase reaction, thereby lowering the rate of glutamate transamination, more glutamate becomes accessible to the glutamate decarboxylase pathway, thereby favoring the synthesis of GABA.

Ketones blood test

MedlinePlus

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 ...

Uptake of aldehydes and ketones at typical indoor concentrations by houseplants.

PubMed

Tani, Akira; Hewitt, C Nicholas

2009-11-01

The uptake rates of low-molecular weight aldehydes and ketones by peace lily (Spathiphyllum clevelandii) and golden pothos (Epipremnum aureum) leaves at typical indoor ambient concentrations (10(1)-10(2) ppbv) were determined. The C3-C6 aldehydes and C4-C6 ketones were taken up by the plant leaves, but the C3 ketone acetone was not. The uptake rate normalized to the ambient concentration C(a) ranged from 7 to 19 mmol m(-2) s(-1) and from 2 to 7 mmol m(-2) s(-1) for the aldehydes and ketones, respectively. Longer-term fumigation results revealed that the total uptake amounts were 30-100 times as much as the amounts dissolved in the leaf, suggesting that volatile organic carbons are metabolized in the leaf and/or translocated through the petiole. The ratio of the intercellular concentration to the external (ambient) concentration (C(i)/C(a)) was significantly lower for most aldehydes than for most ketones. In particular, a linear unsaturated aldehyde, crotonaldehyde, had a C(i)/C(a) ratio of approximately 0, probably because of its highest solubility in water.

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

PubMed

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

Involvement of brain ketone bodies and the noradrenergic pathway in diabetic hyperphagia in rats.

PubMed

Iwata, Kinuyo; Kinoshita, Mika; Yamada, Shunji; Imamura, Takuya; Uenoyama, Yoshihisa; Tsukamura, Hiroko; Maeda, Kei-Ichiro

2011-03-01

Uncontrolled type 1 diabetes leads to hyperphagia and severe ketosis. This study was conducted to test the hypothesis that ketone bodies act on the hindbrain as a starvation signal to induce diabetic hyperphagia. Injection of an inhibitor of monocarboxylate transporter 1, a ketone body transporter, into the fourth ventricle normalized the increase in food intake in streptozotocin (STZ)-induced diabetic rats. Blockade of catecholamine synthesis in the hypothalamic paraventricular nucleus (PVN) also restored food intake to normal levels in diabetic animals. On the other hand, hindbrain injection of the ketone body induced feeding, hyperglycemia, and fatty acid mobilization via increased sympathetic activity and also norepinephrine release in the PVN. This result provides evidence that hyperphagia in STZ-induced type 1 diabetes is signaled by a ketone body sensed in the hindbrain, and mediated by noradrenergic inputs to the PVN.

Ketones urine test

MedlinePlus

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 ...

The Failing Heart Relies on Ketone Bodies as a Fuel.

PubMed

Aubert, Gregory; Martin, Ola J; Horton, Julie L; Lai, Ling; Vega, Rick B; Leone, Teresa C; Koves, Timothy; Gardell, Stephen J; Krüger, Marcus; Hoppel, Charles L; Lewandowski, E Douglas; Crawford, Peter A; Muoio, Deborah M; Kelly, Daniel P

2016-02-23

Significant evidence indicates that the failing heart is energy starved. During the development of heart failure, the capacity of the heart to utilize fatty acids, the chief fuel, is diminished. Identification of alternate pathways for myocardial fuel oxidation could unveil novel strategies to treat heart failure. Quantitative mitochondrial proteomics was used to identify energy metabolic derangements that occur during the development of cardiac hypertrophy and heart failure in well-defined mouse models. As expected, the amounts of proteins involved in fatty acid utilization were downregulated in myocardial samples from the failing heart. Conversely, expression of β-hydroxybutyrate dehydrogenase 1, a key enzyme in the ketone oxidation pathway, was increased in the heart failure samples. Studies of relative oxidation in an isolated heart preparation using ex vivo nuclear magnetic resonance combined with targeted quantitative myocardial metabolomic profiling using mass spectrometry revealed that the hypertrophied and failing heart shifts to oxidizing ketone bodies as a fuel source in the context of reduced capacity to oxidize fatty acids. Distinct myocardial metabolomic signatures of ketone oxidation were identified. These results indicate that the hypertrophied and failing heart shifts to ketone bodies as a significant fuel source for oxidative ATP production. Specific metabolite biosignatures of in vivo cardiac ketone utilization were identified. Future studies aimed at determining whether this fuel shift is adaptive or maladaptive could unveil new therapeutic strategies for heart failure. © 2016 American Heart Association, Inc.

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

PubMed

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.

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

PubMed

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)

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

PubMed Central

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

2013-01-01

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. PMID:23233542

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

PubMed

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.

Cerebral utilization of glucose, ketone bodies and oxygen in starving infant rats and the effect of intrauterine growth retardation.

PubMed

Dahlquist, G

1976-10-01

Cerebral arteriovenous differences of acetoacetate, D-beta-hydroxybutyrate, glucose, lactate and oxygen and brain DNA content was measured at 20 days of age in intrauterine growth retarded (IUGR) rats and normal littermates after 48 and 72 h of starvation. Cerebral blood flow (CBF) was measured with labeled microspheres in other comparable groups of IUGR and control rats. CBF was similar in IUGR and normal littermates (0.57+/-0.09 and 0.58+/-0.10 ml/min respectively). After 48 h of starvation, arterial glucose was significantly lower in IUGR than control animals but the arterial concentrations of ketone bodies were similar. After 48 h of starvation, cerebral arteriovenous difference of beta-hydroxybutyrate was significantly higher in control than IUGR rats also when expressed per mg brain DNA as was the fractional uptake of D-beta-hydroxybutyrate. After 72 h of starvation, arterial concentrations of ketone bodies were significantly lower in IUGR rats than controls but the fractional uptake of D-beta-hydroxybutyrate was increased compared to IUGR rats starved for 48 h. The average percentage of calculated total substrate uptake (mumol/min) accounted for by ketone bodies increased in control animals from 31.1% after 48 h of starvation to 41.0% after 72 h of starvation. In IUGR rats these percentage values were 26.5 and 25.7 respectively. After 72 h of starvation the fraction of total cerebral uptake of substrates accounted for by ketone bodies was significantly higher in control that IUGR rats. As total cerebral uptake of substrates was similar between IUGR and control animals it is concluded that IUGR rats are more dependent on glucose as a substrate for the brain during starvation.

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

PubMed

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.

Ketone bodies do not directly alter excitatory or inhibitory hippocampal synaptic transmission.

PubMed

Thio, L L; Wong, M; Yamada, K A

2000-01-25

To determine the effect of the ketone bodies beta-hydroxybutyrate (betaHB) and acetoacetate (AA) on excitatory and inhibitory neurotransmission in the mammalian CNS. The ketogenic diet is presumed to be an effective anticonvulsant regimen for some children with medically intractable seizures. However, its mechanism of action remains a mystery. According to one hypothesis, ketone bodies have anticonvulsant properties. The authors examined the effect of betaHB and AA on excitatory and inhibitory synaptic transmission in rat hippocampal-entorhinal cortex slices and cultured hippocampal neurons. In cultured neurons, their effect was also directly assayed on postsynaptic receptor properties. Finally, their ability to prevent spontaneous seizures was determined in a hippocampal-entorhinal cortex slice model. betaHB and AA did not alter synaptic transmission in these models. The anticonvulsant properties of the ketogenic diet do not result from a direct effect of ketone bodies on the primary voltage and ligand gated ion channels mediating excitatory or inhibitory neurotransmission in the hippocampus.

Cerebral ketone body metabolism.

PubMed

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.

The neuroprotective properties of calorie restriction, the ketogenic diet, and ketone bodies.

PubMed

Maalouf, Marwan; Rho, Jong M; Mattson, Mark P

2009-03-01

Both calorie restriction and the ketogenic diet possess broad therapeutic potential in various clinical settings and in various animal models of neurological disease. Following calorie restriction or consumption of a ketogenic diet, there is notable improvement in mitochondrial function, a decrease in the expression of apoptotic and inflammatory mediators and an increase in the activity of neurotrophic factors. However, despite these intriguing observations, it is not yet clear which of these mechanisms account for the observed neuroprotective effects. Furthermore, limited compliance and concern for adverse effects hamper efforts at broader clinical application. Recent research aimed at identifying compounds that can reproduce, at least partially, the neuroprotective effects of the diets with less demanding changes to food intake suggests that ketone bodies might represent an appropriate candidate. Ketone bodies protect neurons against multiple types of neuronal injury and are associated with mitochondrial effects similar to those described during calorie restriction or ketogenic diet treatment. The present review summarizes the neuroprotective effects of calorie restriction, of the ketogenic diet and of ketone bodies, and compares their putative mechanisms of action.

Leptin controls ketone body utilization in hypothalamic neuron.

PubMed

Narishima, Ryota; Yamasaki, Masahiro; Hasegawa, Shinya; Yoshida, Saki; Tanaka, Shinya; Fukui, Tetsuya

2011-03-03

Leptin is an appetite-controlling peptide secreted from adipose tissue. Previously, we showed that the gene expression of acetoacetyl-CoA synthetase (AACS), the ketone body-utilizing enzyme for lipid synthesis, was suppressed by leptin deficiency-induced obesity in white adipose tissue. In this study, to clarify the effects of leptin on ketone body utilization in the central nervous system, we examined the effects of leptin signaling on AACS expression. In situ hybridization analysis of ob/ob and db/db mice revealed that AACS mRNA level was reduced by leptin deficiency in the arcuate nucleus (Arc) and ventromedial hypothalamic nucleus (VMH) in hypothalamus but not in other brain regions. Moreover, AACS mRNA level was increased by leptin treatment both in primary cultured neural cells and in N41 neural-like cells. In N41 cells, AACS level was decreased by AMPK inducer but increased by AMPK inhibitor. These results suggest that the up-regulation of AACS expression by leptin is due to the suppression of AMPK activity via neural leptin signaling and that the deficiency of this regulation may be responsible for neurological disorders in central appetite control. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Ketone bodies protection against HIV-1 Tat-induced neurotoxicity.

PubMed

Hui, Liang; Chen, Xuesong; Bhatt, Dhaval; Geiger, Nicholas H; Rosenberger, Thad A; Haughey, Norman J; Masino, Susan A; Geiger, Jonathan D

2012-07-01

HIV-1-associated neurocognitive disorder (HAND) is a syndrome that ranges clinically from subtle neuropsychological impairments to profoundly disabling HIV-associated dementia. Not only is the pathogenesis of HAND unclear, but also effective treatments are unavailable. The HIV-1 transactivator of transcription protein (HIV-1 Tat) is strongly implicated in the pathogenesis of HAND, in part, because of its well-characterized ability to directly excite neurons and cause neurotoxicity. Consistent with previous findings from others, we demonstrate here that HIV-1 Tat induced neurotoxicity, increased intracellular calcium, and disrupted a variety of mitochondria functions, such as reducing mitochondrial membrane potential, increasing levels of reactive oxygen species, and decreasing bioenergetic efficiency. Of therapeutic importance, we show that treatment of cultured neurons with ketone bodies normalized HIV-1 Tat induced changes in levels of intracellular calcium, mitochondrial function, and neuronal cell death. Ketone bodies are normally produced in the body and serve as alternative energy substrates in tissues including brain and can cross the blood-brain barrier. Ketogenic strategies have been used clinically for treatment of neurological disorders and our current results suggest that similar strategies may also provide clinical benefits in the treatment of HAND. © 2012 The Authors. Journal of Neurochemistry © 2012 International Society for Neurochemistry.

Role of VMH ketone bodies in adjusting caloric intake to increased dietary fat content in DIO and DR rats.

PubMed

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

2015-05-15

The objective of this study was to determine the potential role of astrocyte-derived ketone bodies in regulating the early changes in caloric intake of diet induced-obese (DIO) versus diet-resistant (DR) rats fed a 31.5% fat high-energy (HE) diet. After 3 days on chow or HE diet, DR and DIO rats were assessed for their ventromedial hypothalamic (VMH) ketone bodies levels and neuronal ventromedial hypothalamic nucleus (VMN) sensing using microdialysis coupled to continuous food intake monitoring and calcium imaging in dissociated neurons, respectively. DIO rats ate more than DR rats over 3 days of HE diet intake. On day 3 of HE diet intake, DR rats reduced their caloric intake while DIO rats remained hyperphagic. Local VMH astrocyte ketone bodies production was similar between DR and DIO rats during the first 6 h after dark onset feeding but inhibiting VMH ketone body production in DR rats on day 3 transiently returned their intake of HE diet to the level of DIO rats consuming HE diet. In addition, dissociated VMN neurons from DIO and DR rats were equally sensitive to the largely excitatory effects of β-hydroxybutyrate. Thus while DR rats respond to increased VMH ketone levels by decreasing their intake after 3 days of HE diet, this is not the case of DIO rats. These data suggest that DIO inherent leptin resistance prevents ketone bodies inhibitory action on food intake.

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

PubMed

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.

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

PubMed

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.

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

PubMed

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.

Regulation of Hypothalamic Neuronal Sensing and Food Intake by Ketone Bodies and Fatty Acids

PubMed Central

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

2014-01-01

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. PMID:24379353

Sources and concentrations of aldehydes and ketones in indoor environments in the UK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crump, D.R.; Gardiner, D.

1989-01-01

Individual aldehydes and ketones can be separated, identified and quantitatively estimated by trapping the 2,4-dinitrophenylhydrazine (DNPH) derivatives and analysis by HPLC. Appropriate methods and detection limits are reported. Many sources of formaldehyde have been identified by this means and some are found to emit other aldehydes and ketones. The application of this method to determine the concentration of these compounds in the atmospheres of buildings is described and the results compared with those obtained using chromotropic acid or MBTH.

21 CFR 862.1435 - Ketones (nonquantitative) test system.

Code of Federal Regulations, 2013 CFR

2013-04-01

... (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test...) test system is a device intended to identify ketones in urine and other body fluids. Identification of... acidity of body fluids) or ketosis (a condition characterized by increased production of ketone bodies...

21 CFR 862.1435 - Ketones (nonquantitative) test system.

Code of Federal Regulations, 2011 CFR

2011-04-01

... (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test...) test system is a device intended to identify ketones in urine and other body fluids. Identification of... acidity of body fluids) or ketosis (a condition characterized by increased production of ketone bodies...

21 CFR 862.1435 - Ketones (nonquantitative) test system.

Code of Federal Regulations, 2012 CFR

2012-04-01

... (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test...) test system is a device intended to identify ketones in urine and other body fluids. Identification of... acidity of body fluids) or ketosis (a condition characterized by increased production of ketone bodies...

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

PubMed Central

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

2016-01-01

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 for cerebral glucose hypometabolism and unravel the functionality of cerebral mitochondria in type 2 diabetes mellitus. Acutely isolated cerebral cortical and hippocampal slices of db/db mice were incubated in media containing [U-13C]glucose, [1,2-13C]acetate or [U-13C]β-hydroxybutyrate and tissue extracts were analysed by mass spectrometry. Oxygen consumption and ATP synthesis of brain mitochondria of db/db mice were assessed by Seahorse XFe96 and luciferin-luciferase assay, respectively. Glucose hypometabolism was observed for both cerebral cortical and hippocampal slices of db/db mice. Significant increased metabolism of [1,2-13C]acetate and [U-13C]β-hydroxybutyrate was observed for hippocampal slices of db/db mice. Furthermore, brain mitochondria of db/db mice exhibited elevated oxygen consumption and ATP synthesis rate. This study provides evidence of several changes in brain energy 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. PMID:28058963

Optimized preoperative fasting times decrease ketone body concentration and stabilize mean arterial blood pressure during induction of anesthesia in children younger than 36 months: a prospective observational cohort study.

PubMed

Dennhardt, Nils; Beck, Christiane; Huber, Dirk; Sander, Bjoern; Boehne, Martin; Boethig, Dietmar; Leffler, Andreas; Sümpelmann, Robert

2016-08-01

In pediatric anesthesia, preoperative fasting guidelines are still often exceeded. The objective of this noninterventional clinical observational cohort study was to evaluate the effect of an optimized preoperative fasting management (OPT) on glucose concentration, ketone bodies, acid-base balance, and change in mean arterial blood pressure (MAP) during induction of anesthesia in children. Children aged 0-36 months scheduled for elective surgery with OPT (n = 50) were compared with peers studied before optimizing preoperative fasting time (OLD) (n = 50) who were matched for weight, age, and height. In children with OPT (n = 50), mean fasting time (6.0 ± 1.9 h vs 8.5 ± 3.5 h, P < 0.001), deviation from guideline (ΔGL) (1.2 ± 1.4 h vs 3.7 ± 3.1 h, P < 0.001, ΔGL>2 h 8% vs 70%), ketone bodies (0.2 ± 0.2 mmol·l(-1) vs 0.6 ± 0.6 mmol·l(-1) , P < 0.001), and incidence of hypotension (MAP <40 mmHg, 0 vs 5, P = 0.022) were statistically significantly lower and MAP after induction was statistically significantly higher (55.2 ± 9.5 mmHg vs 50.3 ± 9.8 mmHg, P = 0.015) as compared to children in the OLD (n = 50) group. Glucose, lactate, bicarbonate, base excess, and anion gap did not significantly differ. Optimized fasting times improve the metabolic and hemodynamic condition during induction of anesthesia in children younger than 36 months of age. © 2016 John Wiley & Sons Ltd.

Clinical review: Ketones and brain injury

PubMed Central

2011-01-01

Although much feared by clinicians, the ability to produce ketones has allowed humans to withstand prolonged periods of starvation. At such times, ketones can supply up to 50% of basal energy requirements. More interesting, however, is the fact that ketones can provide as much as 70% of the brain's energy needs, more efficiently than glucose. Studies suggest that during times of acute brain injury, cerebral uptake of ketones increases significantly. Researchers have thus attempted to attenuate the effects of cerebral injury by administering ketones exogenously. Hypertonic saline is commonly utilized for management of intracranial hypertension following cerebral injury. A solution containing both hypertonic saline and ketones may prove ideal for managing the dual problems of refractory intracranial hypertension and low cerebral energy levels. The purpose of the present review is to explore the physiology of ketone body utilization by the brain in health and in a variety of neurological conditions, and to discuss the potential for ketone supplementation as a therapeutic option in traumatic brain injury. PMID:21489321

Sirtuin 3 mediates neuroprotection of ketones against ischemic stroke

PubMed Central

Yin, Junxiang; Han, Pengcheng; Tang, Zhiwei; Liu, Qingwei; Shi, Jiong

2015-01-01

Stroke is one of the leading causes of death. Growing evidence indicates that ketone bodies have beneficial effects in treating stroke, but their underlying mechanism remains unclear. Our previous study showed ketone bodies reduced reactive oxygen species by using NADH as an electron donor, thus increasing the NAD+/NADH ratio. In this study, we investigated whether mitochondrial NAD+-dependent Sirtuin 3 (SIRT3) could mediate the neuroprotective effects of ketone bodies after ischemic stroke. We injected mice with either normal saline or ketones (beta-hydroxybutyrate and acetoacetate) at 30 minutes after ischemia induced by transient middle cerebral artery (MCA) occlusion. We found that ketone treatment enhanced mitochondria function, reduced oxidative stress, and therefore reduced infarct volume. This led to improved neurologic function after ischemia, including the neurologic score and the performance in Rotarod and open field tests. We further showed that ketones' effects were achieved by upregulating NAD+-dependent SIRT3 and its downstream substrates forkhead box O3a (FoxO3a) and superoxide dismutase 2 (SOD2) in the penumbra region since knocking down SIRT3 in vitro diminished ketones' beneficial effects. These results provide us a foundation to develop novel therapeutics targeting this SIRT3-FoxO3a-SOD2 pathway. PMID:26058697

Ketone esters increase brown fat in mice and overcome insulin resistance in other tissues in the rat.

PubMed

Veech, Richard L

2013-10-01

Brown adipose tissue (BAT) is classically activated by sympathetic nervous stimulation resulting from exposure to cold. Feeding a high-fat diet also induces development of brown fat, but is decreased by caloric restriction. Blood ketone bodies, which function as alternative energy substrates to glucose, are increased during caloric restriction. Here we discuss the unexpected observation that feeding an ester of ketone bodies to the mouse, which increases blood ketone body concentrations, results in an activation of brown fat. The mechanism of this activation of brown fat is similar to that occurring from cold exposure in that cyclic adenosine monophosphate (AMP) levels are increased as are levels of the transcription factor cyclic AMP-responsive element-binding protein, which is also increased by ketone ester feeding. Other effects of feeding ketone esters, in addition to their ability to induce brown fat, are discussed such as their ability to overcome certain aspects of insulin resistance and to ameliorate the accumulation of amyloid and phosphorylated tau protein in brain, and improve cognitive function, in a triple transgenic mouse model of Alzheimer's disease. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

Cerebral Ketone Metabolism During Development and Injury

PubMed Central

Prins, Mayumi L.

2011-01-01

Cerebral metabolism of ketones is a normal part of the process of brain development. While the mature brain relies on glucose as a primary fuel source, metabolism of ketone bodies remains an alternative energy source under conditions of starvation. The neuroprotective properties of brain ketone metabolism make this alternative substrate a viable therapeutic option for various pathologies. Since the ability to revert to utilizing ketones as an alternative substrate is greatest in the younger post-weaned brain, this particular therapeutic approach remains an untapped resource particularly for pediatric pathological conditions. PMID:22104087

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

PubMed

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.

Ketones and Human Performance.

PubMed

Scott, Jonathan M; Deuster, Patricia A

Everyone is seeking nutritional strategies that might benefit performance. One approach receiving much attention is ketones, or ketosis. Ketones are very simple compounds made of hydrogen, carbon, and oxygen, and ketosis is a metabolic state whereby the body uses predominantly ketones. Ketosis can be achieved by fasting for longer than 72 hours or by following a very lowcarbohydrate, high-fat diet (ketogenic diet) for several days to weeks. Alternatively, ketone supplements purportedly induce ketosis rapidly and do not require strict adherence to any specific type of diet; however, much of the touted benefits are anecdotal. A potential role for ketosis as a performance enhancer was first introduced in 1983 with the idea that chronic ketosis without caloric restriction could preserve submaximal exercise capability by sparing glycogen or conserving the limited carbohydrate stores. Few human studies on the effects of a ketogenic diet on performance have yielded positive results, and most studies have yielded equivocal or null results, and a few negative results. Many questions about ketones relevant to Special Operations Forces (SOF) remain unanswered. At present, a ketogenic diet and/or a ketone supplement do not appear confer performance benefits for SOF. Instead, Operators should engage with their unit dietitian to develop individualized nutritional strategies based on unique mission requirements. The authors review the concept of a ketogenic diet, describe some potential benefits and risks of ketosis, review the performance literature and how to measure ketone status, and then summarize the landscape in 2017. 2017.

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

PubMed

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 < 0.0001). During the 2-h glucose clamps, insulin levels were twofold higher (31 vs 16 mU·L, P < 0.01) and glucose uptake 32% faster (1.66 vs 1.26 g·kg, P < 0.001). The ketone drink increased by 61 g, the total glucose infused for 2 h, from 197 to 258 g, and muscle glycogen was 50% higher (246 vs 164 mmol glycosyl units per kilogram dry weight, P < 0.05) than after the control drink. In the presence of constant high glucose concentrations, a ketone ester drink increased endogenous insulin levels, glucose uptake, and muscle glycogen synthesis.

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

PubMed

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.

Regulation of Ketone Body Metabolism and the Role of PPARα

PubMed Central

Grabacka, Maja; Pierzchalska, Malgorzata; Dean, Matthew; Reiss, Krzysztof

2016-01-01

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. PMID:27983603

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

PubMed

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.

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

PubMed

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.

Solvent, Temperature And Concentration Effects on the Optical Activity of Chiral FIVE-And-SIX Membered Ring Ketones Conformers

NASA Astrophysics Data System (ADS)

Al-Basheer, Watheq

2017-06-01

Chiral five-and-six membered ring ketones are important molecules that are found in many biological systems and can exist in many possible conformers. In this talk, experimental and computational investigation of solvent, temperature and concentration effects on the circular dichroism (CD) and optical rotation (OR) of (R)-3 -methylcyclohexanone (R3MCH), (R)-3-methylcyclopentanone (R3MCP) and carvone conformers will be discussed. CD and OR measurements of these ketones gaseous samples and in ten common solvents of wide polarity range for different concentrations and sample temperatures were recorded and related to molecular conformation. Density functional theoretical calculations were performed using Gaussian09 at B3LYP functions with aug-cc-pVDZ level of theory. Also, CD and OR spectra for the optimized geometries of the ketones dominant conformers were computed over the ultraviolet and visible region in the gas phase as well as in ten solvents of varying polarity range, and under the umbrella of the polarizable continuum model (PCM). By comparing theoretical and experimental results, few thermodynamic parameters were deduced for the individual equatorial and axial conformers of each molecule in gas phase and in solvation.

HMGCS2 promotes autophagic degradation of the amyloid-β precursor protein through ketone body-mediated mechanisms.

PubMed

Hu, Li-Tian; Zhu, Bing-Lin; Lai, Yu-Jie; Long, Yan; Zha, Jing-Si; Hu, Xiao-Tong; Zhang, John H; Chen, Guo-Jun

2017-04-29

HMGCS2 (mitochondrial 3-hydroxy-3-methylglutaryl-COA synthase 2) is a control enzyme in ketogenesis. The mitochondrial localization and interaction with APP (β-amyloid precursor protein) suggest that HMGCS2 may play a role in the pathophysiology of AD (Alzheimer's disease). Here we report that overexpression of HMGCS2 decreased levels of APP and related CTFs (carboxy-terminal fragments), which was largely prevented by an autophagic inhibitor chloroquine. In addition, HMGCS2 enhancement of autophagic marker LC3II was diminished by rapamycin, an inhibitor of mechanistic target of rapamycin. Moreover, deprivation of EBSS (Earle's Balanced Salt Solution) significantly augmented the effect of HMGCS2 on LC3II, while acetoacetate reversed the reduction of LC3II, APP and CTFs which was induced by HMGCS2 knockdown. In the presence of acetoacetate, rapamycin failed to induce further increase of LC3II, which mimicked the effect of HMGCS2 overexpression. Finally, HMGCS2 enhanced the antioxidant response. Collectively, HMGCS2 shares with ketone bodies common features in autophagic clearance of APP and CTFs, suggesting that ketone bodies play an important role in HMGCS2 regulation of the autophagy. Copyright © 2017 Elsevier Inc. All rights reserved.

Ketone body β-hydroxybutyrate blocks the NLRP3 inflammasome-mediated inflammatory disease

PubMed Central

Youm, Yun-Hee; Nguyen, Kim Y.; Grant, Ryan W.; Goldberg, Emily L.; Bodogai, Monica; Kim, Dongin; D'Agostino, Dominic; Planavsky, Noah; Lupfer, Christopher; Kanneganti, Thirumala D.; Kang, Seokwon; Horvath, Tamas L.; Fahmy, Tarek M.; Crawford, Peter A.; Biragyn, Arya; Alnemri, Emad; Dixit, Vishwa Deep

2015-01-01

Ketone bodies , β-hydroxybutyrate (BHB) and acetoacetate support mammalian survival during states of energy deficit by serving as alternative source of ATP1. BHB levels are elevated during starvation, high-intensity exercise or by the low carbohydrate ketogenic diet2. Prolonged caloric restriction or fasting reduces inflammation as immune system adapts to low glucose supply and energy metabolism switches towards mitochondrial fatty acid oxidation, ketogenesis and ketolysis2-6. However, role of ketones bodies in regulation of innate immune response is unknown. We report that BHB, but neither acetoacetate nor structurally-related short chain fatty acids, butyrate and acetate, suppresses activation of the NLRP3 inflammasome in response to several structurally unrelated NLRP3 activators, without impacting NLRC4, AIM2 or non-canonical caspase-11 inflammasome activation. Mechanistically, BHB inhibits NLRP3 inflammasome by preventing K+ efflux and reducing ASC oligomerization and speck formation. The inhibitory effects of BHB on NLRP3 were not dependent on chirality or classical starvation regulated mechanisms like AMPK, reactive oxygen species (ROS), autophagy or glycolytic inhibition. BHB blocked NLRP3 inflammasome without undergoing oxidation in TCA cycle, independently of uncoupling protein-2 (UCP2), Sirt2, receptor Gpr109a and inhibition of NLRP3 did not correlate with magnitude of histone acetylation in macrophages. BHB reduced the NLRP3 inflammasome mediated IL-1β and IL-18 production in human monocytes. In vivo, BHB attenuates caspase-1 activation and IL-1β secretion in mouse models of NLRP3-mediated diseases like Muckle-Wells Syndrome (MWS), Familial Cold Autoinflammatory syndrome (FCAS) and urate crystal induce body cavity inflammation. Taken together, these findings suggest that the anti-inflammatory effects of caloric restriction or ketogenic diets may be mechanistically linked to BHB-mediated inhibition of the NLRP3 inflammasome, and point to the potential

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

PubMed

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 < 0.001). 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.

On the Metabolism of Exogenous Ketones in Humans

PubMed Central

Stubbs, Brianna J.; Cox, Pete J.; Evans, Rhys D.; Santer, Peter; Miller, Jack J.; Faull, Olivia K.; Magor-Elliott, Snapper; Hiyama, Satoshi; Stirling, Matthew; Clarke, Kieran

2017-01-01

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 and

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

PubMed

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.

Monocarboxylate transporter 1 deficiency and ketone utilization.

PubMed

van Hasselt, Peter M; Ferdinandusse, Sacha; Monroe, Glen R; Ruiter, Jos P N; Turkenburg, Marjolein; Geerlings, Maartje J; Duran, Karen; Harakalova, Magdalena; van der Zwaag, Bert; Monavari, Ardeshir A; Okur, Ilyas; Sharrard, Mark J; Cleary, Maureen; O'Connell, Nuala; Walker, Valerie; Rubio-Gozalbo, M Estela; de Vries, Maaike C; Visser, Gepke; Houwen, Roderick H J; van der Smagt, Jasper J; Verhoeven-Duif, Nanda M; Wanders, Ronald J A; van Haaften, Gijs

2014-11-13

Ketoacidosis is a potentially lethal condition caused by the imbalance between hepatic production and extrahepatic utilization of ketone bodies. We performed exome sequencing in a patient with recurrent, severe ketoacidosis and identified a homozygous frameshift mutation in the gene encoding monocarboxylate transporter 1 (SLC16A1, also called MCT1). Genetic analysis in 96 patients suspected of having ketolytic defects yielded seven additional inactivating mutations in MCT1, both homozygous and heterozygous. Mutational status was found to be correlated with ketoacidosis severity, MCT1 protein levels, and transport capacity. Thus, MCT1 deficiency is a novel cause of profound ketoacidosis; the present work suggests that MCT1-mediated ketone-body transport is needed to maintain acid-base balance.

Depolarizing actions of GABA in immature neurons depend neither on ketone bodies nor on pyruvate.

PubMed

Tyzio, Roman; Allene, Camille; Nardou, Romain; Picardo, Michel A; Yamamoto, Sumii; Sivakumaran, Sudhir; Caiati, Maddalena D; Rheims, Sylvain; Minlebaev, Marat; Milh, Mathieu; Ferré, Pascal; Khazipov, Rustem; Romette, Jean-Louis; Lorquin, Jean; Cossart, Rosa; Khalilov, Ilgam; Nehlig, Astrid; Cherubini, Enrico; Ben-Ari, Yehezkel

2011-01-05

GABA depolarizes immature neurons because of a high [Cl(-)](i) and orchestrates giant depolarizing potential (GDP) generation. Zilberter and coworkers (Rheims et al., 2009; Holmgren et al., 2010) showed recently that the ketone body metabolite DL-3-hydroxybutyrate (DL-BHB) (4 mM), lactate (4 mM), or pyruvate (5 mM) shifted GABA actions to hyperpolarizing, suggesting that the depolarizing effects of GABA are attributable to inadequate energy supply when glucose is the sole energy source. We now report that, in rat pups (postnatal days 4-7), plasma D-BHB, lactate, and pyruvate levels are 0.9, 1.5, and 0.12 mM, respectively. Then, we show that DL-BHB (4 mM) and pyruvate (200 μM) do not affect (i) the driving force for GABA(A) receptor-mediated currents (DF(GABA)) in cell-attached single-channel recordings, (2) the resting membrane potential and reversal potential of synaptic GABA(A) receptor-mediated responses in perforated patch recordings, (3) the action potentials triggered by focal GABA applications, or (4) the GDPs determined with electrophysiological recordings and dynamic two-photon calcium imaging. Only very high nonphysiological concentrations of pyruvate (5 mM) reduced DF(GABA) and blocked GDPs. Therefore, DL-BHB does not alter GABA signals even at the high concentrations used by Zilberter and colleagues, whereas pyruvate requires exceedingly high nonphysiological concentrations to exert an effect. There is no need to alter conventional glucose enriched artificial CSF to investigate GABA signals in the developing brain.

Ketone supplementation decreases tumor cell viability and prolongs survival of mice with metastatic cancer

PubMed Central

Poff, AM; Ari, C; Arnold, P; Seyfried, TN; D’Agostino, DP

2014-01-01

Cancer cells express an abnormal metabolism characterized by increased glucose consumption owing to genetic mutations and mitochondrial dysfunction. Previous studies indicate that unlike healthy tissues, cancer cells are unable to effectively use ketone bodies for energy. Furthermore, ketones inhibit the proliferation and viability of cultured tumor cells. As the Warburg effect is especially prominent in metastatic cells, we hypothesized that dietary ketone supplementation would inhibit metastatic cancer progression in vivo. Proliferation and viability were measured in the highly metastatic VM-M3 cells cultured in the presence and absence of β-hydroxybutyrate (βHB). Adult male inbred VM mice were implanted subcutaneously with firefly luciferase-tagged syngeneic VM-M3 cells. Mice were fed a standard diet supplemented with either 1,3-butanediol (BD) or a ketone ester (KE), which are metabolized to the ketone bodies βHB and acetoacetate. Tumor growth was monitored by in vivo bioluminescent imaging. Survival time, tumor growth rate, blood glucose, blood βHB and body weight were measured throughout the survival study. Ketone supplementation decreased proliferation and viability of the VM-M3 cells grown in vitro, even in the presence of high glucose. Dietary ketone supplementation with BD and KE prolonged survival in VM-M3 mice with systemic metastatic cancer by 51 and 69%, respectively (p < 0.05). Ketone administration elicited anticancer effects in vitro and in vivo independent of glucose levels or calorie restriction. The use of supplemental ketone precursors as a cancer treatment should be further investigated in animal models to determine potential for future clinical use. PMID:24615175

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

PubMed

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.

Cerebral metabolic adaptation and ketone metabolism after brain injury

PubMed Central

Prins, Mayumi L

2010-01-01

The developing central nervous system has the capacity to metabolize ketone bodies. It was once accepted that on weaning, the ‘post-weaned/adult’ brain was limited solely to glucose metabolism. However, increasing evidence from conditions of inadequate glucose availability or increased energy demands has shown that the adult brain is not static in its fuel options. The objective of this review is to summarize the body of literature specifically regarding cerebral ketone metabolism at different ages, under conditions of starvation and after various pathologic conditions. The evidence presented supports the following findings: (1) there is an inverse relationship between age and the brain’s capacity for ketone metabolism that continues well after weaning; (2) neuroprotective potentials of ketone administration have been shown for neurodegenerative conditions, epilepsy, hypoxia/ischemia, and traumatic brain injury; and (3) there is an age-related therapeutic potential for ketone as an alternative substrate. The concept of cerebral metabolic adaptation under various physiologic and pathologic conditions is not new, but it has taken the contribution of numerous studies over many years to break the previously accepted dogma of cerebral metabolism. Our emerging understanding of cerebral metabolism is far more complex than could have been imagined. It is clear that in addition to glucose, other substrates must be considered along with fuel interactions, metabolic challenges, and cerebral maturation. PMID:17684514

Novel ketone diet enhances physical and cognitive performance

PubMed Central

Murray, Andrew J.; Knight, Nicholas S.; Cole, Mark A.; Cochlin, Lowri E.; Carter, Emma; Tchabanenko, Kirill; Pichulik, Tica; Gulston, Melanie K.; Atherton, Helen J.; Schroeder, Marie A.; Deacon, Robert M. J.; Kashiwaya, Yoshihiro; King, M. Todd; Pawlosky, Robert; Rawlins, J. Nicholas P.; Tyler, Damian J.; Griffin, Julian L.; Robertson, Jeremy; Veech, Richard L.; Clarke, Kieran

2016-01-01

Ketone bodies are the most energy-efficient fuel and yield more ATP per mole of substrate than pyruvate and increase the free energy released from ATP hydrolysis. Elevation of circulating ketones via high-fat, low-carbohydrate diets has been used for the treatment of drug-refractory epilepsy and for neurodegenerative diseases, such as Parkinson’s disease. Ketones may also be beneficial for muscle and brain in times of stress, such as endurance exercise. The challenge has been to raise circulating ketone levels by using a palatable diet without altering lipid levels. We found that blood ketone levels can be increased and cholesterol and triglycerides decreased by feeding rats a novel ketone ester diet: chow that is supplemented with (R)-3-hydroxybutyl (R)-3-hydroxybutyrate as 30% of calories. For 5 d, rats on the ketone diet ran 32% further on a treadmill than did control rats that ate an isocaloric diet that was supplemented with either corn starch or palm oil (P < 0.05). Ketone-fed rats completed an 8-arm radial maze test 38% faster than did those on the other diets, making more correct decisions before making a mistake (P < 0.05). Isolated, perfused hearts from rats that were fed the ketone diet had greater free energy available from ATP hydrolysis during increased work than did hearts from rats on the other diets as shown by using [31P]-NMR spectroscopy. The novel ketone diet, therefore, improved physical performance and cognitive function in rats, and its energy-sparing properties suggest that it may help to treat a range of human conditions with metabolic abnormalities.—Murray, A. J., Knight, N. S., Cole, M. A., Cochlin, L. E., Carter, E., Tchabanenko, K., Pichulik, T., Gulston, M. K., Atherton, H. J., Schroeder, M. A., Deacon, R. M. J., Kashiwaya, Y., King, M. T., Pawlosky, R., Rawlins, J. N. P., Tyler, D. J., Griffin, J. L., Robertson, J., Veech, R. L., Clarke, K. Novel ketone diet enhances physical and cognitive performance. PMID:27528626

Combination of aerobic exercise and an arginine, alanine, and phenylalanine mixture increases fat mobilization and ketone body synthesis.

PubMed

Ueda, Keisuke; Sanbongi, Chiaki; Takai, Shoko; Ikegami, Shuji; Fujita, Satoshi

2017-07-01

During exercise, blood levels of several hormones increase acutely. We hypothesized that consumption of a specific combination of amino acids (arginine, alanine, and phenylalanine; A-mix) may be involved in secretion of glucagon, and when combined with exercise may promote fat catabolism. Ten healthy male volunteers were randomized in a crossover study to ingest either A-mix (3 g/dose) or placebo (3 g of dextrin/dose). Thirty minutes after ingesting, each condition subsequently performed workload trials on a cycle ergometer at 50% of maximal oxygen consumption for 1 h. After oral intake of A-mix, the concentrations of plasma ketone bodies and adrenalin during and post-exercise were significantly increased. The area under the curve for glycerol and glucagon was significantly increased in the post-exercise by A-mix administration. These results suggest that pre-exercise ingestion of A-mix causes a shift of energy source from carbohydrate to fat combustion by increasing secretion of adrenalin and glucagon.

Pyruvate and ketone-body transport across the mitochondrial membrane. Exchange properties, pH-dependence and mechanism of the carrier.

PubMed

Halestrap, A P

1978-06-15

The effects of exchangeable ions and pH on the efflux of pyruvate from preloaded mitochondria are reported. Efflux obeys first-order kinetics, and the stimulation of efflux by exchangeable ions such as acetoacetate and lactate obeys Michaelis--Menten kinetics. The apparent Km value +/- S.E. for acetoacetate was 0.56 +/- 0.14 mM (n = 5) and that for lactate 12.3 +/- 2.3 mM (n = 6). The Vmax. values +/- S.E. at 0 degrees C were 16.2 +/- 2.0 and 21.9 +/- 2.7 nmol/min per mg of protein. The exchange of a variety of other substituted monocarboxylates was also studied. Efflux was also stimulated by increasing the external pH. The data gave a pK for the transport process of 8.35 and a Vmax. of 3.31 +/- 0.14 nmol/min per mg. The similarity of the Vmax. values for various exchangeable ions but the difference of this from the Vmax. in the absence of exchangeable ions may indicate that transport of pyruvate occurs with H+ and not in exchange for an OH- ion. The inhibition of transport by alpha-cyano-4-hydroxycinnamate took several seconds to reach completion at 0 degrees C. It is proposed that inhibition occurs by binding to the substrate site and subsequent reaction with an -SH group on the inside of the membrane. The inhibitor can be displaced by substrates that can also enter the mitochondria independently of the carrier and so compete with the inhibitor for the substrate-binding site on the inside of the membrane. A mechanism for transport is proposed that invokes a transition state of pyruvate involving addition of an -SH group to the 2-carbon of pyruvate. Evidence is presented that suggests that ketone bodies may cross the mitochondrial membrane either on the carrier or by free diffusion. The physiological involvement of the carrier in ketone-body metabolism is discussed. The role of ketone bodies and pH in the physiological regulation of pyruvate transport is considered.

Hyperpolarized ketone body metabolism in the rat heart.

PubMed

Miller, Jack J; Ball, Daniel R; Lau, Angus Z; Tyler, Damian J

2018-06-01

The aim of this work was to investigate the use of 13 C-labelled acetoacetate and β-hydroxybutyrate as novel hyperpolarized substrates in the study of cardiac metabolism. [1- 13 C]Acetoacetate was synthesized by catalysed hydrolysis, and both it and [1- 13 C]β-hydroxybutyrate were hyperpolarized by dissolution dynamic nuclear polarization (DNP). Their metabolism was studied in isolated, perfused rat hearts. Hyperpolarized [1- 13 C]acetoacetate metabolism was also studied in the in vivo rat heart in the fed and fasted states. Hyperpolarization of [1- 13 C]acetoacetate and [1- 13 C]β-hydroxybutyrate provided liquid state polarizations of 8 ± 2% and 3 ± 1%, respectively. The hyperpolarized T 1 values for the two substrates were 28 ± 3 s (acetoacetate) and 20 ± 1 s (β-hydroxybutyrate). Multiple downstream metabolites were observed within the perfused heart, including acetylcarnitine, citrate and glutamate. In the in vivo heart, an increase in acetylcarnitine production from acetoacetate was observed in the fed state, as well as a potential reduction in glutamate. In this work, methods for the generation of hyperpolarized [1- 13 C]acetoacetate and [1- 13 C]β-hydroxybutyrate were investigated, and their metabolism was assessed in both isolated, perfused rat hearts and in the in vivo rat heart. These preliminary investigations show that DNP can be used as an effective in vivo probe of ketone body metabolism in the heart. © 2018 The Authors. NMR in Biomedicine published by John Wiley & Sons Ltd.

Raspberry Ketone

MedlinePlus

... raspberry ketone solution to the scalp might increase hair growth in people with hair loss. Male pattern baldness ( ... raspberry ketone solution to the scalp might increase hair growth in people with male pattern baldness Obesity. Early ...

Ketones block amyloid entry and improve cognition in an Alzheimer's model.

PubMed

Yin, Jun Xiang; Maalouf, Marwan; Han, Pengcheng; Zhao, Minglei; Gao, Ming; Dharshaun, Turner; Ryan, Christopher; Whitelegge, Julian; Wu, Jie; Eisenberg, David; Reiman, Eric M; Schweizer, Felix E; Shi, Jiong

2016-03-01

Sporadic Alzheimer's disease (AD) is responsible for 60%-80% of dementia cases, and the most opportune time for preventive intervention is in the earliest stage of its preclinical phase. As traditional mitochondrial energy substrates, ketone bodies (ketones, for short), beta-hydroxybutyrate, and acetoacetate, have been reported to provide symptomatic improvement and disease-modifying activity in epilepsy and neurodegenerative disorders. Recently, ketones are thought as more than just metabolites and also as endogenous factors protecting against AD. In this study, we discovered a novel neuroprotective mechanism of ketones in which they blocked amyloid-β 42, a pathologic hallmark protein of AD, entry into neurons. The suppression of intracellular amyloid-β 42 accumulation rescued mitochondrial complex I activity, reduced oxidative stress, and improved synaptic plasticity. Most importantly, we show that peripheral administration of ketones significantly reduced amyloid burden and greatly improved learning and memory ability in a symptomatic mouse model of AD. These observations provide us insights to understand and to establish a novel therapeutic use of ketones in AD prevention. Copyright © 2016 Elsevier Inc. All rights reserved.

Engineering ..beta..-Oxidation in Yarrowia lipolytica for Methyl Ketone Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanchez i Nogue, Violeta; Ramirez, Kelsey J; Singer, Christine

Medium- and long-chain methyl ketones are fatty acid-derived compounds that can be used as biofuel blending agents, flavors and fragrances. However, their large-scale production from sustainable feedstocks is currently limited due to the lack of robust microbial biocatalysts. The oleaginous yeast Yarrowia lipolytica is a promising biorefinery platform strain for the production of methyl ketones from renewable lignocellulosic biomass due to its natively high flux towards fatty acid biosynthesis. In this study, we report the metabolic engineering of Y. lipolytica to produce long- and very long-chain methyl ketones. Truncation of peroxisomal ..beta..-oxidation by chromosomal deletion of pot1 resulted in themore » biosynthesis of saturated, mono-, and diunsaturated methyl ketones in the C13-C23 range. Additional overexpression and peroxisomal targeting of a heterologous bacterial methyl ketone biosynthesis pathway yielded an initial titer of 151.5 mg/L of saturated methyl ketones. Dissolved oxygen concentrations in the cultures were found to substantially impact cell morphology and methyl ketone biosynthesis. Bioreactor cultivation under optimized conditions resulted in a titer of 314.8 mg/L of total methyl ketones, representing more than a 6000-fold increase over the parental strain. This work highlights the potential of Y. lipolytica to serve as chassis organism for the biosynthesis of acyl-thioester derived long- and very long-chain methyl ketones.« less

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

PubMed

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.

Engineering β-oxidation in Yarrowia lipolytica for methyl ketone production.

PubMed

Hanko, Erik K R; Denby, Charles M; Sànchez I Nogué, Violeta; Lin, Weiyin; Ramirez, Kelsey J; Singer, Christine A; Beckham, Gregg T; Keasling, Jay D

2018-05-28

Medium- and long-chain methyl ketones are fatty acid-derived compounds that can be used as biofuel blending agents, flavors and fragrances. However, their large-scale production from sustainable feedstocks is currently limited due to the lack of robust microbial biocatalysts. The oleaginous yeast Yarrowia lipolytica is a promising biorefinery platform strain for the production of methyl ketones from renewable lignocellulosic biomass due to its natively high flux towards fatty acid biosynthesis. In this study, we report the metabolic engineering of Y. lipolytica to produce long- and very long-chain methyl ketones. Truncation of peroxisomal β-oxidation by chromosomal deletion of pot1 resulted in the biosynthesis of saturated, mono-, and diunsaturated methyl ketones in the C 13 -C 23 range. Additional overexpression and peroxisomal targeting of a heterologous bacterial methyl ketone biosynthesis pathway yielded an initial titer of 151.5 mg/L of saturated methyl ketones. Dissolved oxygen concentrations in the cultures were found to substantially impact cell morphology and methyl ketone biosynthesis. Bioreactor cultivation under optimized conditions resulted in a titer of 314.8 mg/L of total methyl ketones, representing more than a 6000-fold increase over the parental strain. This work highlights the potential of Y. lipolytica to serve as chassis organism for the biosynthesis of acyl-thioester derived long- and very long-chain methyl ketones. Copyright © 2018 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

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

PubMed

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.

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

PubMed

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.

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

PubMed Central

Le Foll, Christelle

2016-01-01

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. PMID:27122369

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

PubMed

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.

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

PubMed

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 < 0.0001), combined lactate + pyruvate and endogenous contributions were unchanged, and [U-(13)C]3-hydroxybutyrate became the major acetyl-CoA contributor (68 ± 3%)--about three-times higher than glucose. A direct analysis of the GABA carbon 2 multiplet revealed that [U-(13)C]3-hydroxybutyrate contributed approximately the same acetyl-CoA fraction as glucose, indicating that it was less avidly oxidized by GABAergic than glutamatergic 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.

Ketone bodies are protective against oxidative stress in neocortical neurons.

PubMed

Kim, Do Young; Davis, Laurie M; Sullivan, Patrick G; Maalouf, Marwan; Simeone, Timothy A; van Brederode, Johannes; Rho, Jong M

2007-06-01

Ketone bodies (KB) have been shown to prevent neurodegeneration in models of Parkinson's and Alzheimer's diseases, but the mechanisms underlying these effects remain unclear. One possibility is that KB may exert antioxidant activity. In the current study, we explored the effects of KB on rat neocortical neurons exposed to hydrogen peroxide (H(2)O(2)) or diamide - a thiol oxidant and activator of mitochondrial permeability transition (mPT). We found that: (i) KB completely blocked large inward currents induced by either H(2)O(2) or diamide; (ii) KB significantly decreased the number of propidium iodide-labeled cells in neocortical slices after exposure to H(2)O(2) or diamide; (iii) KB significantly decreased reactive oxygen species (ROS) levels in dissociated neurons and in isolated neocortical mitochondria; (iv) the electrophysiological effects of KB in neurons exposed to H(2)O(2) or diamide were mimicked by bongkrekic acid and cyclosporin A, known inhibitors of mPT, as well as by catalase and DL - dithiothreitol, known antioxidants; (v) diamide alone did not significantly alter basal ROS levels in neurons, supporting previous studies indicating that diamide-induced neuronal injury may be mediated by mPT opening; and (vi) KB significantly increased the threshold for calcium-induced mPT in isolated mitochondria. Taken together, our data suggest that KB may prevent mPT and oxidative injury in neocortical neurons, most likely by decreasing mitochondrial ROS production.

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

PubMed Central

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

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

PubMed

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.

Identity of SMCT1 (SLC5A8) as a neuron-specific Na+-coupled transporter for active uptake of L-lactate and ketone bodies in the brain.

PubMed

Martin, Pamela M; Gopal, Elangovan; Ananth, Sudha; Zhuang, Lina; Itagaki, Shiro; Prasad, Balakrishna M; Smith, Sylvia B; Prasad, Puttur D; Ganapathy, Vadivel

2006-07-01

SMCT1 is a sodium-coupled (Na(+)-coupled) transporter for l-lactate and short-chain fatty acids. Here, we show that the ketone bodies, beta-d-hydroxybutyrate and acetoacetate, and the branched-chain ketoacid, alpha-ketoisocaproate, are also substrates for the transporter. The transport of these compounds via human SMCT1 is Na(+)-coupled and electrogenic. The Michaelis constant is 1.4 +/- 0.1 mm for beta-d-hydroxybutyrate, 0.21 +/- 0.04 mm for acetoacetate and 0.21 +/- 0.03 mm for alpha-ketoisocaproate. The Na(+) : substrate stoichiometry is 2 : 1. As l-lactate and ketone bodies constitute primary energy substrates for neurons, we investigated the expression pattern of this transporter in the brain. In situ hybridization studies demonstrate widespread expression of SMCT1 mRNA in mouse brain. Immunofluorescence analysis shows that SMCT1 protein is expressed exclusively in neurons. SMCT1 protein co-localizes with MCT2, a neuron-specific Na(+)-independent monocarboxylate transporter. In contrast, there was no overlap of signals for SMCT1 and MCT1, the latter being expressed only in non-neuronal cells. We also demonstrate the neuron-specific expression of SMCT1 in mixed cultures of rat cortical neurons and astrocytes. This represents the first report of an Na(+)-coupled transport system for a major group of energy substrates in neurons. These findings suggest that SMCT1 may play a critical role in the entry of l-lactate and ketone bodies into neurons by a process driven by an electrochemical Na(+) gradient and hence, contribute to the maintenance of the energy status and function of neurons.

Nile Red Detection of Bacterial Hydrocarbons and Ketones in a High-Throughput Format

PubMed Central

Pinzon, Neissa M.; Aukema, Kelly G.; Gralnick, Jeffrey A.; Wackett, Lawrence P.

2011-01-01

ABSTRACT A method for use in high-throughput screening of bacteria for the production of long-chain hydrocarbons and ketones by monitoring fluorescent light emission in the presence of Nile red is described. Nile red has previously been used to screen for polyhydroxybutyrate (PHB) and fatty acid esters, but this is the first report of screening for recombinant bacteria making hydrocarbons or ketones. The microtiter plate assay was evaluated using wild-type and recombinant strains of Shewanella oneidensis and Escherichia coli expressing the enzyme OleA, previously shown to initiate hydrocarbon biosynthesis. The strains expressing exogenous Stenotrophomonas maltophilia oleA, with increased levels of ketone production as determined by gas chromatography-mass spectrometry, were distinguished with Nile red fluorescence. Confocal microscopy images of S. oneidensis oleA-expressing strains stained with Nile red were consistent with a membrane localization of the ketones. This differed from Nile red staining of bacterial PHB or algal lipid droplets that showed intracellular inclusion bodies. These results demonstrated the applicability of Nile red in a high-throughput technique for the detection of bacterial hydrocarbons and ketones. PMID:21712420

Glycemia, ketonemia, and brain enzymes of ketone body utilization in suckling and adult rats undernourished from intrauterine life.

PubMed

Escrivá, F; Rodríguez, C; Pascual-Leone, A M

1985-05-01

The effect of undernutrition from the 16th day of pregnancy up to 70th day of life on blood glucose and ketone bodies and on several brain mitochondrial enzymes related to energy metabolism or biosynthetic function was investigated. Undernutrition in perinatal period was established by means of a food restriction to pregnant rats and, later, to the lactating mother; undernourished postweaned rats received half the diet consumed by the controls. Body and brain weight from undernourished rats was less than controls throughout the entire period studied. Glycemia and ketonemia were also always lower than controls. Cytochrome c oxidase, citrate synthase, 3-hydroxybutyrate dehydrogenase, 3-oxoacid coenzyme A transferase, and acetoacetyl-coenzyme A thiolase activities during the suckling period were in most stages lower than controls; subsequently, activities in undernourished rats reached or surpassed the control values. These results could explain the "catch up" phenomenon in several ultrastructural parameters found by other authors in undernourished postweaned rats.

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

PubMed

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.

Excitatory action of GABA on immature neurons is not due to absence of ketone bodies metabolites or other energy substrates.

PubMed

Ben-Ari, Yehezkel; Tyzio, Roman; Nehlig, Astrid

2011-09-01

Brain slices incubated with glucose have provided most of our knowledge on cellular, synaptic, and network driven mechanisms. It has been recently suggested that γ-aminobutyric acid (GABA) excites neonatal neurons in conventional glucose-perfused slices but not when ketone bodies metabolites, pyruvate, and/or lactate are added, suggesting that the excitatory actions of GABA are due to energy deprivation when glucose is the sole energy source. In this article, we review the vast number of studies that show that slices are not energy deprived in glucose-containing medium, and that addition of other energy substrates at physiologic concentrations does not alter the excitatory actions of GABA on neonatal neurons. In contrast, lactate, like other weak acids, can produce an intracellular acidification that will cause a reduction of intracellular chloride and a shift of GABA actions. The effects of high concentrations of lactate, and particularly of pyruvate (4-5 mm), as used are relevant primarily to pathologic conditions; these concentrations not being found in the brain in normal "control" conditions. Slices in glucose-containing medium may not be ideal, but additional energy substrates neither correspond to physiologic conditions nor alter GABA actions. In keeping with extensive observations in a wide range of animal species and brain structures, GABA depolarizes immature neurons and the reduction of the intracellular concentration of chloride ([Cl(-)](i)) is a basic property of brain maturation that has been preserved throughout evolution. In addition, this developmental sequence has important clinical implications, notably concerning the higher incidence of seizures early in life and their long-lasting deleterious sequels. Immature neurons have difficulties exporting chloride that accumulates during seizures, leading to permanent increase of [Cl(-)](i) that converts the inhibitory actions of GABA to excitatory and hampers the efficacy of GABA-acting antiepileptic

EXTRACTION OF TETRAVALENT PLUTONIUM VALUES WITH METHYL ETHYL KETONE, METHYL ISOBUTYL KETONE ACETOPHENONE OR MENTHONE

DOEpatents

Seaborg, G.T.

1961-08-01

A process is described for extracting tetravalent plutonium from an aqueous acid solution with methyl ethyl ketone, methyl isobutyl ketone, or acetophenone and with the extraction of either tetravalent or hexavalent plutonium into menthone. (AEC)

A reactive and sensitive diffusion sampler for the determination of aldehydes and ketones in ambient air

NASA Astrophysics Data System (ADS)

Uchiyama, Shigehisa; Hasegawa, Shuji

We developed a diffusive sampling device (DSD-carbonyl) for organic carbonyl compounds (aldehydes and ketones) which is suitable for collection and analysis of low concentration levels. This sampling device is composed of three parts, an exposure part made of a porous polytetrafluoroethylene (PPTFE) tube, an analysis part made of polypropylene (PP) tubing and an absorbent part made of 2,4-dinitrophenylhydrazine (DNPH) coated silica gel (DNPH-silica). Aldehydes and ketones diffuse to the DSD-carbonyl through PPTFE-tube by the mechanism of molecular diffusion and react specifically with DNPH to form a stable DNPH-derivatives. Collection is controlled by moving the absorbent from the exposure part to the analysis part by changing the posture of the DSD-carbonyl. DNPH-derivatives were eluted from an analysis part of DSD-carbonyl with acetonitrile directly and analyzed by high performance liquid chromatography (HPLC). The advantages of the DSD-carbonyl are the following: (1) The DSD-carbonyl can be used in a wide range of concentration of aldehydes and ketones in atmosphere, as the DSD-carbonyl exposure part has a variable diffusion area, (2) DNPH-derivatives are eluted from DNPH-silica without contamination of air. (3) The sampler can be applied to active sampling by connecting it with a pump. The limit of detection (LOD) for concentrations of major aldehydes and ketones ranged from 0.072 to 0.13 ppb, and the limit of quantitation (LOQ) ranged from 0.24 to 0.42 ppb. The coefficient variation (CV) for concentrations of major aldehydes and ketones ranged from 2.5 to 3.0% in laboratory air. The DSD-carbonyl method and active sampling method (US EPA method IP-6A) showed a good correlation (formaldehyde, r2=0.995). The uptake rates for formaldehyde, acetaldehyde, and acetone were estimated as 0.078, 0.062 and 0.079 nmol ppb -1 h -1, respectively. It is possible to estimate atmospheric aldehydes and ketones at parts per billion (ppb), with high sensitivity and precision, by

A Bio-Catalytic Approach to Aliphatic Ketones

PubMed Central

Xiong, Mingyong; Deng, Jin; Woodruff, Adam P.; Zhu, Minshan; Zhou, Jun; Park, Sun Wook; Li, Hui; Fu, Yao; Zhang, Kechun

2012-01-01

Depleting oil reserves and growing environmental concerns have necessitated the development of sustainable processes to fuels and chemicals. Here we have developed a general metabolic platform in E. coli to biosynthesize carboxylic acids. By engineering selectivity of 2-ketoacid decarboxylases and screening for promiscuous aldehyde dehydrogenases, synthetic pathways were constructed to produce both C5 and C6 acids. In particular, the production of isovaleric acid reached 32 g/L (0.22 g/g glucose yield), which is 58% of the theoretical yield. Furthermore, we have developed solid base catalysts to efficiently ketonize the bio-derived carboxylic acids such as isovaleric acid and isocaproic acid into high volume industrial ketones: methyl isobutyl ketone (MIBK, yield 84%), diisobutyl ketone (DIBK, yield 66%) and methyl isoamyl ketone (MIAK, yield 81%). This hybrid “Bio-Catalytic conversion” approach provides a general strategy to manufacture aliphatic ketones, and represents an alternate route to expanding the repertoire of renewable chemicals. PMID:22416247

A bio-catalytic approach to aliphatic ketones.

PubMed

Xiong, Mingyong; Deng, Jin; Woodruff, Adam P; Zhu, Minshan; Zhou, Jun; Park, Sun Wook; Li, Hui; Fu, Yao; Zhang, Kechun

2012-01-01

Depleting oil reserves and growing environmental concerns have necessitated the development of sustainable processes to fuels and chemicals. Here we have developed a general metabolic platform in E. coli to biosynthesize carboxylic acids. By engineering selectivity of 2-ketoacid decarboxylases and screening for promiscuous aldehyde dehydrogenases, synthetic pathways were constructed to produce both C5 and C6 acids. In particular, the production of isovaleric acid reached 32 g/L (0.22 g/g glucose yield), which is 58% of the theoretical yield. Furthermore, we have developed solid base catalysts to efficiently ketonize the bio-derived carboxylic acids such as isovaleric acid and isocaproic acid into high volume industrial ketones: methyl isobutyl ketone (MIBK, yield 84%), diisobutyl ketone (DIBK, yield 66%) and methyl isoamyl ketone (MIAK, yield 81%). This hybrid "Bio-Catalytic conversion" approach provides a general strategy to manufacture aliphatic ketones, and represents an alternate route to expanding the repertoire of renewable chemicals.

Emission of volatile aldehydes and ketones from wood pellets under controlled conditions.

PubMed

Arshadi, Mehrdad; Geladi, Paul; Gref, Rolf; Fjällström, Pär

2009-11-01

Different qualities of biofuel pellets were made from pine and spruce sawdust according to an industrial experimental design. The fatty/resin acid compositions were determined by gas chromatography-mass spectrometry for both newly produced pellets and those after 2 and 4 weeks of storage. The aldehydes/ketones compositions were determined by high performance liquid chromatography at 0, 2, and 4 weeks. The designs were analyzed for the response variables: total fatty/resin acids and total aldehydes/ketones. The design showed a strong correlation between the pine fraction in the pellets and the fatty/resin acid content but the influence decreased over storage time. The amount of fatty/resin acids decreased approximately 40% during 4 weeks. The influence of drying temperature on the aldehyde/ketone emission of fresh pellets was also shown. The amounts of emitted aldehydes/ketones generally decreased by 45% during storage as a consequence of fatty/resin acid oxidation. The matrices of individual concentrations were subjected to multivariate data analysis. This showed clustering of the different experimental runs and demonstrated the important mechanism of fatty/resin acid conversion.

40 CFR 721.4568 - Methylpolychloro aliphatic ketone.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Methylpolychloro aliphatic ketone. 721... Substances § 721.4568 Methylpolychloro aliphatic ketone. (a) Chemical substance and significant new uses... ketone (PMN No. P-91-1321) is subject to reporting under this section for the significant new uses...

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

PubMed

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.

Spider monkeys (Ateles geoffroyi) are less sensitive to the odor of aliphatic ketones than to the odor of other classes of aliphatic compounds.

PubMed

Eliasson, Moa; Hernandez Salazar, Laura Teresa; Laska, Matthias

2015-10-01

Aliphatic ketones are widely present in body-borne and food odors of primates. Therefore, we used an operant conditioning paradigm and determined olfactory detection thresholds in four spider monkeys for a homologous series of aliphatic 2-ketones (2-butanone to 2-nonanone) and two of their isomers (3- and 4-heptanone). We found that, with the exception of the two shortest-chained ketones, all animals detected concentrations <1 ppm (parts per million), and with five odorants individual animals even reached threshold values <0.1 ppm. Further, we found a significant correlation between olfactory sensitivity of the spider monkeys and carbon chain length of the 2-ketones which can best be described as a U-shaped function. In contrast, no significant correlation was found between olfactory sensitivity and position of the functional carbonyl group. Across-odorant and across-species comparisons revealed the following: spider monkeys are significantly less sensitive to the odors of aliphatic ketones than to the odor of other classes of aliphatic compounds (1-alcohols, n-aldehydes, n-acetic esters, and n-carboxylic acids) sharing the same carbon length. Spider monkeys do not differ significantly in their olfactory sensitivity for aliphatic ketones from squirrel monkeys and pigtail macaques, but are significantly less sensitive to these odorants compared to human subjects and mice. These findings support the notion that neuroanatomical and genetic properties do not allow for reliable predictions with regard to a species' olfactory sensitivity. Further, we conclude that the frequency of occurrence of a class of odorants in a species' chemical environment does not allow for reliable predictions of the species' olfactory sensitivity. Copyright © 2015 Elsevier Ireland Ltd and the Japan Neuroscience Society. All rights reserved.

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

PubMed

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.

Volatilization of ketones from water

USGS Publications Warehouse

Rathbun, R.E.; Tai, D.Y.

1982-01-01

The overall mass-transfer coefficients for the volatilization from water of acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-heptanone, and 2-octanone were measured simultaneously with the oxygen-absorption coefficient in a laboratory stirred water bath. The liquid-film and gas-film coefficients of the two-film model were determined for the ketones from the overall coefficients, and both film resistances were important for volatilization of the ketones.The liquid-film coefficients for the ketones varied with the 0.719 power of the molecular-diffusion coefficient, in agreement with the literature. The liquid-film coefficients showed a variable dependence on molecular weight, with the dependence ranging from the −0.263 power for acetone to the −0.378 power for 2-octanone. This is in contrast with the literature where a constant −0.500 power dependence on the molecular weight is assumed.The gas-film coefficients for the ketones showed no dependence on molecular weight, in contrast with the literature where a −0.500 power is assumed.

Ketone-DNA: a versatile postsynthetic DNA decoration platform.

PubMed

Dey, S; Sheppard, T L

2001-12-13

[reaction: see text] A general strategy for the functional diversification of DNA oligonucleotides under physiological conditions was developed. We describe the synthesis of DNA molecules bearing ketone ports (ketone-DNA) and the efficient postsynthetic decoration of ketone-DNA with structurally diverse aminooxy compounds.

Ketone EC50 values in the Microtox test.

PubMed

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.

The collective therapeutic potential of cerebral ketone metabolism in traumatic brain injury

PubMed Central

Prins, Mayumi L.; Matsumoto, Joyce H.

2014-01-01

The postinjury period of glucose metabolic depression is accompanied by adenosine triphosphate decreases, increased flux of glucose through the pentose phosphate pathway, free radical production, activation of poly-ADP ribose polymerase via DNA damage, and inhibition of glyceraldehyde dehydrogenase (a key glycolytic enzyme) via depletion of the cytosolic NAD pool. Under these post-brain injury conditions of impaired glycolytic metabolism, glucose becomes a less favorable energy substrate. Ketone bodies are the only known natural alternative substrate to glucose for cerebral energy metabolism. While it has been demonstrated that other fuels (pyruvate, lactate, and acetyl-L-carnitine) can be metabolized by the brain, ketones are the only endogenous fuel that can contribute significantly to cerebral metabolism. Preclinical studies employing both pre- and postinjury implementation of the ketogenic diet have demonstrated improved structural and functional outcome in traumatic brain injury (TBI) models, mild TBI/concussion models, and spinal cord injury. Further clinical studies are required to determine the optimal method to induce cerebral ketone metabolism in the postinjury brain, and to validate the neuroprotective benefits of ketogenic therapy in humans. PMID:24721741

Engineering E. coli for simultaneous glucose–xylose utilization during methyl ketone production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xi; Goh, Ee-Been; Beller, Harry R.

Previously, we developed an E. coli strain that overproduces medium-chain methyl ketones for potential use as diesel fuel blending agents or as flavors and fragrances. To date, the strain's performance has been optimized during growth with glucose. However, lignocellulosic biomass hydrolysates also contain a substantial portion of hemicellulose-derived xylose, which is typically the second most abundant sugar after glucose. Commercialization of the methyl ketone-producing technology would benefit from the increased efficiency resulting from simultaneous, rather than the native sequential (diauxic), utilization of glucose and xylose. In this study, genetic manipulations were performed to alleviate carbon catabolite repression in our mostmore » efficient methyl ket one-producing strain. A strain engineered for constitutive expression of xylF and xylA (involved in xylose transport and metabolism) showed synchronized glucose and xylose consumption rates. However, this newly acquired capability came at the expense of methyl ketone titer, which decreased fivefold. Further efforts were made to improve methyl ketone production in this strain, and we found that two strategies were effective at enhancing methyl ketone titer: (1) chromosomal deletion of pgi (glucose-6-phosphate isomerase) to increase intracellular NADPH supply and (2) downregulation of CRP (cAMP receptor protein) expression by replacement of the native RBS with an RBS chosen based upon mutant library screening results. Combining these strategies resulted in the most favorable overall phenotypes for simultaneous glucose-xylose consumption without compromising methyl ketone titer at both 1 and 2% total sugar concentrations in shake flasks. This work demonstrated a strategy for engineering simultaneous utilization of C 6 and C 5 sugars in E. coli without sacrificing production of fatty acid-derived compounds.« less

Engineering E. coli for simultaneous glucose–xylose utilization during methyl ketone production

DOE PAGES

Wang, Xi; Goh, Ee-Been; Beller, Harry R.

2018-01-27

Previously, we developed an E. coli strain that overproduces medium-chain methyl ketones for potential use as diesel fuel blending agents or as flavors and fragrances. To date, the strain's performance has been optimized during growth with glucose. However, lignocellulosic biomass hydrolysates also contain a substantial portion of hemicellulose-derived xylose, which is typically the second most abundant sugar after glucose. Commercialization of the methyl ketone-producing technology would benefit from the increased efficiency resulting from simultaneous, rather than the native sequential (diauxic), utilization of glucose and xylose. In this study, genetic manipulations were performed to alleviate carbon catabolite repression in our mostmore » efficient methyl ket one-producing strain. A strain engineered for constitutive expression of xylF and xylA (involved in xylose transport and metabolism) showed synchronized glucose and xylose consumption rates. However, this newly acquired capability came at the expense of methyl ketone titer, which decreased fivefold. Further efforts were made to improve methyl ketone production in this strain, and we found that two strategies were effective at enhancing methyl ketone titer: (1) chromosomal deletion of pgi (glucose-6-phosphate isomerase) to increase intracellular NADPH supply and (2) downregulation of CRP (cAMP receptor protein) expression by replacement of the native RBS with an RBS chosen based upon mutant library screening results. Combining these strategies resulted in the most favorable overall phenotypes for simultaneous glucose-xylose consumption without compromising methyl ketone titer at both 1 and 2% total sugar concentrations in shake flasks. This work demonstrated a strategy for engineering simultaneous utilization of C 6 and C 5 sugars in E. coli without sacrificing production of fatty acid-derived compounds.« less

Nile Red Detection of Bacterial Hydrocarbons and Ketones in a High-Throughput Format

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pinzon, NM; Aukema, KG; Gralnick, JA

A method for use in high-throughput screening of bacteria for the production of long-chain hydrocarbons and ketones by monitoring fluorescent light emission in the presence of Nile red is described. Nile red has previously been used to screen for polyhydroxybutyrate (PHB) and fatty acid esters, but this is the first report of screening for recombinant bacteria making hydrocarbons or ketones. The microtiter plate assay was evaluated using wild-type and recombinant strains of Shewanella oneidensis and Escherichia coli expressing the enzyme OleA, previously shown to initiate hydrocarbon biosynthesis. The strains expressing exogenous Stenotrophomonas maltophilia oleA, with increased levels of ketone productionmore » as determined by gas chromatography-mass spectrometry, were distinguished with Nile red fluorescence. Confocal microscopy images of S. oneidensis oleA-expressing strains stained with Nile red were consistent with a membrane localization of the ketones. This differed from Nile red staining of bacterial PHB or algal lipid droplets that showed intracellular inclusion bodies. These results demonstrated the applicability of Nile red in a high-throughput technique for the detection of bacterial hydrocarbons and ketones. IMPORTANCE In recent years, there has been renewed interest in advanced biofuel sources such as bacterial hydrocarbon production. Previous studies used solvent extraction of bacterial cultures followed by gas chromatography-mass spectrometry (GC-MS) to detect and quantify ketones and hydrocarbons (Beller HR, Goh EB, Keasling JD, Appl. Environ. Microbiol. 76: 1212-1223, 2010; Sukovich DJ, Seffernick JL, Richman JE, Gralnick JA, Wackett LP, Appl. Environ. Microbiol. 76: 3850-3862, 2010). While these analyses are powerful and accurate, their labor-intensive nature makes them intractable to high-throughput screening; therefore, methods for rapid identification of bacterial strains that are overproducing hydrocarbons are needed. The use of high

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

NASA Astrophysics Data System (ADS)

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.

Engineering of bacterial methyl ketone synthesis for biofuels.

PubMed

Goh, Ee-Been; Baidoo, Edward E K; Keasling, Jay D; Beller, Harry R

2012-01-01

We have engineered Escherichia coli to overproduce saturated and monounsaturated aliphatic methyl ketones in the C₁₁ to C₁₅ (diesel) range; this group of methyl ketones includes 2-undecanone and 2-tridecanone, which are of importance to the flavor and fragrance industry and also have favorable cetane numbers (as we report here). We describe specific improvements that resulted in a 700-fold enhancement in methyl ketone titer relative to that of a fatty acid-overproducing E. coli strain, including the following: (i) overproduction of β-ketoacyl coenzyme A (CoA) thioesters achieved by modification of the β-oxidation pathway (specifically, overexpression of a heterologous acyl-CoA oxidase and native FadB and chromosomal deletion of fadA) and (ii) overexpression of a native thioesterase (FadM). FadM was previously associated with oleic acid degradation, not methyl ketone synthesis, but outperformed a recently identified methyl ketone synthase (Solanum habrochaites MKS2 [ShMKS2], a thioesterase from wild tomato) in β-ketoacyl-CoA-overproducing strains tested. Whole-genome transcriptional (microarray) studies led to the discovery that FadM is a valuable catalyst for enhancing methyl ketone production. The use of a two-phase system with decane enhanced methyl ketone production by 4- to 7-fold in addition to increases from genetic modifications.

40 CFR 721.4925 - Methyl n-butyl ketone.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Methyl n-butyl ketone. 721.4925... Substances § 721.4925 Methyl n-butyl ketone. (a) Chemical substance and significant new use subject to reporting. (1) The chemical substance methyl n-butyl ketone, CAS Number 591-78-6, is subject to reporting...

40 CFR 721.4925 - Methyl n-butyl ketone.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Methyl n-butyl ketone. 721.4925... Substances § 721.4925 Methyl n-butyl ketone. (a) Chemical substance and significant new use subject to reporting. (1) The chemical substance methyl n-butyl ketone, CAS Number 591-78-6, is subject to reporting...

Homologation Reaction of Ketones with Diazo Compounds.

PubMed

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.

Study of the antibacterial and antifungal activities of synthetic benzyl bromides, ketones, and corresponding chalcone derivatives.

PubMed

Shakhatreh, Muhamad Ali K; Al-Smadi, Mousa L; Khabour, Omar F; Shuaibu, Fatima A; Hussein, Emad I; Alzoubi, Karem H

2016-01-01

Several applications of chalcones and their derivatives encouraged researchers to increase their synthesis as an alternative for the treatment of pathogenic bacterial and fungal infections. In the present study, chalcone derivatives were synthesized through cross aldol condensation reaction between 4-( N , N -dimethylamino)benzaldehyde and multiarm aromatic ketones. The multiarm aromatic ketones were synthesized through nucleophilic substitution reaction between 4-hydroxy acetophenone and benzyl bromides. The benzyl bromides, multiarm aromatic ketones, and corresponding chalcone derivatives were evaluated for their activities against eleven clinical pathogenic Gram-positive, Gram-negative bacteria, and three pathogenic fungi by the disk diffusion method. The minimum inhibitory concentration was determined by the microbroth dilution technique. The results of the present study demonstrated that benzyl bromide derivatives have strong antibacterial and antifungal properties as compared to synthetic chalcone derivatives and ketones. Benzyl bromides (1a and 1c) showed high ester activity against Gram-positive bacteria and fungi but moderate activity against Gram-negative bacteria. Therefore, these compounds may be considered as good antibacterial and antifungal drug discovery. However, substituted ketones (2a-b) as well as chalcone derivatives (3a-c) showed no activity against all the tested strains except for ketone (2c), which showed moderate activity against Candida albicans .

Study of the antibacterial and antifungal activities of synthetic benzyl bromides, ketones, and corresponding chalcone derivatives

PubMed Central

Shakhatreh, Muhamad Ali K; Al-Smadi, Mousa L; Khabour, Omar F; Shuaibu, Fatima A; Hussein, Emad I; Alzoubi, Karem H

2016-01-01

Several applications of chalcones and their derivatives encouraged researchers to increase their synthesis as an alternative for the treatment of pathogenic bacterial and fungal infections. In the present study, chalcone derivatives were synthesized through cross aldol condensation reaction between 4-(N,N-dimethylamino)benzaldehyde and multiarm aromatic ketones. The multiarm aromatic ketones were synthesized through nucleophilic substitution reaction between 4-hydroxy acetophenone and benzyl bromides. The benzyl bromides, multiarm aromatic ketones, and corresponding chalcone derivatives were evaluated for their activities against eleven clinical pathogenic Gram-positive, Gram-negative bacteria, and three pathogenic fungi by the disk diffusion method. The minimum inhibitory concentration was determined by the microbroth dilution technique. The results of the present study demonstrated that benzyl bromide derivatives have strong antibacterial and antifungal properties as compared to synthetic chalcone derivatives and ketones. Benzyl bromides (1a and 1c) showed high ester activity against Gram-positive bacteria and fungi but moderate activity against Gram-negative bacteria. Therefore, these compounds may be considered as good antibacterial and antifungal drug discovery. However, substituted ketones (2a–b) as well as chalcone derivatives (3a–c) showed no activity against all the tested strains except for ketone (2c), which showed moderate activity against Candida albicans. PMID:27877017

Using solubility and Henry`s law constant data for ketones in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yaws, C.L.; Sheth, S.D.; Han, M.

When a chemical spill occurs in water, the extent of chemical contamination is determined by the chemical`s solubility in the water. If contaminated water comes into contact with air, such as in a pond or a storage vessel, the contaminant`s emissions into the air can be determined based upon Henry`s law constant for that particular constituent. A high Henry`s law constant value translates into a greater emissions level. The engineering design and operation of strippers to remove contaminants from water require data for both water solubility and Henry`s law constant. A new correlation developed by researchers at Lamar University providesmore » reliable values down to very, very low concentrations for the solubility of ketones in water. The correlation is based on the boiling point temperature of the ketone and can be used for engineering studies involving health, safety and environmental considerations. Results for water solubility and Henry`s law constant are provided here for a wide variety of ketones. Representative values are about 249,000 parts per million (ppm) per weight (wt) for methyl ethyl ketone (C{sub 4}H{sub 8}O) and 360 ppm/wt for 5-nonanone (C{sub 9}H{sub 18}O).« less

The collective therapeutic potential of cerebral ketone metabolism in traumatic brain injury.

PubMed

Prins, Mayumi L; Matsumoto, Joyce H

2014-12-01

The postinjury period of glucose metabolic depression is accompanied by adenosine triphosphate decreases, increased flux of glucose through the pentose phosphate pathway, free radical production, activation of poly-ADP ribose polymerase via DNA damage, and inhibition of glyceraldehyde dehydrogenase (a key glycolytic enzyme) via depletion of the cytosolic NAD pool. Under these post-brain injury conditions of impaired glycolytic metabolism, glucose becomes a less favorable energy substrate. Ketone bodies are the only known natural alternative substrate to glucose for cerebral energy metabolism. While it has been demonstrated that other fuels (pyruvate, lactate, and acetyl-L-carnitine) can be metabolized by the brain, ketones are the only endogenous fuel that can contribute significantly to cerebral metabolism. Preclinical studies employing both pre- and postinjury implementation of the ketogenic diet have demonstrated improved structural and functional outcome in traumatic brain injury (TBI) models, mild TBI/concussion models, and spinal cord injury. Further clinical studies are required to determine the optimal method to induce cerebral ketone metabolism in the postinjury brain, and to validate the neuroprotective benefits of ketogenic therapy in humans. Copyright © 2014 by the American Society for Biochemistry and Molecular Biology, Inc.

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

PubMed

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.

Ketones prevent synaptic dysfunction induced by mitochondrial respiratory complex inhibitors

PubMed Central

Kim, Do Young; Vallejo, Johana; Rho, Jong M

2010-01-01

Abstract Ketones have previously shown beneficial effects in models of neurodegenerative disorders, particularly against associated mitochondrial dysfunction and cognitive impairment. However, evidence of a synaptic protective effect of ketones remains lacking. We tested the effects of ketones on synaptic impairment induced by mitochondrial respiratory complex (MRC) inhibitors using electrophysiological, reactive oxygen species (ROS) imaging and biochemical techniques. MRC inhibitors dose-dependently suppressed both population spike (PS) and field potential amplitudes in the CA1 hippocampus. Pre-treatment with ketones strongly prevented changes in the PS, whereas partial protection was seen in the field potential. Rotenone (Rot; 100 nmol/L), a MRC I inhibitor, suppressed synaptic function without altering ROS levels and PS depression by Rot was unaffected by antioxidants. In contrast, antioxidant-induced PS recovery against the MRC II inhibitor 3-nitropropionic acid (3-NP; 1 mmol/L) was similar to the synaptic protective effects of ketones. Ketones also suppressed ROS generation induced by 3-NP. Finally, ketones reversed the decreases in ATP levels caused by Rot and 3-NP. In summary, our data demonstrate that ketones can preserve synaptic function in CA1 hippocampus induced by MRC dysfunction, likely through an antioxidant action and enhanced ATP generation. PMID:20374433

Colorimetric Recognition of Aldehydes and Ketones.

PubMed

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.

Lanthanum tricyanide-catalyzed acyl silane-ketone benzoin additions.

PubMed

Tarr, James C; Johnson, Jeffrey S

2009-09-03

Lanthanum tricyanide efficiently catalyzes a benzoin-type coupling between acyl silanes and ketones. Yields range from moderate to excellent over a broad substrate scope encompassing aryl, alkyl, electron-rich, and sterically hindered ketones.

27 CFR 21.117 - Methyl isobutyl ketone.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Methyl isobutyl ketone. 21.117 Section 21.117 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....117 Methyl isobutyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

27 CFR 21.117 - Methyl isobutyl ketone.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Methyl isobutyl ketone. 21.117 Section 21.117 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....117 Methyl isobutyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

Lanthanum Tricyanide-Catalyzed Acyl Silane-Ketone Benzoin Additions

PubMed Central

Tarr, James C.; Johnson, Jeffrey S.

2009-01-01

Lanthanum tricyanide efficiently catalyzes a benzoin-type coupling between acyl silanes and ketones. Yields range from moderate to excellent over a broad substrate scope encompassing aryl, alkyl, electron-rich, and sterically hindered ketones. PMID:19655731

Ketones Prevent Oxidative Impairment of Hippocampal Synaptic Integrity through KATP Channels

PubMed Central

Kim, Do Young; Abdelwahab, Mohammed G.; Lee, Soo Han; O’Neill, Derek; Thompson, Roger J.; Duff, Henry J.; Sullivan, Patrick G.; Rho, Jong M.

2015-01-01

Dietary and metabolic therapies are increasingly being considered for a variety of neurological disorders, based in part on growing evidence for the neuroprotective properties of the ketogenic diet (KD) and ketones. Earlier, we demonstrated that ketones afford hippocampal synaptic protection against exogenous oxidative stress, but the mechanisms underlying these actions remain unclear. Recent studies have shown that ketones may modulate neuronal firing through interactions with ATP-sensitive potassium (KATP) channels. Here, we used a combination of electrophysiological, pharmacological, and biochemical assays to determine whether hippocampal synaptic protection by ketones is a consequence of KATP channel activation. Ketones dose-dependently reversed oxidative impairment of hippocampal synaptic integrity, neuronal viability, and bioenergetic capacity, and this action was mirrored by the KATP channel activator diazoxide. Inhibition of KATP channels reversed ketone-evoked hippocampal protection, and genetic ablation of the inwardly rectifying K+ channel subunit Kir6.2, a critical component of KATP channels, partially negated the synaptic protection afforded by ketones. This partial protection was completely reversed by co-application of the KATP blocker, 5-hydoxydecanoate (5HD). We conclude that, under conditions of oxidative injury, ketones induce synaptic protection in part through activation of KATP channels. PMID:25848768

Production of methyl-vinyl ketone from levulinic acid

DOEpatents

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.

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

NASA Astrophysics Data System (ADS)

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.

Determination of acetone and methyl ethyl ketone in water

USGS Publications Warehouse

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)

Spectroscopic properties of a perfluorinated ketone for PLIF applications

NASA Astrophysics Data System (ADS)

Roy, Arnab; Gustavsson, Jonas P. R.; Segal, Corin

2011-11-01

This work identifies the fluorescence characteristics of a perfluorinated ketone, 2-trifluoromethyl-1,1,1,2,4,4,5,5,5-nonafluoro-3-pentanone, further referred to as fluoroketone. This compound is suitable for use with the third harmonic of an Nd:YAG laser for quantitative concentration measurements, as it exhibits strong emission even for relatively low excitation and has a near-linear response of fluorescence intensity with concentration. This makes it suitable for a broad range of fluorescence applications. The absorption cross-section of 3.81 × 10-19 cm2 was found to be constant for a temperature range of 293-441 K and a pressure range of 1-18 atm. A calibration line has been generated that relates the concentration of gaseous and liquid fluoroketone with its absorption coefficient.

Effects of Insecticidal Ketones Present in Mint Plants on GABAA Receptor from Mammalian Neurons

PubMed Central

Sánchez-Borzone, Mariela Eugenia; Marin, Leticia Delgado; García, Daniel Asmed

2017-01-01

Background: The genus Mentha, an important member of the Lamiaceae family, is represented by many species commonly known as mint. The insecticidal activity of Mentha oil and its main components has been tested and established against various insects/pests. Among these, the ketone monoterpenes that are most common in different Mentha species demonstrated insect toxicity, with pulegone being the most active, followed by carvone and menthone. Considering that the GABAA receptor (GABAA-R) is one of the main insecticide targets on neurons, and that pulegone would modulate the insect GABA system, it may be expected that the insecticidal properties of Mentha ketones are mediated by their interaction with this receptor. Objective: In order to discern the pharmacological actions of these products when used as insecticides on mammalian organisms, we evaluated the pharmacologic activity of ketones, commonly present in Mentha plants, on native GABAA-R from rats. Materials and Methods: Determination of ketones effects on allosterically enhanced benzodiazepine binding, using primary cultures of cortical neurons, which express functional receptors and MTT assay to evaluate their cell toxicity. Results: Our results seem to indicate that ketone components of Mentha, with proven repellent or insecticide activity, were able to behave as GABAA-R negative allosteric modulators in murine cells and consequently could exhibit convulsant activity in mammalians. Only pulegone at the highest assayed concentration (2 mM) showed a significant reduction in cell viability after exposure for 24 hr. Conclusion: The present results strongly suggest that the ketone components of Mentha are able to exhibit convulsant activity in mammalian organisms, but functional assays and in vivo experiments would be necessary to corroborate this proposed action. SUMMARY The pharmacological activity of insecticide ketones, commonly present in Mentha plants, was evaluated on native GABAA receptor from mammalian

Rapid Intravenous Sodium Acetoacetate Infusion in Man METABOLIC AND KINETIC RESPONSES

PubMed Central

Owen, O. E.; Reichard, G. A.; Markus, H.; Boden, G.; Mozzoli, M. A.; Shuman, C. R.

1973-01-01

The metabolic and kinetic responses to rapidly intravenously administered sodium acetoacetate (1.0 mmol/kg body wt) was studied after an overnight fast in 12 male and female adults weighing between 88 and 215% of average body weight. Blood was obtained before, during, and after the infusion for determination of circulating concentrations of immunoreactive insulin, glucose, acetoacetate, β-hydroxybutyrate and free fatty acids. In three obese subjects the studies were repeated after 3 and 24 days of total starvation. After the overnight fast acetoacetate rose rapidly reaching a peak concentration at the end of the infusion; β-hydroxybutyrate concentrations also increased rapidly and exceeded those of acetoacetate 10 min postinfusion. Total ketone body concentration at the end of the infusion period was comparable to that found after prolonged starvation. After the initial mixing period, acetoacetate, β-hydroxybutyrate and total ketone bodies rapidly declined in a parallel manner. There were no obvious differences between the subjects with regard to their blood concentrations of ketone bodies. The mean plasma free fatty acid concentration decreased significantly during the 20th to 90th min postinfusion period; for example the control concentration of 0.61 mmol/liter fell to 0.43 mmol/liter at 60 min. In the three obese subjects studied repeatedly, fasting plasma free fatty acids decreased with acetoacetate infusion from 0.92 to 0.46 mmol/liter after the 3 day fast and from 1.49 to 0.71 mmol/liter after the 24 day fast. Acetoacetate infusion caused no changes in blood glucose concentration after an overnight fast. However, in the three obese subjects restudied after 3- and 24-day fasts blood glucose decreased, respectively, from 3.49 to 3.22 mmol/liter and from 4.07 to 3.49 mmol/liter. The mean serum insulin concentration in all subjects significantly increased from 21 to 46 μU/ml at the completion of the infusion and rapidly declined. In the three obese subjects

27 CFR 21.118 - Methyl n-butyl ketone.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Methyl n-butyl ketone. 21.118 Section 21.118 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....118 Methyl n-butyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

27 CFR 21.118 - Methyl n-butyl ketone.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Methyl n-butyl ketone. 21.118 Section 21.118 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....118 Methyl n-butyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

Et3B-mediated radical-polar crossover reaction for single-step coupling of O,Te-acetal, α,β-unsaturated ketones, and aldehydes/ketones.

PubMed

Kamimura, Daigo; Urabe, Daisuke; Nagatomo, Masanori; Inoue, Masayuki

2013-10-04

Et3B-mediated three-component coupling reactions between O,Te-acetal, α,β-unsaturated ketones, and aldehydes/ketones were developed. Et3B promoted the generation of the potently reactive bridgehead radical from the O,Te-acetal of the trioxaadamantane structure and converted the α-carbonyl radical of the resultant two-component adduct to the boron enolate, which then underwent a stereoselective aldol reaction with the aldehyde/ketone. This powerful, yet mild, radical-polar crossover reaction efficiently connected the hindered linkages between the three units and selectively introduced three new stereocenters.

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

PubMed

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.

Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors

DOE PAGES

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.; ...

2017-06-21

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

IRIS Toxicological Review of Methyl Ethyl Ketone (2003 Final)

EPA Science Inventory

EPA announced the release of the final report, Toxicological Review of Methyl Ethyl Ketone: in support of the Integrated Risk Information System (IRIS). The updated Summary for Methyl Ethyl Ketone and accompanying toxicological review have been added to the IRIS Database....

Low dielectric fluorinated poly(phenylene ether ketone) film and coating

NASA Technical Reports Server (NTRS)

Cassidy, Patrick E. (Inventor); Tullos, Gordon L. (Inventor); St.clair, Anne K. (Inventor)

1990-01-01

The present invention relates to film and coating materials prepared from novel fluorinated poly(phenylene ether ketones). A fluorinated poly(phenylene ether ketone) is prepared by reacting a bisphenol with 1,1,1,3,3,3 hexafluoro-2,2-bis 4-(4-halobenzoyl) phenyl propane (wherein halo is fluoro or chloro), which is a novel monomer formed as the reaction product of halobenzene (wherein halo is fluoro or chloro) and 1,1,1,3,3,3 hexafluoro-2,2-bis (p-chloro formyl phenyl) propane. Especially beneficial results of this invention are that films and coating materials prepared from the novel fluorinated poly(phenylene ether ketone) are essentially optically transparent/colorless and have a lower dielectric constant than otherwise comparable, commercially available poly(phenylene ether ketones). Moreover, unlike the otherwise comparable commercially available materials, the novel fluorinated poly(phenylene ether ketones) of the present invention can be solution cast or sprayed to produce the films and coatings. Furthermore, the long term thermal stability of the polymers of the present invention is superior to that of the commercially available materials.

Methyl ethyl ketone (MEK)

Integrated Risk Information System (IRIS)

Methyl ethyl ketone ( MEK ) ( CASRN 78 - 93 - 3 ) Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Nonc

Methyl isobutyl ketone (MIBK)

Integrated Risk Information System (IRIS)

Methyl Isobutyl Ketone ( MIBK ) ; CASRN 108 - 10 - 1 ; Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

Enantioselective Organocatalytic α-Fluorination of Cyclic Ketones

PubMed Central

Kwiatkowski, Piotr; Beeson, Teresa D.; Conrad, Jay C.

2011-01-01

The first highly enantioselective α-fluorination of ketones using organocatalysis has been accomplished. The long-standing problem of enantioselective ketone α-fluorination via enamine activation has been overcome via high-throughput evaluation of a new library of amine catalysts. The optimal system, a primary amine functionalized Cinchona alkaloid, allows the direct and asymmetric α-fluorination of a variety of carbo- and heterocyclic substrates. Furthermore, this protocol also provides diastereo-, regio- and chemoselective catalyst control in fluorinations involving complex carbonyl systems. PMID:21247133

Direct α-alkylation of ketones with alcohols in water.

PubMed

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.

Electrical properties of binary mixtures of amino silicone oil and methyl iso butyl ketone

NASA Astrophysics Data System (ADS)

Shah, K. N.; Rana, V. A.; Vankar, H. P.

2018-05-01

The real and imaginary parts of the dielectric function of the binary mixtures of the methyl iso butyl ketone and amino silicone oil in the frequency range 100 Hz to 2 MHz were measured using precision LCR meter at 305.15 K. The electrical properties such as electrical modulus M*(ω), electrical conductivity σ*(ω) and complex impedance Z*(ω) were calculated using the dielectric function ɛ*(ω). The ionic polarization relaxation time (Τσ) and D.C. conductivity (σdc) were also calculated using electrical properties. The ionic behavior of methyl iso butyl ketone and non-ionic behavior of amino silicone oil are also explained. The electrical parameters are used to gain information about the effect of concentration variation of components of the mixtures on the electrical properties.

The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

ERIC Educational Resources Information Center

Nicholson, John W.; Wilson, Alan D.

2004-01-01

The conversion of carboxylic acids to ketones is a useful chemical transformation with a long history. Several chemists have claimed that they discovered the conversion of carboxylic acids to ketones yet in fact the reaction is actually known for centuries.

Extractive recovery of phenol and p-alkylphenols from aqueous solutions with hydrophobic ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korenman, Ya.I.; Ermolaeva, T.N.; Podolina, E.A.

1994-03-10

Aliphatic and cyclic hydrophobic ketones were used for extractive recovery of phenol and p-alkylphenols from aqueous solutions, giving a 95-98% extraction of toxicants under the recommended conditions. The extracting agents were cyclohexanone, methylcyclohexanone, butyl methyl ketone, and isobutyl methyl ketone.

Bacterial production of methyl ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beller, Harry R.; Goh, Ee-Been

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.

Mitoketoscins: Novel mitochondrial inhibitors for targeting ketone metabolism in cancer stem cells (CSCs)

PubMed Central

Ozsvari, Bela; Sotgia, Federica; Simmons, Katie; Trowbridge, Rachel; Foster, Richard; Lisanti, Michael P.

2017-01-01

Previous studies have now well-established that epithelial cancer cells can utilize ketone bodies (3-hydroxybutyrate and aceto-acetate) as mitochondrial fuels, to actively promote tumor growth and metastatic dissemination. The two critical metabolic enzymes implicated in this process are OXCT1 and ACAT1, which are both mitochondrial proteins. Importantly, over-expression of OXCT1 or ACAT1 in human breast cancer cells is sufficient to genetically drive tumorigenesis and/or lung metastasis, validating that they indeed behave as metabolic “tumor promoters”. Here, we decided to target these two enzymes, which give cancer cells the ability to recycle ketone bodies into Acetyl-CoA and, therefore, to produce increased ATP. Briefly, we used computational chemistry (in silico drug design) to select a sub-set of potentially promising compounds that spatially fit within the active site of these enzymes, based on their known 3D crystal structures. These libraries of compounds were then phenotypically screened for their effects on total cellular ATP levels. Positive hits were further validated by metabolic flux analysis. Our results indicated that four of these compounds effectively inhibited mitochondrial oxygen consumption. Two of these compounds also induced a reactive glycolytic phenotype in cancer cells. Most importantly, using the mammosphere assay, we showed that these compounds can be used to functionally inhibit cancer stem cell (CSC) activity and propagation. Finally, our molecular modeling studies directly show how these novel compounds are predicted to bind to the active catalytic sites of OXCT1 and ACAT1, within their Coenzyme A binding site. As such, we speculate that these mitochondrial inhibitors are partially mimicking the structure of Coenzyme A. Thus, we conclude that OXCT1 and ACAT1 are important new therapeutic targets for further drug development and optimization. We propose that this new class of drugs should be termed “mitoketoscins”, to reflect

Stereoselective Borylative Ketone-Diene Coupling

PubMed Central

Cho, Hee Yeon; Yu, Zhiyong; Morken, James P.

2011-01-01

In the presence of catalytic Ni(cod)2 and P(t-Bu)3, ketones, dienes, and B2(pin)2 undergo a stereoselective multicomponent coupling reaction. Upon oxidation, the reaction furnishes 1,3-diols as the major reaction product. PMID:21905748

Short-term effects of air temperature on plasma metabolite concentrations in patients undergoing cardiac catheterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hampel, Regina, E-mail: regina.hampel@helmholtz-mu

Background: Epidemiological studies have shown associations between air temperature and cardiovascular health outcomes. Metabolic dysregulation might also play a role in the development of cardiovascular disease. Objectives: To investigate short-term temperature effects on metabolites related to cardiovascular disease. Methods: Concentrations of 45 acylcarnitines, 15 amino acids, ketone bodies and total free fatty acids were available in 2869 participants from the CATHeterization GENetics cohort recruited at the Duke University Cardiac Catheterization Clinic (Durham, NC) between 2001 and 2007. Ten metabolites were selected based on quality criteria and cluster analysis. Daily averages of meteorological variables were obtained from the North American Regionalmore » Reanalysis project. Immediate, lagged, and cumulative temperature effects on metabolite concentrations were analyzed using (piecewise) linear regression models. Results: Linear temperature effects were found for glycine, C16-OH:C14:1-DC, and aspartic acid/asparagine. A 5 °C increase in temperature was associated with a 1.8% [95%-confidence interval: 0.3%; 3.3%] increase in glycine (5-day average), a 3.2% [0.1%; 6.3%] increase in C16-OH:C14:1-DC (lag of four days), and a −1.4% [−2.4%; −0.3%] decrease in aspartic acid/asparagine (lag of two days). Non-linear temperature effects were observed for alanine and total ketone bodies with breakpoint of 4 °C and 20 °C, respectively. Both a 5 °C decrease in temperature on colder days (<4 °C)and a 5 °C increase in temperature on warmer days (≥4 °C) were associated with a four day delayed increase in alanine by 6.6% [11.7; 1.8%] and 1.9% [0.3%; 3.4%], respectively. For ketone bodies we found immediate (0-day lag) increases of 4.2% [−0.5%; 9.1%] and 12.3% [0.1%; 26.0%] associated with 5 °C decreases on colder (<20 °C) days and 5 °C increases on warmer days (≥20 °C), respectively. Conclusions: We observed multiple effects of air temperature on

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

USGS Publications Warehouse

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.

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

PubMed

Jalilov, Almaz S; Young, Ryan M; Eaton, Samuel W; Wasielewski, Michael R; Lewis, Frederick D

2015-01-01

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases. © 2014 The American Society of Photobiology.

Gas-film coefficients for the volatilization of ketones from water

USGS Publications Warehouse

Rathbun, R.E.; Tai, D.Y.

1986-01-01

Volatilization is a significant process in determining the fate of many organic compounds in streams and rivers. Quantifying this process requires knowledge of the mass-transfer coefficient from water, which is a function of the gas-film and liquid-film coefficients. The gas-film coefficient can be determined by measuring the flux for the volatilization of pure organic liquids. Volatilization fluxes for acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-heptanone, and 2-octanone were measured in the laboratory over a range of temperatures. Gas-film coefficients were then calculated from these fluxes and from vapor pressure data from the literature. An equation was developed for predicting the volatilization flux of pure liquid ketones as a function of vapor pressure and molecular weight. Large deviations were found for acetone, and these were attributed to the possibility that acetone may be hydrogen bonded. A second equation for predicting the flux as a function of molecular weight and temperature resulted in large deviations for 4methyl-2-pentanone. These deviations were attributed to the branched structure of this ketone. Four factors based on the theory of volatilization and relating the volatilization flux or rate to the vapor pressure, molecular weight, temperature, and molecular diffusion coefficient were not constant as suggested by the literature. The factors generally increased with molecular weight and with temperature. Values for acetone corresponded to ketones with a larger molecular weight, and the acetone factors showed the greatest dependence on temperature. Both of these results are characteristic of compounds that are hydrogen bonded. Relations from the literature commonly used for describing the dependence of the gas-film coefficient on molecular weight and molecular diffusion coefficient were not applicable to the ketone gas-film coefficients. The dependence on molecular weight and molecular diffusion coefficient was in

Stereoselective borylative ketone-diene coupling.

PubMed

Cho, Hee Yeon; Yu, Zhiyong; Morken, James P

2011-10-07

In the presence of catalytic Ni(cod)(2) and P(t-Bu)(3), ketones, dienes, and B(2)(pin)(2) undergo a stereoselective multicomponent coupling reaction. Upon oxidation, the reaction furnishes 1,3-diols as the major reaction product. © 2011 American Chemical Society

Gallium (III) triflate catalyzed efficient Strecker reaction of ketones and their fluorinated analogs

PubMed Central

Prakash, G. K. Surya; Mathew, Thomas; Panja, Chiradeep; Alconcel, Steevens; Vaghoo, Habiba; Do, Clement; Olah, George A.

2007-01-01

The synthesis of α-aminonitriles and their fluorinated analogs has been carried out in high yield and purity by the Strecker reaction from the corresponding ketones and amines with trimethylsilyl cyanide using gallium triflate in dichloromethane. Monofluoro-, difluro-, or trifluoromethyl groups can be incorporated into the α-aminonitrile product by varying the nature of the fluorinated ketones. Study with various fluorinated and nonfluorinated ketones reveals that the choice of proper catalyst and the solvent system (suitable metal triflates as a catalyst and dichloromethane as a solvent) plays the key role in the direct Strecker reactions of ketones. PMID:17360416

Bioactivities of Ketones Terpenes: Antifungal Effect on F. verticillioides and Repellents to Control Insect Fungal Vector, S. zeamais.

PubMed

Pizzolitto, Romina P; Herrera, Jimena M; Zaio, Yesica P; Dambolena, Jose S; Zunino, Maria P; Gallucci, Mauro N; Zygadlo, Julio A

2015-11-12

Maize is one the most important staple foods in the world. However, numerous pests, such as fungal pathogens, e.g., Fusarium verticillioides, and insects, such as Sitophlilus zeamais, attack maize grains during storage. Many F. verticillioides strains produce fumonisins, one of the most important mycotoxin that causes toxic effects on human and animal health. This situation is aggravated by the insect fungal vector, Sitophlilus zeamais, which contributes to the dispersal of fungal spores, and through feeding damage, provide entry points for fungal infections. The aim of this study was to evaluate in vitro bioassays, the antifungal activity on F. verticillioides M3125 and repellent effects against S. zeamais of ketone terpenes. In addition, we performed Quantitative structure-activity relationship (Q-SAR) studies between physico-chemical properties of ketone terpenes and the antifungal effect. Thymoquinone was the most active compound against F. verticillioides (Minimum Inhibitory Concentration, MIC: 0.87) affecting the lag phase and the growth rate showing a total inhibition of growth at concentration higher than 2 mM (p < 0.05). The Q-SAR model revealed that the antifungal activity of ketone compounds is related to the electronic descriptor, Pi energy. Thymoquinone showed a strong repellent effect (-77.8 ± 8.5, p < 0.001) against S. zeamais. These findings make an important contribution to the search for new compounds to control two stored pests of maize.

Bioactivities of Ketones Terpenes: Antifungal Effect on F. verticillioides and Repellents to Control Insect Fungal Vector, S. zeamais

PubMed Central

Pizzolitto, Romina P.; Herrera, Jimena M.; Zaio, Yesica P.; Dambolena, Jose S.; Zunino, Maria P.; Gallucci, Mauro N.; Zygadlo, Julio A.

2015-01-01

Maize is one the most important staple foods in the world. However, numerous pests, such as fungal pathogens, e.g., Fusarium verticillioides, and insects, such as Sitophlilus zeamais, attack maize grains during storage. Many F. verticillioides strains produce fumonisins, one of the most important mycotoxin that causes toxic effects on human and animal health. This situation is aggravated by the insect fungal vector, Sitophlilus zeamais, which contributes to the dispersal of fungal spores, and through feeding damage, provide entry points for fungal infections. The aim of this study was to evaluate in vitro bioassays, the antifungal activity on F. verticillioides M3125 and repellent effects against S. zeamais of ketone terpenes. In addition, we performed Quantitative structure–activity relationship (Q-SAR) studies between physico-chemical properties of ketone terpenes and the antifungal effect. Thymoquinone was the most active compound against F. verticillioides (Minimum Inhibitory Concentration, MIC: 0.87) affecting the lag phase and the growth rate showing a total inhibition of growth at concentration higher than 2 mM (p < 0.05). The Q-SAR model revealed that the antifungal activity of ketone compounds is related to the electronic descriptor, Pi energy. Thymoquinone showed a strong repellent effect (−77.8 ± 8.5, p < 0.001) against S. zeamais. These findings make an important contribution to the search for new compounds to control two stored pests of maize. PMID:27682121

The role of changes in the sensitivity of hepatic mitochondrial overt carnitine palmitoyltransferase in determining the onset of the ketosis of starvation in the rat.

PubMed Central

Drynan, L; Quant, P A; Zammit, V A

1996-01-01

The relationships between the increase in blood ketone-body concentrations and several parameters that can potentially influence the rate of hepatic fatty acid oxidation were studied during progressive starvation (up to 24 h) in the rat in order to discover whether the sensitivity of mitochondrial overt carnitine palmitoyltransferase (CPT I) to malonyl-CoA plays an important part in determining the intrahepatic potential for fatty acid oxidation during the onset of ketogenic conditions. A rapid increase in blood ketone-body concentration occurred between 12 and 16 h of starvation, several hours after the marked fall in hepatic malonyl-CoA and in serum insulin concentrations and doubling of plasma non-esterfied fatty acid (NEFA) concentration. Consequently, both the changes in hepatic malonyl-CoA and serum NEFA preceded the increase in blood ketone-body concentration by several hours. The maximal activity of CPT I increased gradually throughout the 24 h period of starvation, but the increases did not become significant before 18 h of starvation. By contrast, the sensitivity of CPT I to malonyl-CoA and the increase in blood ketone-body concentration followed an identical time course, demonstrating the central importance of this parameter in determining the ketogenic response of the liver to the onset of the starved state. PMID:8836117

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

PubMed Central

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

Effect of weight loss and ketosis on postprandial cholecystokinin and free fatty acid concentrations.

PubMed

Chearskul, Supornpim; Delbridge, Elizabeth; Shulkes, Arthur; Proietto, Joseph; Kriketos, Adamandia

2008-05-01

Weight regain after weight loss may not be due primarily to voluntary return to social habits but may be explained by changes in peripheral hormonal signals activating hunger and encouraging feeding behavior. The objective of this study was to investigate physiologic adaptations to weight loss that may encourage weight regain. The study had a within-subject repeated-measure design [12 healthy, obese men, 33-64 y, body mass index (in kg/m(2)) 30-46] and was a clinical intervention investigation of circulating metabolites and hunger-satiety responses before and after weight loss. Measures included anthropometry (bioelectrical impedance, body weight, and waist circumference), concentrations of circulating hormones and metabolites [ketone bodies, free fatty acids (FFAs), insulin, leptin, glucose, and cholecystokinin (CCK)], and measures of hunger and satiety at baseline, 8 wk after weight loss with a very-low-energy diet, and 1 wk after weight maintenance. Weight loss led to a reduction in postprandial CCK secretion (P = 0.016). However, when subjects were ketotic (elevated circulating beta-hydroxybutyrate concentrations), CCK secretion was sustained at concentrations before weight loss. After weight loss, there were reduced postprandial FFA concentrations (P = 0.0005). The presence of ketosis sustained FFA to concentrations before weight loss (P = 0.60). Rapid weight loss of approximately 10% of initial body weight results in a reduction in postprandial CCK and FFA concentrations.

Acyl hydrazides as acyl donors for the synthesis of diaryl and aryl alkyl ketones.

PubMed

Akhbar, Ahmed R; Chudasama, Vijay; Fitzmaurice, Richard J; Powell, Lyn; Caddick, Stephen

2014-01-21

In this communication we describe a novel strategy for the formation of valuable diaryl and aryl alkyl ketones from acyl hydrazides. A wide variety of ketones are prepared and the mild reaction conditions allow for the use of a range of functionalities, especially in the synthesis of diaryl ketones.

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

NASA Astrophysics Data System (ADS)

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.

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2012 CFR

2012-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2014 CFR

2014-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2013 CFR

2013-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

Effects of very-low-carbohydrate (horsemeat- or beef-based) diets and restricted feeding on weight gain, feed and energy efficiency, as well as serum levels of cholesterol, triacylglycerol, glucose, insulin and ketone bodies in adult rats.

PubMed

Kim, Jae-Youn; Yang, Young-Hoon; Kim, Choong-Nam; Lee, Chong-Eon; Kim, Kyu-Il

2008-01-01

The beneficial or harmful effect of the low-carbohydrate (low-carb), high-protein, high-fat diet (Atkins diet) has not been clearly demonstrated. We determined the effect of a low-carb diet and restricted feeding (70% ad libitum intake) on serum levels of cholesterol, triacylglycerol, glucose, ketone bodies and insulin in rats. In experiment 1, each of 4 groups with 10 adult rats was assigned to a high-carb diet (AIN-93G) + ad libitum intake or restricted feeding, or a low-carb diet (53% horsemeat) + ad libitum intake or restricted feeding (2 x 2 factorial). In experiment 2, each of 3 groups with 10 adult rats was assigned to a control (AIN-93G) or low-carb diets (53% beef or horsemeat). Restricted feeding and the low-carb diet reduced (p<0.01) serum triacylglycerol compared with ad libitum intake and the AIN-93G diet, respectively (experiment 1). The dietary effect on serum total cholesterol, high-density or low-density lipid cholesterol appeared to be inconsistent, but restricted feeding increased the low-density lipoprotein cholesterol level. The serum ketone body level was increased by the low-carb diet compared with AIN-93G (experiment 2). Restricted feeding and a low-carb diet are beneficial for alleviating cardiovascular disease risk factors, and their effects are additive, restricted feeding being more pronounced. Copyright 2009 S. Karger AG, Basel.

Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

DOE PAGES

Jiang, Xingyu; Chen, Wenyong; Hartwig, John F.

2016-04-01

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.

Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Xingyu; Chen, Wenyong; Hartwig, John F.

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.

Enantioselective synthesis of 2,2-disubstituted terminal epoxides via catalytic asymmetric Corey-Chaykovsky epoxidation of ketones.

PubMed

Sone, Toshihiko; Yamaguchi, Akitake; Matsunaga, Shigeki; Shibasaki, Masakatsu

2012-02-07

Catalytic asymmetric Corey-Chaykovsky epoxidation of various ketones with dimethyloxosulfonium methylide using a heterobimetallic La-Li(3)-BINOL complex (LLB) is described. The reaction proceeded smoothly at room temperature in the presence of achiral phosphine oxide additives, and 2,2-disubstituted terminal epoxides were obtained in high enantioselectivity (97%-91% ee) and yield ( > 99%-88%) from a broad range of methyl ketones with 1-5 mol% catalyst loading. Enantioselectivity was strongly dependent on the steric hindrance, and other ketones, such as ethyl ketones and propyl ketones resulted in slightly lower enantioselectivity (88%-67% ee).

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

PubMed

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.

The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

NASA Astrophysics Data System (ADS)

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 .

Efficient palladium-catalyzed asymmetric allylic alkylation of ketones and aldehydes.

PubMed

Zhao, Xiaohu; Liu, Delong; Xie, Fang; Liu, Yangang; Zhang, Wanbin

2011-03-21

Palladium-catalyzed asymmetric allylic alkylation of ketones, via enamines generated in situ as nucleophiles, were carried out smoothly with chiral metallocene-based P,N-ligands. Under the same conditions, however, reactions of aldehydes could hardly be observed. Subsequently, this obstacle was resolved by using chiral metallocene-based P,P-ligands. Both ketones and aldehydes afforded excellent enantioselectivities with up to 98% ee and 94% ee, respectively.

Interaction of gabaergic ketones with model membranes: A molecular dynamics and experimental approach.

PubMed

Miguel, Virginia; Sánchez-Borzone, Mariela E; García, Daniel A

2018-08-01

γ-Aminobutyric-acid receptor (GABA A -R), a membrane intrinsic protein, is activated by GABA and modulated by a wide variety of recognized drugs. GABA A -R is also target for several insecticides which act by recognition of a non-competitive blocking site. Mentha oil is rich in several ketones with established activity against various insects/pests. Considering that mint ketones are highly lipophilic, their action mechanism could involve, at least in part, a non-specific receptor modulation by interacting with the surrounding lipids. In the present work, we studied in detail the effect on membranes of five cyclic ketones present in mint plants, with demonstrated insecticide and gabaergic activity. Particularly, we have explored their effect on the organization and dynamics of the membrane, by using Molecular Dynamics (MD) Simulation studies in a bilayer model of DPPC. We performed free diffusion MD and obtained spatially resolved free energy profiles of ketones partition into bilayers based on umbrella sampling. The most favored location of ketones in the membrane corresponded to the lower region of the carbonyl groups. Both hydrocarbon chains were slightly affected by the presence of ketones, presenting an ordering effect for the methylene groups closer to the carbonyl. MD simulations results were also contrasted with experimental data from fluorescence anisotropy studies which evaluate changes in membrane fluidity. In agreement, these assays indicated that the presence of ketones between lipid molecules induced an enhancement of the intermolecular interaction, increasing the molecular order throughout the bilayer thickness. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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.

[Determination of nitroaromatics and cyclo ketones in sea water' by gas chromatography coupled with activated carbon fiber solid-phase micro-extraction].

PubMed

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.

Versatile Alkylation of (Hetero)Aryl Iodides with Ketones via β-C(sp3)-H Activation.

PubMed

Zhu, Ru-Yi; Liu, Luo-Yan; Park, Han Seul; Hong, Kai; Wu, Yongwei; Senanayake, Chris H; Yu, Jin-Quan

2017-11-15

We report Pd(II)-catalyzed β-C(sp 3 )-H (hetero)arylation of a variety of ketones using a commercially available 2,2-dimethyl aminooxyacetic acid auxiliary. Facile installation and removal of the auxiliary as well as its superior scope for both ketones and (hetero)aryl iodides overcome the significant limitations of the previously reported β-C(sp 3 )-H arylation of ketones. The ready availability of ketones renders this reaction a broadly useful method for alkyl-(hetero)aryl coupling involving both primary and secondary alkyls.

Photochemical Production of Aldehydes and Ketones from Petroleum Films on Seawater

NASA Astrophysics Data System (ADS)

Tarr, M. A.; Rebet, K.; Monin, L.; Bastian, G.

2016-02-01

While numerous reports have demonstrated that sunlight results in oxygenation of petroleum in environmental systems, few details are available regarding the specific mechanisms of these reactions. Previous studies have not been able to identify specific chemicals formed when oil is subjected to photochemical transformation. In this study, we have utilized several petroleum samples to investigate the formation of aldehyde and ketone photoproducts. These samples included oil from the MC252 well (source of the Deepwater Horizon spill), surrogate oil provided by BP to represent the MC252 oil, and residual fuel oil (NIST 2717a). Thin films of oil ( 100 μm) were placed over water and irradiated with a solar simulator for the equivalent of 1.5-12 days. After irradiation, the water was carefully separated from the oil and derivatized with 2,4-dinitrophenylhydrazine, a selective derivatization agent for aldehydes and ketones. The derivatized material was then analyzed by HPLC. Additional analysis by electrospray MS was also performed, and absorbance and fluorescence spectra of the underivatized aqueous phase were recorded. For all oils, exposure to sunlight resulted in release of aldehydes and ketones to the aqueous phase. The amount of released photoproducts was proportional to the length of solar exposure, but no production was seen for dark controls. Despite some similarities, the pattern of product formation varied from oil to oil. Addition of dispersant (Corexit 9500a or 9527a) resulted in larger amounts of aldehydes and ketones detected in the aqueous phase after solar irradiation of the oil. Electrospray mass spectrometry was utilized in an attempt to provide structural information about the aldehydes and ketones formed. Results of this study demonstrate that aldehydes and ketones are important photoproducts resulting from solar irradiation of oil on water. These products will affect the transport and bioavailability of oil spilled in aquatic systems.

Whole-body to tissue concentration ratios for use in biota dose assessments for animals.

PubMed

Yankovich, Tamara L; Beresford, Nicholas A; Wood, Michael D; Aono, Tasuo; Andersson, Pål; Barnett, Catherine L; Bennett, Pamela; Brown, Justin E; Fesenko, Sergey; Fesenko, J; Hosseini, Ali; Howard, Brenda J; Johansen, Mathew P; Phaneuf, Marcel M; Tagami, Keiko; Takata, Hyoe; Twining, John R; Uchida, Shigeo

2010-11-01

Environmental monitoring programs often measure contaminant concentrations in animal tissues consumed by humans (e.g., muscle). By comparison, demonstration of the protection of biota from the potential effects of radionuclides involves a comparison of whole-body doses to radiological dose benchmarks. Consequently, methods for deriving whole-body concentration ratios based on tissue-specific data are required to make best use of the available information. This paper provides a series of look-up tables with whole-body:tissue-specific concentration ratios for non-human biota. Focus was placed on relatively broad animal categories (including molluscs, crustaceans, freshwater fishes, marine fishes, amphibians, reptiles, birds and mammals) and commonly measured tissues (specifically, bone, muscle, liver and kidney). Depending upon organism, whole-body to tissue concentration ratios were derived for between 12 and 47 elements. The whole-body to tissue concentration ratios can be used to estimate whole-body concentrations from tissue-specific measurements. However, we recommend that any given whole-body to tissue concentration ratio should not be used if the value falls between 0.75 and 1.5. Instead, a value of one should be assumed.

High-performance liquid chromatography determination of ketone bodies in human plasma by precolumn derivatization with p-nitrobenzene diazonium fluoroborate.

PubMed

Yamato, Susumu; Shinohara, Kumiko; Nakagawa, Saori; Kubota, Ai; Inamura, Katsushi; Watanabe, Gen; Hirayama, Satoshi; Miida, Takashi; Ohta, Shin

2009-01-01

We developed and validated a sensitive and convenient high-performance liquid chromatography (HPLC) method for the specific determination of ketone bodies (acetoacetate and D-3-hydroxybutyrate) in human plasma. p-Nitrobenzene diazonium fluoroborate (diazo reagent) was used as a precolumn derivatization agent, and 3-(2-hydroxyphenyl) propionic acid was used as an internal standard. After the reaction, excess diazo reagent and plasma proteins were removed by passing through a solid-phase cartridge (C(18)). The derivatives retained on the cartridge were eluted with methanol, introduced into the HPLC system, and then detected with UV at 380 nm. A calibration curve for acetoacetate standard solution with a 20-microl injection volume showed good linearity in the range of 1 to 400 microM with a 0.9997 correlation coefficient. For the determination of D-3-hydroxybutyrate, it was converted to acetoacetate before reaction with the diazo reagent by an enzymatic coupling method using D-3-hydroxybutyrate dehydrogenase and lactate dehydrogenase. A calibration curve for D-3-hydroxybutyrate standard solution also showed good linearity in the range of 1.5 to 2000 microM with a 0.9988 correlation coefficient. Analytical recoveries of acetoacetate and D-3-hydroxybutyrate in human plasma were satisfactory. The method was successfully applied to samples from diabetic patients, and results were consistent with those obtained using the thio-NAD enzymatic cycling method used in clinical laboratories.

Methodology for in situ protection of aldehydes and ketones using trimethylsilyl trifluoromethanesulfonate and phosphines: selective alkylation and reduction of ketones, esters, amides, and nitriles.

PubMed

Yahata, Kenzo; Minami, Masaki; Yoshikawa, Yuki; Watanabe, Kei; Fujioka, Hiromichi

2013-01-01

A methodology for selective transformations of ketones, esters, Weinreb amides, and nitriles in the presence of aldehydes has been developed. The use of a combination of PPh(3)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) promotes selective transformation of aldehydes to their corresponding, temporarily protected, O,P-acetal type phosphonium salts. Because, hydrolytic work-up following ensuing reactions of other carbonyl moieties in the substrates liberates the aldehyde moiety, a sequence involving aldehyde protection, transformation of other carbonyl groups, and deprotection can be accomplished in a one-pot manner. Furthermore, the use of PEt(3) instead of PPh(3) enables ketones to be converted in situ to their corresponding O,P-ketal type phosphonium salts and, consequently, selective transformations of esters, Weinreb amides, and nitriles in the presence of ketones can be performed. This methodology is applicable to various dicarbonyl compounds, including substrates that possess heteroaromatic skeletons and hydroxyl protecting groups.

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

PubMed Central

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

Childhood obesity treatment; Effects on BMI SDS, body composition, and fasting plasma lipid concentrations.

PubMed

Nielsen, Tenna Ruest Haarmark; Fonvig, Cilius Esmann; Dahl, Maria; Mollerup, Pernille Maria; Lausten-Thomsen, Ulrik; Pedersen, Oluf; Hansen, Torben; Holm, Jens-Christian

2018-01-01

The body mass index (BMI) standard deviation score (SDS) may not adequately reflect changes in fat mass during childhood obesity treatment. This study aimed to investigate associations between BMI SDS, body composition, and fasting plasma lipid concentrations at baseline and during childhood obesity treatment. 876 children and adolescents (498 girls) with overweight/obesity, median age 11.2 years (range 1.6-21.7), and median BMI SDS 2.8 (range 1.3-5.7) were enrolled in a multidisciplinary outpatient treatment program and followed for a median of 1.8 years (range 0.4-7.4). Height and weight, body composition measured by dual-energy X-ray absorptiometry, and fasting plasma lipid concentrations were assessed at baseline and at follow-up. Lipid concentrations (total cholesterol (TC), low-density lipoprotein (LDL), high-density lipoprotein (HDL), non-HDL, and triglycerides (TG)) were available in 469 individuals (264 girls). Linear regressions were performed to investigate the associations between BMI SDS, body composition indices, and lipid concentrations. At baseline, BMI SDS was negatively associated with concentrations of HDL (p = 6.7*10-4) and positively with TG (p = 9.7*10-6). Reductions in BMI SDS were associated with reductions in total body fat percentage (p<2*10-16) and percent truncal body fat (p<2*10-16). Furthermore, reductions in BMI SDS were associated with improvements in concentrations of TC, LDL, HDL, non-HDL, LDL/HDL-ratio, and TG (all p <0.0001). Changes in body fat percentage seemed to mediate the changes in plasma concentrations of TC, LDL, and non-HDL, but could not alone explain the changes in HDL, LDL/HDL-ratio or TG. Among 81 individuals with available lipid concentrations, who increased their BMI SDS, 61% improved their body composition, and 80% improved their lipid concentrations. Reductions in the degree of obesity during multidisciplinary childhood obesity treatment are accompanied by improvements in body composition and fasting plasma

Portable method of measuring gaseous acetone concentrations.

PubMed

Worrall, Adam D; Bernstein, Jonathan A; Angelopoulos, Anastasios P

2013-08-15

Measurement of acetone in human breath samples has been previously shown to provide significant non-invasive diagnostic insight into the control of a patient's diabetic condition. In patients with diabetes mellitus, the body produces excess amounts of ketones such as acetone, which are then exhaled during respiration. Using various breath analysis methods has allowed for the accurate determination of acetone concentrations in exhaled breath. However, many of these methods require instrumentation and pre-concentration steps not suitable for point-of-care use. We have found that by immobilizing resorcinol reagent into a perfluorosulfonic acid polymer membrane, a controlled organic synthesis reaction occurs with acetone in a dry carrier gas. The immobilized, highly selective product of this reaction (a flavan) is found to produce a visible spectrum color change which could measure acetone concentrations to less than ppm. We here demonstrate how this approach can be used to produce a portable optical sensing device for real-time, non-invasive acetone analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

40 CFR 721.10417 - Biphenyl alkyl morpholino ketone (generic) (P-11-338).

Code of Federal Regulations, 2014 CFR

2014-07-01

... (generic) (P-11-338). 721.10417 Section 721.10417 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10417 Biphenyl alkyl morpholino ketone (generic) (P-11-338). (a... generically as biphenyl alkyl morpholino ketone (PMN P-11-338) is subject to reporting under this section for...

40 CFR 721.10417 - Biphenyl alkyl morpholino ketone (generic) (P-11-338).

Code of Federal Regulations, 2013 CFR

2013-07-01

... (generic) (P-11-338). 721.10417 Section 721.10417 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10417 Biphenyl alkyl morpholino ketone (generic) (P-11-338). (a... generically as biphenyl alkyl morpholino ketone (PMN P-11-338) is subject to reporting under this section for...

40 CFR 721.10417 - Biphenyl alkyl morpholino ketone (generic) (P-11-338).

Code of Federal Regulations, 2012 CFR

2012-07-01

... (generic) (P-11-338). 721.10417 Section 721.10417 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10417 Biphenyl alkyl morpholino ketone (generic) (P-11-338). (a... generically as biphenyl alkyl morpholino ketone (PMN P-11-338) is subject to reporting under this section for...

Unlocking the chemotherapeutic potential of beta-aminovinyl ketones and related compounds.

PubMed

Gaber, Hatem M; Bagley, Mark C

2009-07-01

The role of beta-aminovinyl ketones as synthetic intermediates has been well categorised, but recent developments have shown an interesting array of applications and new chemotherapeutic potential, both in the preparation of biologically active heterocycles and as pharmacophores in their own right.Medicinal chemists are accustomed to using the products of Knoevenagel-type condensations as auxiliaries for the synthesis of N-containing heteroaromatic compounds. One such example of these chemical building blocks are beta-aminovinyl ketones-valuable synthetic intermediates that have been used in the preparation of pyridines, pyrimidines, pyrazoles, and many other heterocyclic motifs. This review highlights their recent use in the synthesis of biologically active targets as part of drug discovery programmes and in natural product synthesis. However, it is becoming increasingly evident that the enaminone motif may serve as a therapeutic pharmacophore in its own right. This review highlights the range of biological responses that beta-aminovinyl ketones elicit, including as antitumour, antibacterial, and anticonvulsant agents. Thus, with a broad spectrum of biological properties and as versatile chemical intermediates, it is clear that beta-aminovinyl ketones offer great potential in the search for new chemotherapeutic agents.

Effects of iron-containing minerals on hydrothermal reactions of ketones

NASA Astrophysics Data System (ADS)

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.

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

DOE PAGES

Griffith, David A.; Kung, Daniel W.; Esler, William P.; ...

2014-11-25

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. 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 formore » 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. In conclusion, this demonstration of target engagement validates the use of compound 9 to evaluate the role of DNL in human disease.« less

Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS)

NASA Astrophysics Data System (ADS)

Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

2017-05-01

Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH- as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H]+ [mass-to-charge ratio ( m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H]- ( m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones.

Childhood obesity treatment; Effects on BMI SDS, body composition, and fasting plasma lipid concentrations

PubMed Central

Fonvig, Cilius Esmann; Dahl, Maria; Mollerup, Pernille Maria; Lausten-Thomsen, Ulrik; Pedersen, Oluf; Hansen, Torben; Holm, Jens-Christian

2018-01-01

Objective The body mass index (BMI) standard deviation score (SDS) may not adequately reflect changes in fat mass during childhood obesity treatment. This study aimed to investigate associations between BMI SDS, body composition, and fasting plasma lipid concentrations at baseline and during childhood obesity treatment. Methods 876 children and adolescents (498 girls) with overweight/obesity, median age 11.2 years (range 1.6–21.7), and median BMI SDS 2.8 (range 1.3–5.7) were enrolled in a multidisciplinary outpatient treatment program and followed for a median of 1.8 years (range 0.4–7.4). Height and weight, body composition measured by dual-energy X-ray absorptiometry, and fasting plasma lipid concentrations were assessed at baseline and at follow-up. Lipid concentrations (total cholesterol (TC), low-density lipoprotein (LDL), high-density lipoprotein (HDL), non-HDL, and triglycerides (TG)) were available in 469 individuals (264 girls). Linear regressions were performed to investigate the associations between BMI SDS, body composition indices, and lipid concentrations. Results At baseline, BMI SDS was negatively associated with concentrations of HDL (p = 6.7*10−4) and positively with TG (p = 9.7*10−6). Reductions in BMI SDS were associated with reductions in total body fat percentage (p<2*10−16) and percent truncal body fat (p<2*10−16). Furthermore, reductions in BMI SDS were associated with improvements in concentrations of TC, LDL, HDL, non-HDL, LDL/HDL-ratio, and TG (all p <0.0001). Changes in body fat percentage seemed to mediate the changes in plasma concentrations of TC, LDL, and non-HDL, but could not alone explain the changes in HDL, LDL/HDL-ratio or TG. Among 81 individuals with available lipid concentrations, who increased their BMI SDS, 61% improved their body composition, and 80% improved their lipid concentrations. Conclusion Reductions in the degree of obesity during multidisciplinary childhood obesity treatment are accompanied by

STIMULATION OF TARSAL RECEPTORS OF THE BLOWFLY BY ALIPHATIC ALDEHYDES AND KETONES

PubMed Central

Chadwick, L. E.; Dethier, V. G.

1949-01-01

Rejection of eight aldehydes, eight ketones, five secondary alcohols, and 3-pentanol has been studied in the blowfly Phormia regina Meigen. The data agree with results previously reported for normal alcohols and several series of glycols in showing a logarithmic increase in stimulating effect with increasing chain length. The order of increasing effectiveness among the different species of compounds thus far investigated is the following: polyglycols, diols, secondary alcohols, iso-alcohols, normal alcohols, ketones, iso-aldehydes, normal aldehydes. Curves relating the logarithms of threshold concentration to the logarithms of chain length for diols, alcohols, aldehydes, and ketones show inflections in the 3 to 6 carbon range. Above and below the region of inflection the curves are nearly rectilinear. The slopes for the upper limbs (smaller molecules) are of the order of –2; for the lower limbs, about –10. Comparisons of the threshold data with numerical values for molecular weights, molecular areas and volumes, oil-water distribution coefficients, activity coefficients, standard free energies, vapor pressures, boiling points, melting points, dipole moments, dielectric constants, and degree of association are discussed briefly, and it is concluded that none of the comparisons serves to bring the data from the several series and from the two portions of each series into a single homogeneous system. A qualitative comparison with water solubilities shows fewer discrepancies. It is suggested that the existence of a combination of aqueous and lipoid phases at the receptor surface would fit best with what is presently known about the relationship between chemical structure and stimulating effect in contact chemoreception. In this hypothesis the smaller and more highly water-soluble compounds are envisaged as gaining access to the receptors partly through the aqueous phase, the larger molecules predominantly through the lipoid phase. PMID:18114559

Hyperketonemia and ketosis increase the risk of complications in type 1 diabetes.

PubMed

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.

Exogenous Ketone Supplements Reduce Anxiety-Related Behavior in Sprague-Dawley and Wistar Albino Glaxo/Rijswijk Rats

PubMed Central

Ari, Csilla; Kovács, Zsolt; Juhasz, Gabor; Murdun, Cem; Goldhagen, Craig R.; Koutnik, Andrew P.; Poff, Angela M.; Kesl, Shannon L.; D’Agostino, Dominic P.

2016-01-01

Nutritional ketosis has been proven effective for seizure disorders and other neurological disorders. The focus of this study was to determine the effects of ketone supplementation on anxiety-related behavior in Sprague-Dawley (SPD) and Wistar Albino Glaxo/Rijswijk (WAG/Rij) rats. We tested exogenous ketone supplements added to food and fed chronically for 83 days in SPD rats and administered sub-chronically for 7 days in both rat models by daily intragastric gavage bolus followed by assessment of anxiety measures on elevated plus maze (EPM). The groups included standard diet (SD) or SD + ketone supplementation. Low-dose ketone ester (LKE; 1,3-butanediol-acetoacetate diester, ~10 g/kg/day, LKE), high dose ketone ester (HKE; ~25 g/kg/day, HKE), beta-hydroxybutyrate-mineral salt (βHB-S; ~25 g/kg/day, KS) and βHB-S + medium chain triglyceride (MCT; ~25 g/kg/day, KSMCT) were used as ketone supplementation for chronic administration. To extend our results, exogenous ketone supplements were also tested sub-chronically on SPD rats (KE, KS and KSMCT; 5 g/kg/day) and on WAG/Rij rats (KE, KS and KSMCT; 2.5 g/kg/day). At the end of treatments behavioral data collection was conducted manually by a blinded observer and with a video-tracking system, after which blood βHB and glucose levels were measured. Ketone supplementation reduced anxiety on EPM as measured by less entries to closed arms (sub-chronic KE and KS: SPD rats and KSMCT: WAG/Rij rats), more time spent in open arms (sub-chronic KE: SPD and KSMCT: WAG/Rij rats; chronic KSMCT: SPD rats), more distance traveled in open arms (chronic KS and KSMCT: SPD rats) and by delayed latency to entrance to closed arms (chronic KSMCT: SPD rats), when compared to control. Our data indicates that chronic and sub-chronic ketone supplementation not only elevated blood βHB levels in both animal models, but reduced anxiety-related behavior. We conclude that ketone supplementation may represent a promising anxiolytic strategy through a

Examination of Body Composition, Flexibility, Balance, and Concentration Related to Dance Exercise

ERIC Educational Resources Information Center

Bastug, Gulsum

2018-01-01

In this study was to examine the body composition, flexibility, balance and concentration characteristics of dance exercise. Total of 268 university students whose average age was 20.59 ± 1.59 years were included. Height measurements, body weight measurements, flexibility measurements, balance test, concentration test of the students who had dance…

Field validation of the dnph method for aldehydes and ketones. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Workman, G.S.; Steger, J.L.

1996-04-01

A stationary source emission test method for selected aldehydes and ketones has been validated. The method employs a sampling train with impingers containing 2,4-dinitrophenylhydrazine (DNPH) to derivatize the analytes. The resulting hydrazones are recovered and analyzed by high performance liquid chromatography. Nine analytes were studied; the method was validated for formaldehyde, acetaldehyde, propionaldehyde, acetophenone and isophorone. Acrolein, menthyl ethyl ketone, menthyl isobutyl ketone, and quinone did not meet the validation criteria. The study employed the validation techniques described in EPA method 301, which uses train spiking to determine bias, and collocated sampling trains to determine precision. The studies were carriedmore » out at a plywood veneer dryer and a polyester manufacturing plant.« less

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 9 2011-07-01 2011-07-01 false Deletion of methyl ethyl ketone from... Designations, Source Category List § 63.61 Deletion of methyl ethyl ketone from the list of hazardous air pollutants. The substance methyl ethyl ketone (MEK, 2-Butanone) (CAS Number 78-93-3) is deleted from the list...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Deletion of methyl ethyl ketone from... Designations, Source Category List § 63.61 Deletion of methyl ethyl ketone from the list of hazardous air pollutants. The substance methyl ethyl ketone (MEK, 2-Butanone) (CAS Number 78-93-3) is deleted from the list...

An experimental study of the combined effects of n-hexane and methyl ethyl ketone.

PubMed Central

Takeuchi, Y; Ono, Y; Hisanaga, N; Iwata, M; Aoyama, M; Kitoh, J; Sugiura, Y

1983-01-01

This study was intended to determine whether or not methyl ethyl ketone (MEK) enhances the neurotoxicity of n-hexane at low concentration and after long term exposure. Separate groups of eight rats were exposed to 100 ppm n-hexane, 200 ppm MEK, 100 ppm n-hexane plus 200 ppm MEK, or fresh air in an exposure chamber for 12 hours a day for 24 weeks. The body weight, motor nerve conduction velocity (MCV), distal motor latency (DL), and mixed nerve conduction velocities (MNCVs) were measured before exposure and after four, eight, 12, 16, 20, and 24 weeks' exposure. One rat of each group was histopathologically examined after 24 weeks' exposure. Exposure of 100 ppm n-hexane did not significantly decrease the functions of the peripheral nerve throughout the experiment. Exposure to 200 ppm MEK significantly increased MCV and MNCVs and decreased DL after four weeks' exposure, but at this later stage no significant changes were found throughout the experiment by comparison with the controls. Mixed exposure to 100 ppm n-hexane plus 200 ppm MEK significantly decreased by comparison with the controls. On histopathological examination of the tail nerve, however, no changes were found in any of the exposed groups or the controls. These results suggest that MEK might enhance the neurotoxicity of n-hexane at a low concentration, and mixed exposures to n-hexane and MEK should be avoided. PMID:6830718

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

PubMed

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.

Photoredox activation for the direct β-arylation of ketones and aldehydes.

PubMed

Pirnot, Michael T; Rankic, Danica A; Martin, David B C; MacMillan, David W C

2013-03-29

The direct β-activation of saturated aldehydes and ketones has long been an elusive transformation. We found that photoredox catalysis in combination with organocatalysis can lead to the transient generation of 5π-electron β-enaminyl radicals from ketones and aldehydes that rapidly couple with cyano-substituted aryl rings at the carbonyl β-position. This mode of activation is suitable for a broad range of carbonyl β-functionalization reactions and is amenable to enantioselective catalysis.

Solvation of Esters and Ketones in Supercritical CO2.

PubMed

Kajiya, Daisuke; Imanishi, Masayoshi; Saitow, Ken-ichi

2016-02-04

Vibrational Raman spectra for the C═O stretching modes of three esters with different functional groups (methyl, a single phenyl, and two phenyl groups) were measured in supercritical carbon dioxide (scCO2). The results were compared with Raman spectra for three ketones involving the same functional groups, measured at the same thermodynamic states in scCO2. The peak frequencies of the Raman spectra of these six solute molecules were analyzed by decomposition into the attractive and repulsive energy components, based on the perturbed hard-sphere theory. For all solute molecules, the attractive energy is greater than the repulsive energy. In particular, a significant difference in the attractive energies of the ester-CO2 and ketone-CO2 systems was observed when the methyl group is attached to the ester or ketone. This difference was significantly reduced in the solute systems with a single phenyl group and was completely absent in those with two phenyl groups. The optimized structures among the solutes and CO2 molecules based on quantum chemical calculations indicate that greater attractive energy is obtained for a system where the oxygen atom of the ester is solvated by CO2 molecules.

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

PubMed

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 < 10(-4)). A weak positive relationship was found between blood glucose and breath 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.

KETONES INHIBIT MITOCHONDRIAL PRODUCTION OF REACTIVE OXYGEN SPECIES PRODUCTION FOLLOWING GLUTAMATE EXCITOTOXICITY BY INCREASING NADH OXIDATION

PubMed Central

Maalouf, Marwan; Sullivan, Patrick G.; Davis, Laurie; Kim, Do Young; Rho, Jong M.

2007-01-01

Dietary protocols that increase serum levels of ketones, such as calorie restriction and the ketogenic diet, offer robust protection against a multitude of acute and chronic neurological diseases. The underlying mechanisms, however, remain unclear. Previous studies have suggested that the ketogenic diet may reduce free radical levels in the brain. Thus, one possibility is that ketones may mediate neuroprotection through antioxidant activity. In the present study, we examined the effects of the ketones β-hydroxybutyrate and acetoacetate on acutely dissociated rat neocortical neurons subjected to glutamate excitotoxicity using cellular electrophysiological and single-cell fluorescence imaging techniques. Further, we explored the effects of ketones on acutely isolated mitochondria exposed to high levels of calcium. A combination of β-hydroxybutyrate and acetoacetate (1 mM each) decreased neuronal death and prevented changes in neuronal membrane properties induced by 10 μM glutamate. Ketones also significantly decreased mitochondrial production of reactive oxygen species and the associated excitotoxic changes by increasing NADH oxidation in the mitochondrial respiratory chain, but did not affect levels of the endogenous antioxidant glutathione. In conclusion, we demonstrate that ketones reduce glutamate-induced free radical formation by increasing the NAD+/NADH ratio and enhancing mitochondrial respiration in neocortical neurons. This mechanism may, in part, contribute to the neuroprotective activity of ketones by restoring normal bioenergetic function in the face of oxidative stress. PMID:17240074

Synthesis of α-Halo-α,α-Difluoromethyl Ketones by a Trifluoroacetate Release/Halogenation Protocol

PubMed Central

John, Jinu P.; Colby, David A.

2011-01-01

Three series of α-halo-α,α-difluoromethyl ketones are prepared from highly α-fluorinated gem-diols by exploiting the facile release of trifluoroacetate, followed by immediate trapping of the liberated α,α-difluoroenolate with an electrophilic chlorine, bromine, or iodine source. The products are typically isolated in good yields, even in the case of sensitive, α-iodo-α,α-difluoromethyl ketones. Also, we demonstrate that an α-iodo-α,α-difluoromethyl ketone will participate in a copper-promoted reaction to forge a new carbon–carbon bond. PMID:21995668

Enantioselective Reduction of Ketones Catalyzed by Rare-Earth Metals Complexed with Phenoxy Modified Chiral Prolinols.

PubMed

Song, Peng; Lu, Chengrong; Fei, Zenghui; Zhao, Bei; Yao, Yingming

2018-06-01

Enantioselective reduction of ketones and α,β-unsaturated ketones by pinacolborane (HBpin) has been well-established by using chiral rare-earth metal catalysts with phenoxy modified prolinols. A number of highly optically active alcohols were obtained from reduction of simple ketones catalyzed by ytterbium complex 1 [L 4 Yb(L 4 H)] (H 2 L 4 = ( S)-2- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol). Moreover, α,β-unsaturated ketones were selectively reduced to a wide range of chiral allylic alcohols with excellent yields, high enantioselectivity, and complete chemoselectivity, catalyzed by a single component chiral ytterbium complex 2 [L 1 Yb(L 1 H)] (H 2 L 1 = ( S)-2,4-di- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol).

Lanthanum Tricyanide-Catalyzed Acyl Silane-Ketone Benzoin Additions and Kinetic Resolution of Resultant α-Silyloxyketones

PubMed Central

Tarr, James C.

2010-01-01

We report the full account of our efforts on the lanthanum tricyanide-catalyzed acyl silane-ketone benzoin reaction. The reaction exhibits a wide scope in both acyl silane (aryl, alkyl) and ketone (aryl-alkyl, alkyl-alkyl, aryl-aryl, alkenyl-alkyl, alkynyl-alkyl) coupling partners. The diastereoselectivity of the reaction has been examined in both cyclic and acyclic systems. Cyclohexanones give products arising from equatorial attack by the acyl silane. The diastereoselectivity of acyl silane addition to acyclic α-hydroxy ketones can be controlled by varying the protecting group to obtain either Felkin-Ahn or chelation control. The resultant α-silyloxyketone products can be resolved with selectivity factors from 10 to 15 by subjecting racemic ketone benzoin products to CBS reduction. PMID:20392127

Lanthanum tricyanide-catalyzed acyl silane-ketone benzoin additions and kinetic resolution of resultant alpha-silyloxyketones.

PubMed

Tarr, James C; Johnson, Jeffrey S

2010-05-21

We report the full account of our efforts on the lanthanum tricyanide-catalyzed acyl silane-ketone benzoin reaction. The reaction exhibits a wide scope in both acyl silane (aryl, alkyl) and ketone (aryl-alkyl, alkyl-alkyl, aryl-aryl, alkenyl-alkyl, alkynyl-alkyl) coupling partners. The diastereoselectivity of the reaction has been examined in both cyclic and acyclic systems. Cyclohexanones give products arising from equatorial attack by the acyl silane. The diastereoselectivity of acyl silane addition to acyclic alpha-hydroxy ketones can be controlled by varying the protecting group to obtain either Felkin-Ahn or chelation control. The resultant alpha-silyloxyketone products can be resolved with selectivity factors from 10 to 15 by subjecting racemic ketone benzoin products to CBS reduction.

Thiol reactivity and its impact on the ciliate toxicity of α,β-unsaturated aldehydes, ketones, and esters.

PubMed

Böhme, Alexander; Thaens, Diana; Schramm, Franziska; Paschke, Albrecht; Schüürmann, Gerrit

2010-12-20

A recently introduced chemoassay has been used to determine second-order rate constants of the electrophile-nucleophile reaction of 15 α,β-unsaturated aldehydes with glutathione. The respective kGSH values vary for more than 3 orders of magnitude, and are within the range determined previously for 31 α,β-unsaturated ketones and esters. Structure-reactivity analyses yield distinct relationships between kGSH and structural features of the compounds. Moreover, increasing kGSH increases the aldehyde toxicity toward ciliates in terms of 48 h-EC50 values (effective concentration yielding 50% growth inhibition of Tetrahymena pyriformis within 48 h). A respective log-log regression equation including both kGSH and the octanol/water partition coefficient, Kow, yields a squared correlation coefficient of 0.96. Comparative analysis with corresponding data for 15 ketones and 16 esters reveals systematic differences between the three compound classes with regard to the individual contributions of hydrophobicity and electrophilic reactivity to aquatic toxicity. The former is particularly pronounced for aldehydes, while the ester toxicity is largely governed by reactivity, with ketones showing an intermediate pattern that is more similar to the one of esters than of aldehydes. It follows that within the Michael acceptor domain of α,β-unsaturated carbonyls, a distinction between aldehydes and nonaldehydic derivatives appears necessary when employing electrophilic reactivity as a component for the quantitative prediction of their reactive toxicity toward aquatic organisms.

Photoredox Activation for the Direct β-Arylation of Ketones and Aldehydes

PubMed Central

Pirnot, Michael T.; Rankic, Danica A.; Martin, David B. C.; MacMillan, David W. C.

2013-01-01

The direct β-activation of saturated aldehydes and ketones has long been an elusive transformation. We found that photoredox catalysis in combination with organocatalysis can lead to the transient generation of 5π-electron β-enaminyl radicals from ketones and aldehydes that rapidly couple with cyano-substituted aryl rings at the carbonyl β-position. This mode of activation is suitable for a broad range of carbonyl β-functionalization reactions and is amenable to enantioselective catalysis. PMID:23539600

Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R.

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 hydroxylmore » 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

Direct conversion of alcohols to α-chloro aldehydes and α-chloro ketones.

PubMed

Jing, Yuanyuan; Daniliuc, Constantin G; Studer, Armido

2014-09-19

Direct conversion of primary and secondary alcohols into the corresponding α-chloro aldehydes and α-chloro ketones using trichloroisocyanuric acid, serving both as stoichiometric oxidant and α-halogenating reagent, is reported. For primary alcohols, TEMPO has to be added as an oxidation catalyst, and for the transformation of secondary alcohols (TEMPO-free protocol), MeOH as an additive is essential to promote chlorination of the intermediary ketones.

Clinical utility of Abbott Precision Xceed Pro® ketone meter in diabetic patients.

PubMed

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.

Comparative performance assessment of point-of-care testing devices for measuring glucose and ketones at the patient bedside.

PubMed

Ceriotti, Ferruccio; Kaczmarek, Ewa; Guerra, Elena; Mastrantonio, Fabrizio; Lucarelli, Fausto; Valgimigli, Francesco; Mosca, Andrea

2015-03-01

Point-of-care (POC) testing devices for monitoring glucose and ketones can play a key role in the management of dysglycemia in hospitalized diabetes patients. The accuracy of glucose devices can be influenced by biochemical changes that commonly occur in critically ill hospital patients and by the medication prescribed. Little is known about the influence of these factors on ketone POC measurements. The aim of this study was to assess the analytical performance of POC hospital whole-blood glucose and ketone meters and the extent of glucose interference factors on the design and accuracy of ketone results. StatStrip glucose/ketone, Optium FreeStyle glucose/ketone, and Accu-Chek Performa glucose were also assessed and results compared to a central laboratory reference method. The analytical evaluation was performed according to Clinical and Laboratory Standards Institute (CLSI) protocols for precision, linearity, method comparison, and interference. The interferences assessed included acetoacetate, acetaminophen, ascorbic acid, galactose, maltose, uric acid, and sodium. The accuracies of both Optium ketone and glucose measurements were significantly influenced by varying levels of hematocrit and ascorbic acid. StatStrip ketone and glucose measurements were unaffected by the interferences tested with exception of ascorbic acid, which reduced the higher level ketone value. The accuracy of Accu-Chek glucose measurements was affected by hematocrit, by ascorbic acid, and significantly by galactose. The method correlation assessment indicated differences between the meters in compliance to ISO 15197 and CLSI 12-A3 performance criteria. Combined POC glucose/ketone methods are now available. The use of these devices in a hospital setting requires careful consideration with regard to the selection of instruments not sensitive to hematocrit variation and presence of interfering substances. © 2014 Diabetes Technology Society.

Palladium-catalyzed, pyrrolidine-mediated arylmethylation of ketones and aldehydes with coumarinyl(methyl) acetates.

PubMed

Cattopadhyay, Kalicharan; Recio, Antonio; Tunge, Jon A

2012-09-14

We report the palladium-catalyzed, pyrrolidine-mediated α-benzylation of enamines generated from aldehydes and ketones. The method allows for direct coupling of medicinally relevant coumarin moieties with aldehydes and ketones in good yield under mild conditions. The reaction is believed to proceed via a Pd-π-benzyl complex generated from (coumarinyl)methyl acetates.

Morphology and properties of amine terminated poly(arylene ether ketone) and poly(arylene ether sulfone) modified epoxy resin systems

NASA Technical Reports Server (NTRS)

Cecere, J. A.; Mcgrath, J. E.; Hedrick, J. L.

1986-01-01

Epoxy resin networks cured with DDS were modified by incorporating tough ductile thermoplastics such as the amine terminated polyether sulfones and amine terminated polyether ketones. Both linear copolymers were able to significantly improve the fracture toughness values at the 15 and 30 weight percent concentrations examined. These improvements in fracture toughness were achieved without any significant change in the flexural modulus.

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

USDA-ARS?s Scientific Manuscript database

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...

Organocatalytic C-H bond arylation of aldehydes to bis-heteroaryl ketones.

PubMed

Toh, Qiao Yan; McNally, Andrew; Vera, Silvia; Erdmann, Nico; Gaunt, Matthew J

2013-03-13

An organocatalytic aldehyde C-H bond arylation process for the synthesis of complex heteroaryl ketones has been developed. By exploiting the inherent electrophilicity of diaryliodonium salts, we have found that a commercial N-heterocyclic carbene catalyst promotes the union of heteroaryl aldehydes and these heteroaromatic electrophile equivalents in good yields. This straightforward catalytic protocol offers access to ketones bearing a diverse array of arene and heteroarene substituents that can subsequently be converted into molecules displaying structural motifs commonly found in medicinal agents.

Grasshopper ketone 3-O-primveroside from Sinocrassula indica.

PubMed

Xie, Hai-Hui; Yoshikawa, Masayuki

2012-01-01

A new megastigmane glycoside, grasshopper ketone 3-O-primveroside (1), was isolated from the methanolic extract of the whole herbs of Sinocrassula indica (Crassulaceae). Its structure was elucidated on the basis of spectral and chemical evidence.

Asymmetric Direct 1,2-Addition of Aryl Grignard Reagents to Aryl Alkyl Ketones.

PubMed

Osakama, Kazuki; Nakajima, Makoto

2016-01-15

The enantioselective addition of Grignard reagents to ketones was promoted by a BINOL derivative bearing alkyl chains at the 3,3'-positions. This is the first asymmetric direct aryl Grignard addition to ketones reported to date. A variety of tertiary diaryl alcohols could be obtained in high yields and enantioselectivities without using any other metal source.

Palladium-catalyzed, pyrrolidine-mediated arylmethylation of ketones and aldehydes with coumarinyl(methyl) acetates†

PubMed Central

Cattopadhyay, Kalicharan; Recio, Antonio; Tunge, Jon A.

2012-01-01

We report the palladium-catalyzed, pyrrolidine-mediated α-benzylation of enamines generated from aldehydes and ketones. The method allows for direct coupling of medicinally relevant coumarin moieties with aldehydes and ketones in good yield under mild conditions. The reaction is believed to proceed via a Pd-π-benzyl complex generated from (coumarinyl)methyl acetates. PMID:22832549

Efficient Domino Hydroformylation/Benzoin Condensation: Highly Selective Synthesis of α-Hydroxy Ketones.

PubMed

Dong, Kaiwu; Sang, Rui; Soule, Jean-Francois; Bruneau, Christian; Franke, Robert; Jackstell, Ralf; Beller, Matthias

2015-12-07

An improved domino hydroformylation/benzoin condensation to give α-hydroxy ketones has been developed. Easily available olefins are smoothly converted into the corresponding α-hydroxy ketones in high yields with excellent regioselectivities. Key to success is the use of a specific catalytic system consisting of a rhodium/phosphine complex and the CO2 adduct of an N-heterocyclic carbene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dielectric properties of binary mixtures of methyl iso butyl ketone and amino silicone oil

NASA Astrophysics Data System (ADS)

Shah, K. N.; Rana, V. A.; Trivedi, C. M.; Vankar, H. P.

2017-05-01

Dielectric permittivity ɛ*(ω) = ɛ' - jɛ″ of the binary mixtures of the methyl iso butyl ketone and amino silicone oil in the frequency range 100 Hz to 2 MHz were measured using precision LCR meter at 305.15 K. Relative complex permittivity spectra in the frequency range 100 Hz to 2 MHz, of the mixture solutions of varying concentrations is reported. Determined values of the permittivity at optical frequency of all the samples are also reported. The dielectric parameters are used to gain information about the effect of concentration variation of components of the mixtures on the dielectric properties. It also provides the information about electrode polarization phenomena taking place under the low frequency A.C. electric field.

Cooperative catalysis by tertiary amino-thioureas: mechanism and basis for enantioselectivity of ketone cyanosilylation.

PubMed

Zuend, Stephan J; Jacobsen, Eric N

2007-12-26

The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary amino-thiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally.

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

PubMed

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.

Sequential aldol condensation-transition metal-catalyzed addition reactions of aldehydes, methyl ketones, and arylboronic acids.

PubMed

Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

2011-04-15

Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1'-spirobiindane-7,7'-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step. © 2011 American Chemical Society

Infant Body Composition and Adipokine Concentrations in Relation to Maternal Gestational Weight Gain

PubMed Central

Estampador, Angela C.; Pomeroy, Jeremy; Renström, Frida; Nelson, Scott M.; Mogren, Ingrid; Persson, Margareta; Sattar, Naveed; Domellöf, Magnus; Franks, Paul W.

2014-01-01

OBJECTIVE To investigate associations of maternal gestational weight gain and body composition and their impact on offspring body composition and adipocytokine, glucose, and insulin concentrations at age 4 months. RESEARCH DESIGN AND METHODS This was a prospective study including 31 mother-infant pairs (N = 62). Maternal body composition was assessed using doubly labeled water. Infant body composition was assessed at 4 months using air displacement plethysmography, and venous blood was assayed for glucose, insulin, adiponectin, interleukin-6 (IL-6), and leptin concentrations. RESULTS Rate of gestational weight gain in midpregnancy was significantly associated with infant fat mass (r = 0.41, P = 0.03); rate of gestational weight in late pregnancy was significantly associated with infant fat-free mass (r = 0.37, P = 0.04). Infant birth weight was also strongly correlated with infant fat-free mass at 4 months (r = 0.63, P = 0.0002). Maternal BMI and maternal fat mass were strongly inversely associated with infant IL-6 concentrations (r = −0.60, P = 0.002 and r = −0.52, P = 0.01, respectively). Infant fat-free mass was inversely related to infant adiponectin concentrations (r = −0.48, P = 0.008) and positively correlated with infant blood glucose adjusted for insulin concentrations (r = 0.42, P = 0.04). No significant associations for leptin were observed. CONCLUSIONS Timing of maternal weight gain differentially impacts body composition of the 4-month-old infant, which in turn appears to affect the infant’s glucose and adipokine concentrations. PMID:24623025

Raspberry Ketone Protects Rats Fed High-Fat Diets Against Nonalcoholic Steatohepatitis

PubMed Central

Wang, Lili; Zhang, Fengqing

2012-01-01

Abstract The protective effect of raspberry ketone against nonalcoholic steatohepatitis (NASH) was tested by using a high-fat diet-induced NASH model, and its mechanism was explored. Forty Sprague–Dawley rats with a 1:1 male to female ratio were randomly divided into five groups: the normal control (NC) group (n=8) fed normal diet for 8 weeks, the model control (MC) group (n=8) fed high-fat diet (82% standard diet, 8.3% yolk powder, 9.0% lard, 0.5% cholesterol, and 0.2% sodium taurocholate), and the raspberry ketone low-dose (0.5%) (RKL) group (n=8), the raspberry ketone middle-dose (1%) (RKM) group (n=8), and the raspberry ketone high-dose (2%) (RKH) group (n=8) fed high-fat diet for 4 weeks. After 8 weeks of experiment, all the rats were sacrificed, and blood lipid parameters (total cholesterol [TC], triglycerides [TG], high-density lipoprotein cholesterol [HDL-C], and low-density lipoprotein cholesterol [LDL-C]), liver function parameters (serum alanine aminotransferase [ALT], aspartate aminotransferase [AST], and alkaline phosphatase [ALP]), leptin (LEP), free fatty acid (FFA), tumor necrosis factor α (TNF-α), blood glucose (GLU), and insulin (INS) with calculated INS resistance index (IRI) and INS-sensitive index (ISI) were measured in rats. Therefore, we determined the peroxisome proliferator-activated receptor (PPAR)-α activity in liver homogenate and the levels of low-density lipoprotein receptor (LDLR), high-sensitivity C-reactive protein (hs-CRP), adiponection (APN), superoxide dismutase, and malondialdehyde (MDA). The liver tissues of rats in each group were imaged by electron microscopy with hematoxylin–eosin as the staining agent. The levels of TG, TC, LDL-C, ALT, AST, ALP, GLU, INS, IRI, FFA, LEP, TNF-α, MDA, and hs-CRP of MC rats were significantly increased (P<.05, P<.01). Therefore, the levels of HDL-C, ISI, PPAR-α, LDLR, and APN were significantly decreased (P<.05, P<.01). Compared with the MC group, each parameter in the RKL, RKM, and

Raspberry ketone protects rats fed high-fat diets against nonalcoholic steatohepatitis.

PubMed

Wang, Lili; Meng, Xianjun; Zhang, Fengqing

2012-05-01

The protective effect of raspberry ketone against nonalcoholic steatohepatitis (NASH) was tested by using a high-fat diet-induced NASH model, and its mechanism was explored. Forty Sprague-Dawley rats with a 1:1 male to female ratio were randomly divided into five groups: the normal control (NC) group (n=8) fed normal diet for 8 weeks, the model control (MC) group (n=8) fed high-fat diet (82% standard diet, 8.3% yolk powder, 9.0% lard, 0.5% cholesterol, and 0.2% sodium taurocholate), and the raspberry ketone low-dose (0.5%) (RKL) group (n=8), the raspberry ketone middle-dose (1%) (RKM) group (n=8), and the raspberry ketone high-dose (2%) (RKH) group (n=8) fed high-fat diet for 4 weeks. After 8 weeks of experiment, all the rats were sacrificed, and blood lipid parameters (total cholesterol [TC], triglycerides [TG], high-density lipoprotein cholesterol [HDL-C], and low-density lipoprotein cholesterol [LDL-C]), liver function parameters (serum alanine aminotransferase [ALT], aspartate aminotransferase [AST], and alkaline phosphatase [ALP]), leptin (LEP), free fatty acid (FFA), tumor necrosis factor α (TNF-α), blood glucose (GLU), and insulin (INS) with calculated INS resistance index (IRI) and INS-sensitive index (ISI) were measured in rats. Therefore, we determined the peroxisome proliferator-activated receptor (PPAR)-α activity in liver homogenate and the levels of low-density lipoprotein receptor (LDLR), high-sensitivity C-reactive protein (hs-CRP), adiponection (APN), superoxide dismutase, and malondialdehyde (MDA). The liver tissues of rats in each group were imaged by electron microscopy with hematoxylin-eosin as the staining agent. The levels of TG, TC, LDL-C, ALT, AST, ALP, GLU, INS, IRI, FFA, LEP, TNF-α, MDA, and hs-CRP of MC rats were significantly increased (P<.05, P<.01). Therefore, the levels of HDL-C, ISI, PPAR-α, LDLR, and APN were significantly decreased (P<.05, P<.01). Compared with the MC group, each parameter in the RKL, RKM, and RKH groups was

Blood Ketones: Measurement, Interpretation, Limitations, and Utility in the Management of Diabetic Ketoacidosis

PubMed Central

Dhatariya, Ketan

2016-01-01

Diabetic ketoacidosis (DKA) remains a common medical emergency. Over the last few years, new national guidelines have changed the focus in managing the condition from being glucose-centered to ketone-centered. With the advent of advancing technology and the increasing use of hand-held, point-of-care ketone meters, greater emphasis is placed on making treatment decisions based on these readings. Furthermore, recent warnings about euglycemic DKA occurring in people with diabetes using sodium-glucose co-transporter 2 (SGLT-2) inhibitors urge clinicians to inform their patients of this condition and possible testing options. This review describes the reasons for a change in treating DKA, and outlines the benefits and limitations of using ketone readings, in particular highlighting the difference between urine and capillary readings. PMID:28278308

Ketones in Urine: MedlinePlus Lab Test Information

MedlinePlus

... Association; c1995–2017. DKA (Ketoacidosis) & Ketones; [updated 2015 Mar 18; cited 2017 Mar 19]; [about 3 screens]. Available from: http://www. ... Testing: What You Need to Know; [cited 2017 Mar 19]; [about 3 screens]. Available from: http://www. ...

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

PubMed

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.

Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation

PubMed Central

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-01-01

Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Highly enantioselective alpha-aminoxylation of aldehydes and ketones with a polymer-supported organocatalyst.

PubMed

Font, Daniel; Bastero, Amaia; Sayalero, Sonia; Jimeno, Ciril; Pericàs, Miquel A

2007-05-10

The first catalytic enantioselective alpha-aminoxylation of aldehydes and ketones using an insoluble, polymer-supported organocatalyst (1) derived from trans-4-hydroxyproline is reported (ee: 96-99%). Reaction rates in the aminoxylation of cyclic ketones with 1 are higher than those reported with l-proline. The insoluble nature of 1 simplifies workup conditions and allows catalyst recycling without an apparent decrease in enantioselectivity or yield.

Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation.

PubMed

Binding, N; Müller, W; Witting, U

1996-10-01

Aldehydes and ketones readily react with 2,4-dinitrophenylhydrazine (2,4-DNPH) to form the corresponding hydrazones. This reaction has been frequently used for the quantification of airborne carbonyl compounds. Since unsymmetrical aldehydes and ketones are known to form isomeric 2,4-dinitrophenylhydrazones (syn/ anti-isomers), the influence of isomerization on the practicability and accuracy of the 2,4-DNPH-method using 2,4-dinitrophenylhydrazine-coated solid sorbent samplers has been studied with three ketones (methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), and methyl isobutyl ketone (MIBK)). With all three ketones the reaction with 2,4-DNPH resulted in mixtures of the isomeric hydrazones which were separated by HPLC and GC and identified by mass spectroscopy and (1)H nuclear magnetic resonance spectroscopy. The isomers show similar chromatographic behaviour in HPLC as well as in GC, thus leading to problems in quantification and interpretation of chromatographic results.

Nickel-catalyzed cycloadditions of unsaturated hydrocarbons, aldehydes, and ketones.

PubMed

Tekavec, Thomas N; Louie, Janis

2008-04-04

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon-carbon bond is formed, prior to a competitive beta-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No beta-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C-O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon-carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr).

Nickel-Catalyzed Cycloadditions of Unsaturated Hydrocarbons, Aldehydes, and Ketones

PubMed Central

Tekavec, Thomas N.

2014-01-01

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3, 3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon–carbon bond is formed, prior to a competitive β-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No β-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C–O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon–carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr). PMID:18318544

Enantioselective Reduction of Ketones and Imines Catalyzed by (CN-Box)Re(V)-Oxo Complexes

PubMed Central

Nolin, Kristine A.; Ahn, Richard W.; Kobayashi, Yusuke; Kennedy-Smith, Joshua J.

2012-01-01

The development and application of chiral, non-racemic Re(V)-oxo complexes to the enantioselective reduction of prochiral ketones is described. In addition to the enantioselective reduction of prochiral ketones, we report the application of these complexes to (1) a tandem Meyer-Schuster rearrangement/reduction to access enantioenriched allylic alcohols and (2) the enantioselective reduction of imines. PMID:20623567

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

PubMed

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.

The IGF-I system component concentrations that decrease with ageing are lower in obesity in relationship to body mass index and body fat.

PubMed

Gómez, José Manuel; Maravall, Francisco Javier; Gómez, Núria; Navarro, Miguel Angel; Casamitjana, Roser; Soler, Juan

2004-04-01

The aim of this study was to investigate the GH-IGF-I axis in healthy adults and its relationship to obesity. We studied 268 subjects: 134 men and 134 women, and determined anthropometric and body composition variables. Serum total IGF-I was measured by radioimmunoassay, serum free IGF-I concentrations by enzyme linked immunosorbant assay and serum IGFBP3 concentrations by radioimmunoassay. In men, we observed a decrease in total IGF-I, free IGF-I and IGFBP-3 throughout decades. In women, the body mass index and fat mass were higher throughout decades, and we observed a similar decrease to that in men in total IGF-I, free IGF-I and IGFBP3. In men with obesity, as measured by body fat, free IGF-I concentrations were lower than those without obesity; in women with obesity, total IGF-I concentrations and free IGF-I concentrations were lower than in those with obesity. These changes were observed in relationship to obesity when the subjects were adjusted for differences in age. We showed that in controls randomly selected, the GH-IGF-I axis component concentrations that decrease with increasing age are lower in obesity, especially in women, and that this decrease is related to body mass index and body fat.

Carbon-Carbon Bond Formation and Hydrogen Production in the Ketonization of Aldehydes.

PubMed

Orozco, Lina M; Renz, Michael; Corma, Avelino

2016-09-08

Aldehydes possess relatively high chemical energy, which is the driving force for disproportionation reactions such as Cannizzaro and Tishchenko reactions. Generally, this energy is wasted if aldehydes are transformed into carboxylic acids with a sacrificial oxidant. Here, we describe a cascade reaction in which the surplus energy of the transformation is liberated as molecular hydrogen for the oxidation of heptanal to heptanoic acid by water, and the carboxylic acid is transformed into potentially industrially relevant symmetrical ketones by ketonic decarboxylation. The cascade reaction is catalyzed by monoclinic zirconium oxide (m-ZrO2 ). The reaction mechanism has been studied through cross-coupling experiments between different aldehydes and acids, and the final symmetrical ketones are formed by a reaction pathway that involves the previously formed carboxylic acids. Isotopic studies indicate that the carboxylic acid can be formed by a hydride shift from the adsorbed aldehyde on the metal oxide surface in the absence of noble metals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequential Aldol Condensation – Transition Metal-Catalyzed Addition Reactions of Aldehydes, Methyl Ketones and Arylboronic Acids

PubMed Central

Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

2011-01-01

Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1′-spirobiindane-7,7′-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step. PMID:21417359

21 CFR 862.1435 - Ketones (nonquantitative) test system.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ketones (nonquantitative) test system. 862.1435 Section 862.1435 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test...

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

PubMed

Bredsdorff, Lea; Wedebye, Eva Bay; Nikolov, Nikolai Georgiev; Hallas-Møller, Torben; Pilegaard, Kirsten

2015-10-01

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 effects and potential effects on reproduction/development. Taking into account the high intake via supplements, the compound's toxic potential should be clarified with further experimental studies. In UK the pure compound is regarded as novel food requiring authorisation prior to marketing but raspberry ketone is not withdrawn from Internet sites from this country. Copyright © 2015 Elsevier Inc. All rights reserved.

Regulation of body metal concentrations: Toxicokinetics of cadmium and zinc in crickets.

PubMed

Bednarska, Agnieszka J; Opyd, Marta; Żurawicz, Ewelina; Laskowski, Ryszard

2015-09-01

Previous studies indicated that essential and xenobiotic metals differ substantially in terms of their toxicokinetics. Whether these differences are due to different assimilation rates, different elimination rates, or both, and whether all metals are regulated in a similar manner but with different efficiency remains unclear. To compare the mechanisms responsible for the regulation of different metals, parameters for toxicokinetic models have to be tested under exposures to the identical molar concentration of those metals. In this study, the cricket Gryllus assimilis was exposed to Zn or Cd at 2.5, 10, and 40mMkg(-1) dry food. The body concentrations of the metals were not perfectly regulated by the crickets. For Zn, a clear increase in the body concentration was found only at the highest treatment; whereas at the lowest treatment, the internal concentration remained unchanged throughout the experiment. At the lowest Zn concentration, the assimilation (kA) [day(-1)] and elimination (kE) [day(-1)] rate constants were balanced (kA=0.024, kE=0.024). When increasing the Zn exposure, kA decreased to 0.018 at 10mMkg(-1) and 0.01 at 40mMkg(-1), and kE increased to 0.05 and 0.07, respectively. Therefore, the body concentration of Zn was regulated by simultaneously changing the assimilation and elimination rate. By contrast, even at the lowest treatment, a significant increase in Cd concentration was observed in the crickets. The equilibrium Cd concentration resulted almost exclusively from increasing kE from 0.17, through 0.28 to 0.61 at 2.5, 10 and 40mMkg(-1). The kA for Cd did not reveal any clear trend. Zn was more efficiently regulated by crickets than was Cd: a 16-fold increase in exposure concentration (from 2.5 to 40mM Znkg(-1)) resulted only in a twofold increase of internal concentration, whereas the identical increase in Cd exposure concentration resulted in almost a sevenfold increase in internal concentration of this metal. Copyright © 2015 Elsevier Inc. All

Age and body composition influence TSH concentrations after administration of rhTSH.

PubMed

Holthausen, F F; von Müller, F; Happel, C; Kranert, W T; Grünwald, F

2015-01-01

Previous studies listed body surface area (BSA), lean body mass (LBM), and age as modifying factors on the TSH concentrations after administration of recombinant human thyrotropin (rhTSH). The purpose of this study was to identify the main modifying factors on serum TSH levels and to compare the stimulation via single rhTSH injection after a short thyroid hormone withdrawal (THW) with that of the standard stimulating protocol. 106 patients with differentiated thyroid cancer (DTC) undergoing radioiodine therapy (RIT) after rhTSH administration were obtained through chart review. Two groups were evaluated: Group I was treated with a single rhTSH administration after two weeks of T3 therapy followed by one week of THW. Group II was stimulated according to the international standard protocol via rhTSH injections for two consecutive days. Serum TSH concentrations were documented prior to rhTSH administration (day 1 TSH), one day after (day 3 TSH) and 3-6 days after (mean 4.2 days, day 6 TSH) the last rhTSH injection. The following data was collected: age, gender, weight, height, BMI, LBM, BSA, residual thyroid tissue, CRP, creatinine, GFR, liver enzymes, alkaline phosphatase, cholesterol, and triglycerides. Group I: Age combined with anthropometric factors like BMI (TSH increase and day 6 TSH), BSA (TSH decrease), and gender (day 6 TSH) are the main modifying factors on serum TSH concentrations after rhTSH administration. Group II: Age and lean body mass (LBM) showed a significant impact on day 3 TSH, TSH increase (day 3-day 1), and TSH decrease (day 6-day 3). Day 6 TSH was found to be influenced by GFR (group II). Age and anthropometric parameters have significant independent influence on TSH concentrations after rhTSH injection in both groups. Anthropometric parameters (BSA, LBM) and demographic parameters (female gender) show strong influence on TSH concentrations. Further research should be conducted to examine the influence of body compartments on TSH levels

ANALYSIS OF ALDEHYDES AND KETONES IN THE GAS PHASE

EPA Science Inventory

The development and testing of a 2,4-dinitrophenylhydrazine-acetonitrile (DNPH-ACN) method for the analysis of aldehydes and ketones in ambient air are described. A discussion of interferences, preparation of calibration standards, analytical testing, fluorescence methods and car...

Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

PubMed Central

Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

2015-01-01

Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

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

PubMed

de Souza, Viviane P; Oliveira, Cristiane K; de Souza, Thiago M; Menezes, Paulo H; Alves, Severino; Longo, Ricardo L; Malvestiti, Ivani

2016-11-16

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.

Ketone isosteres of 2-N-acetamidosugars as substrates for metabolic cell surface engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hang, Howard C.; Bertozzi, Carolyn R.

2000-08-22

Novel chemical reactivity can be engendered on cell surfaces by the metabolic incorporation of unnatural sugars into cell surface glycoconjuagtes. 2-N-Acetamido sugars such as GalNAc and GlcNAc are abundant components of cell surface glycoconjugates, and hence attractive targets for metabolic cell surface engineering. Here we report (1) the synthesis of isosteric analogs bearing a ketone group in place of the N-acetamido group, and (2) evaluation of their metabolic incorporation into mammalian cell surface glycans. A ketone isostere of GalNAc was metabolized by CHO cells through the salvage pathway and delivered to O-linked glycoproteins on the cell surface. Its residence atmore » the core position of O-linked glycans is suggested by studies with a-benzyl GalNAc, an inhibitor of O-linked oligosaccharide extension. A mutant CHO cell line lacking endogenous UDP-GalNAc demonstrated enhanced metabolism of the GalNAc analog, suggesting that competition with native intermediates might limits enzymatic transformation in mammalian cells. A ketone isostere of GlcNAc could not be detected on CHO or human cell surfaces after incubation. Thus, the enzymes in the GlcNAc salvage pathway might be less permissive of unnatural substrates than those comprising the GalNAc salvage pathway. Alternatively, high levels of endogenous GlcNAc derivatives might compete with the ketone isostere and prevent its incorporation into oligosaccharides.« less

Process for conversion of levulinic acid to ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dagle, Vanessa M.; Dagle, Robert A.

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.

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

PubMed

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

One-pot synthesis of β-acetamido ketones using boric acid at room temperature.

PubMed

Karimi-Jaberi, Zahed; Mohammadi, Korosh

2012-01-01

β-acetamido ketones were synthesized in excellent yields through one-pot condensation reaction of aldehydes, acetophenones, acetyl chloride, and acetonitrile in the presence of boric acid as a solid heterogeneous catalyst at room temperature. It is the first successful report of boric acid that has been used as solid acid catalyst for the preparation of β-acetamido ketones. The remarkable advantages offered by this method are green catalyst, mild reaction conditions, simple procedure, short reaction times, and good-to-excellent yields of products.

A nickel catalyst for the addition of organoboronate esters to ketones and aldehydes.

PubMed

Bouffard, Jean; Itami, Kenichiro

2009-10-01

A Ni(cod)(2)/IPr catalyst promotes the intermolecular 1,2-addition of arylboronate esters to unactivated aldehydes and ketones. Diaryl, alkyl aryl, and dialkyl ketones show good reactivity under mild reaction conditions (< or = 80 degrees C, nonpolar solvents, no strong base or acid additives). A dramatic ligand effect favors either carbonyl addition (IPr) or C-OR cross-coupling (PCy(3)) with aryl ether substrates. A Ni(0)/Ni(II) catalytic cycle initiated by the oxidative cyclization of the carbonyl substrate is proposed.

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

PubMed

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

Highly stereoselective three-component reactions of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or alpha,beta-unsaturated enals or enones.

PubMed

Huang, Xian; Xie, Meihua

2002-12-13

beta-Phenylseleno-alpha-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or alpha,beta-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of alpha,beta-unsaturated enones, functionalized allylic alcohols or functionalized gamma,delta-unsaturated ketones were obtained, depending on the structures of the ketones.

Metal-free trifluoromethylation of aromatic and heteroaromatic aldehydes and ketones.

PubMed

Qiao, Yupu; Si, Tuda; Yang, Ming-Hsiu; Altman, Ryan A

2014-08-01

The ability to convert simple and common substrates into fluoroalkyl derivatives under mild conditions remains an important goal for medicinal and agricultural chemists. One representative example of a desirable transformation involves the conversion of aromatic and heteroaromatic ketones and aldehydes into aryl and heteroaryl β,β,β-trifluoroethylarenes and -heteroarenes. The traditional approach for this net transformation involves stoichiometric metals and/or multistep reaction sequences that consume excessive time, material, and labor resources while providing low yields of products. To complement these traditional strategies, we report a one-pot metal-free decarboxylative procedure for accessing β,β,β-trifluoroethylarenes and -heteroarenes from readily available ketones and aldehydes. This method features several benefits, including ease of operation, readily available reagents, mild reaction conditions, high functional-group compatibility, and scalability.

Metal-Free Trifluoromethylation of Aromatic and Heteroaromatic Aldehydes and Ketones

PubMed Central

2015-01-01

The ability to convert simple and common substrates into fluoroalkyl derivatives under mild conditions remains an important goal for medicinal and agricultural chemists. One representative example of a desirable transformation involves the conversion of aromatic and heteroaromatic ketones and aldehydes into aryl and heteroaryl β,β,β-trifluoroethylarenes and -heteroarenes. The traditional approach for this net transformation involves stoichiometric metals and/or multistep reaction sequences that consume excessive time, material, and labor resources while providing low yields of products. To complement these traditional strategies, we report a one-pot metal-free decarboxylative procedure for accessing β,β,β-trifluoroethylarenes and -heteroarenes from readily available ketones and aldehydes. This method features several benefits, including ease of operation, readily available reagents, mild reaction conditions, high functional-group compatibility, and scalability. PMID:25001876

Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

PubMed

Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

2017-03-17

A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O 2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O 2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative impairment of hippocampal long-term potentiation involves activation of protein phosphatase 2A and is prevented by ketone bodies.

PubMed

Maalouf, Marwan; Rho, Jong M

2008-11-15

Previous studies have shown that ketone bodies (KB) exert antioxidant effects in experimental models of neurological disease. In the present study, we explored the effects of the KB acetoacetate (ACA) and beta-hydroxybutyrate (BHB) on impairment of hippocampal long-term potentiation (LTP) in rats by hydrogen peroxide (H(2)O(2)) using electrophysiological, fluorescence imaging, and enzyme assay techniques. We found that: 1) a combination of ACA and BHB (1 mM each) prevented impairment of LTP by H(2)O(2) (200 microM); 2) KB significantly lowered intracellular levels of reactive oxygen species (ROS)--measured with the fluorescent indicator carboxy-H(2)DCFDA (carboxy-2',7'-dichlorodihydrofluorescein diacetate)--in CA1 pyramidal neurons exposed to H(2)O(2); 3) the effect of KB on LTP was replicated by the protein phosphatase 2A (PP2A) inhibitor fostriecin; 4) KB prevented impairment of LTP by the PP2A activator C(6) ceramide; 5) fostriecin did not prevent the increase in ROS levels in CA1 pyramidal neurons exposed to H(2)O(2), and C(6) ceramide did not increase ROS levels; 6) PP2A activity was enhanced by both H(2)O(2) and rotenone (a mitochondrial complex I inhibitor that increases endogenous superoxide production); and 7) KB inhibited PP2A activity in protein extracts from brain tissue treated with either H(2)O(2) or ceramide. We propose that oxidative impairment of hippocampal LTP is associated with PP2A activation, and that KB prevent this impairment in part by inducing PP2A inhibition through an antioxidant mechanism.

One-Pot Synthesis of β-Acetamido Ketones Using Boric Acid at Room Temperature

PubMed Central

Karimi-Jaberi, Zahed; Mohammadi, Korosh

2012-01-01

β-acetamido ketones were synthesized in excellent yields through one-pot condensation reaction of aldehydes, acetophenones, acetyl chloride, and acetonitrile in the presence of boric acid as a solid heterogeneous catalyst at room temperature. It is the first successful report of boric acid that has been used as solid acid catalyst for the preparation of β-acetamido ketones. The remarkable advantages offered by this method are green catalyst, mild reaction conditions, simple procedure, short reaction times, and good-to-excellent yields of products. PMID:22666168

Zinc-catalyzed allenylations of aldehydes and ketones.

PubMed

Fandrick, Daniel R; Saha, Jaideep; Fandrick, Keith R; Sanyal, Sanjit; Ogikubo, Junichi; Lee, Heewon; Roschangar, Frank; Song, Jinhua J; Senanayake, Chris H

2011-10-21

The general zinc-catalyzed allenylation of aldehydes and ketones with an allenyl boronate is presented. Preliminary mechanistic studies support a kinetically controlled process wherein, after a site-selective B/Zn exchange to generate a propargyl zinc intermediate, the addition to the electrophile effectively competes with propargyl-allenyl zinc equilibration. The utility of the methodology was demonstrated by application to a rhodium-catalyzed [4+2] cycloaddition. © 2011 American Chemical Society

Introduction of an Aliphatic Ketone into Recombinant Proteins in a Bacterial Strain that Overexpresses an Editing-Impaired Leucyl-tRNA Synthetase

PubMed Central

Tang, Yi; Wang, Pin; Van Deventer, James A.; Link, A. James; Tirrell, David A.

2011-01-01

A leucine analog containing a ketone has been incorporated into proteins in E. coli. Only E. coli strains overexpressing an editing-deficient leucyl-tRNA synthetase were capable of synthesizing proteins with the aliphatic ketone amino acid. Modification of ketone-containing proteins under mild conditions has been demonstrated. PMID:19670197

OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Enantioselective synthesis of chiral oxazolines from unactivated ketones and isocyanoacetate esters by synergistic silver/organocatalysis.

PubMed

Martínez-Pardo, Pablo; Blay, Gonzalo; Muñoz, M Carmen; Pedro, José R; Sanz-Marco, Amparo; Vila, Carlos

2018-03-15

A multicatalytic approach that combines a bifunctional Brønsted base-squaramide organocatalyst and Ag + as Lewis acid has been applied in the reaction of unactivated ketones with tert-butyl isocyanoacetate to give chiral oxazolines bearing a quaternary stereocenter. The formal [3+2] cycloaddition provided high yields of the corresponding cis-oxazolines with good diastereoselectivity and excellent enantioselectivity, being applied to aryl-alkyl and alkyl-alkyl ketones.

Silica gel promotes reductions of aldehydes and ketones by N-heterocyclic carbene boranes.

PubMed

Taniguchi, Tsuyoshi; Curran, Dennis P

2012-09-07

N-Heterocyclic carbene boranes (NHC-boranes) such as 1,3-dimethylimidazol-2-ylidine trihydridoborane (diMe-Imd-BH(3)) serve as practical hydride donors for the reduction of aldehydes and ketones in the presence of silica gel. Primary and secondary alcohols are formed in good yields under ambient conditions. Aldehydes are selectively reduced in the presence of ketones. One, two, or even all three of the boron hydrides can be transferred. The process is attractive because all the components are stable and easy to handle and because both the reaction and isolation procedures are convenient.

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

PubMed

Dong, Cheng; Bai, Xing-Feng; Lv, Ji-Yuan; Cui, Yu-Ming; Cao, Jian; Zheng, Zhan-Jiang; Xu, Li-Wen

2017-05-18

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.

Selective hydrosilylation of alkynes and ketones: contrasting reactivity between cationic 3-iminophosphine palladium and nickel complexes.

PubMed

Tafazolian, Hosein; Yoxtheimer, Robert; Thakuri, Rajendr S; Schmidt, Joseph A R

2017-04-19

The catalytic hydrosilylation of alkynes and ketones has been explored utilizing palladium- and nickel(allyl) complexes supported by 3-iminophosphine ligands. Palladium and nickel demonstrated distinctly different reactivity profiles, with palladium proving very effective for the hydrosilylation of electron-deficient alkynes, while nickel excelled with ketones and internal alkynes. Additionally, in many cases, regioselective hydrosilylation was observed.

Dielectric and conformational studies of hydrogen bonded 2-ethoxyethanol and ethyl methyl ketone system

NASA Astrophysics Data System (ADS)

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.

Two-carbon homologation of aldehydes and ketones to α,β-unsaturated aldehydes.

PubMed

Petroski, Richard J; Vermillion, Karl; Cossé, Allard A

2011-06-17

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps.

A novel microreactor approach for analysis of ketones and aldehydes in breath.

PubMed

Fu, Xiao-An; Li, Mingxiao; Biswas, Souvik; Nantz, Michael H; Higashi, Richard M

2011-11-21

We report a fabricated microreactor with thousands of micropillars in channels. Each micropillar surface is chemically functionalized to selectively preconcentrate gaseous ketones and aldehydes of exhaled breath and to enhance ultra-trace, rapid analysis by direct-infusion Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry (MS). The micropillar reactive coating contains the quaternary ammonium aminooxy salt 2-(aminooxy)ethyl-N,N,N-trimethylammonium iodide (ATM) for capturing trace carbonyl VOCs by means of an oximation reaction. We demonstrate the utility of this approach for detection of C(1) to C(12) aldehydes and ketones in exhaled breath, but the approach is applicable to any gaseous sample.

π-Expanded α,β-unsaturated ketones: synthesis, optical properties, and two-photon-induced polymerization.

PubMed

Nazir, Rashid; Bourquard, Florent; Balčiūnas, Evaldas; Smoleń, Sabina; Gray, David; Tkachenko, Nikolai V; Farsari, Maria; Gryko, Daniel T

2015-02-23

A library of π-expanded α,β-unsaturated ketones was designed and synthesized. They were prepared by a combination of Wittig reaction, Sonogashira reaction, and aldol condensation. It was further demonstrated that the double aldol condensation can be performed effectively for highly polarized styrene- and diphenylacetylene-derived aldehydes. The strategic placement of two dialkylamino groups at the periphery of D-π-A-π-D molecules resulted in dyes with excellent solubility. These ketones absorb light in the region 400-550 nm. Many of them display strong solvatochromism so that the emission ranges from 530-580 nm in toluene to the near-IR region in benzonitrile. Ketones based on cyclobutanone as central moieties display very high fluorescence quantum yields in nonpolar solvents, which decrease drastically in polar media. Photophysical studies of these new functional dyes revealed that they possess an enhanced two-photon absorption cross section when compared with simpler ketone derivatives. Due to strong polarization of the resulting dyes, values of two-photon absorption cross sections on the level of 200-300 GM at 800 nm were achieved, and thanks to that as well as the presence of the keto group, these new two-photon initiators display excellent performance so that the operating region is 5-75 mW in some cases. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

N-triflylthiophosphoramide catalyzed enantioselective Mukaiyama aldol reaction of aldehydes with silyl enol ethers of ketones.

PubMed

Cheon, Cheol Hong; Yamamoto, Hisashi

2010-06-04

The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to the Brønsted acid itself depending on the reaction temperature.

Serum CETP concentration is not associated with measures of body fat: The NEO study.

PubMed

Blauw, Lisanne L; de Mutsert, Renée; Lamb, Hildo J; de Roos, Albert; Rosendaal, Frits R; Jukema, J Wouter; Wang, Yanan; van Dijk, Ko Willems; Rensen, Patrick C N

2016-03-01

Adipose tissue has been postulated to contribute substantially to the serum cholesteryl ester transfer protein (CETP) pool. However, in a recent large cohort study waist circumference was not associated with plasma CETP. The aim of the present study was to further examine associations of accurate measures of body fat and body fat distribution with serum CETP concentration. In this cross-sectional analysis of the Netherlands Epidemiology of Obesity study, we examined in 6606 participants (aged 45-65 years) the associations of total body fat, body mass index (BMI), waist circumference, waist-to-hip ratio (WHR), abdominal subcutaneous (aSAT) and visceral adipose tissue (VAT) assessed with magnetic resonance imaging (n = 2547) and total and trunk fat mass assessed with dual-energy X-ray absorptiometry (n = 909) with serum CETP concentration. Regression models were adjusted for age, ethnicity, sex, dietary intake of fat and cholesterol, physical activity, smoking and menopausal status. Mean (SD) age was 56 (6) years and BMI 26.3 (4.4) kg/m(2), 56% were women. Mean serum CETP concentration was 2.47 μg/mL. The difference in serum CETP was 0.02 μg/mL (95%CI: -0.01, 0.05) per SD total body fat (8.7%), and 0.02 μg/mL (0.00, 0.04) per SD BMI (4.4 kg/m(2)). Similar associations around the null were observed for waist circumference, WHR, aSAT, VAT, total and trunk fat mass. In this population-based study, there was no evidence for clinically relevant associations between several measures of body fat and serum CETP concentration. This finding implies that adipose tissue does not contribute to the CETP pool in serum. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

General and mild Ni(0)-catalyzed α-arylation of ketones using aryl chlorides.

PubMed

Fernández-Salas, José A; Marelli, Enrico; Cordes, David B; Slawin, Alexandra M Z; Nolan, Steven P

2015-03-02

A general methodology for the α-arylation of ketones using a nickel catalyst has been developed. The new well-defined [Ni(IPr*)(cin)Cl] (1 c) pre-catalyst showed great efficiency for this transformation, allowing the coupling of a wide range of ketones, including acetophenone derivatives, with various functionalised aryl chlorides. This cinnamyl-based Ni-N-heterocyclic carbene (NHC) complex has demonstrated a different behaviour to previously reported NHC-Ni catalysts. Preliminary mechanistic studies suggest a Ni(0)/Ni(II) catalytic cycle to be at play. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hyperketonemia and ketosis increase the risk of complications in type 1 diabetes

PubMed Central

Kanikarla-Marie, Preeti; Jain, Sushil K.

2016-01-01

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 (AA), 3-β-hydroxybutyrate (BHB), 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 increasing the risk of morbidity and mortality in patients. PMID:27036365

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

NASA Astrophysics Data System (ADS)

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).

Circulating adiponectin concentration and body composition are altered in response to high-intensity interval training.

PubMed

Shing, Cecilia M; Webb, Jessica J; Driller, Matthew W; Williams, Andrew D; Fell, James W

2013-08-01

Adiponectin influences metabolic adaptations that would prove beneficial to endurance athletes, and yet to date there is little known about the response of adiponectin concentrations to exercise, and, in particular, the response of this hormone to training in an athlete population. This study aimed to determine the response of plasma adiponectin concentrations to acute exercise after 2 different training programs and to determine the influence of the training on body composition. Seven state-level representative rowers (age: 19 ± 1.2 years [mean ± SD], height: 1.77 ± 0.10 m, body mass: 74.0 ± 10.7 kg, VO2peak 62.1 ± 7.0 ml·kg·min) participated in the double-blind, randomized crossover investigation. Rowers performed an incremental graded exercise test before and after completing 4 weeks of high-intensity interval ergometer training and 4 weeks of traditional ergometer rowing training. Rowers' body composition was assessed at baseline and after each training program. Significant increases in plasma adiponectin concentration occurred in response to maximal exercise after completion of the high-intensity interval training (p = 0.016) but not after traditional ergometer rowing training (p = 0.69). The high-intensity interval training also resulted in significant increases in mean 4-minute power output (p = 0.002) and VO2peak (p = 0.05), and a decrease in body fat percentage (p = 0.022). Mean 4-minute power output, VO2peak, and body fat percentage were not significantly different after 4 weeks of traditional ergometer rowing training (p > 0.05). Four weeks of high-intensity interval training is associated with an increase in adiponectin concentration in response to maximal exercise and a reduction in body fat percentage. The potential for changes in adiponectin concentration to reflect positive training adaptations and athlete performance level should be further explored.

Oligofluorenes as polymeric model compounds for providing insight into the triplets of ketone and ketylimine derivatives.

PubMed

Robert, Patricia; Bolduc, Andréanne; Skene, W G

2012-09-20

A series of oligofluorenes ranging between one and three repeating units were prepared as structurally well-defined representative models of polyfluorenes. The photophysics of the oligofluorene models were investigated both by laser flash photolysis and steady-state fluorescence. The effects of the ketone and ketylimine functional groups in the 9-position on the photophysical properties, notably the triplet quantum yield (Φ(TT)) by intersystem crossing and the absolute fluorescence quantum yields (Φ(fl)), were investigated. The singlet depletion method was used to determine both the Φ(TT) and molar absorption coefficients of the observed triplets (ε(TT)). Meanwhile, the absolute Φ(fl) were determined using an integrating sphere. It was found that both the ketone and ketylimine substituents and the degree of oligomerization contributed to quenching the oligofluorene fluorescence. For example, the Φ(fl) was quenched 5-fold with the ketylimine and ketone substituents for the bifluorenyl derivatives compared to their corresponding 9,9-dihexyl bifluorenyl counterparts. Meanwhile, the Φ(fl) quenching increased 14 times with the trifluorenyl ketone and ketylimine derivatives. Measured Φ(TT) values ranged between 22 and 43% for the difluorenyl derivatives with ε(TT) on the order of 13 000 cm(-1) M(-1). The Φ(TT) decreased to <10% concomitant with doubling of the ε(TT) when the degree of oligomerization was increased to 3. A new fluorescence emission at 545 nm formed at low temperatures for the ketone and ketylimine oligofluorene derivatives. The emission intensity was dependent on the temperature, and it disappeared at room temperature.

Facile Rearrangement of 3-Oxoalkyl Radicals is Evident in Low-Temperature Gas-Phase Oxidation of Ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheer, Adam M.; Welz, Oliver; Sasaki, Darryl Y.

The pulsed photolytic chlorine-initiated oxidation of methyl-tert-butyl ketone (MTbuK), di-tert-butyl ketone (DTbuK), and a series of partially deuterated diethyl ketones (DEK) is studied in the gas phase at 8 Torr and 550–650 K. Products are monitored as a function of reaction time, mass, and photoionization energy using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. The results establish that the primary 3-oxoalkyl radicals of those ketones, formed by abstraction of a hydrogen atom from the carbon atom in γ-position relative to the carbonyl oxygen, undergo a rapid rearrangement resulting in an effective 1,2-acyl group migration, similar to that inmore » a Dowd–Beckwith ring expansion. Without this rearrangement, peroxy radicals derived from MTbuK and DTbuK cannot undergo HO2 elimination to yield a closed-shell unsaturated hydrocarbon coproduct. However, not only are these coproducts observed, but they represent the dominant oxidation channels of these ketones under the conditions of this study. For MTbuK and DTbuK, the rearrangement yields a more stable tertiary radical, which provides the thermodynamic driving force for this reaction. Even in the absence of such a driving force in the oxidation of partially deuterated DEK, the 1,2-acyl group migration is observed. Quantum chemical (CBS-QB3) calculations show the barrier for gas-phase rearrangement to be on the order of 10 kcal mol–1. The MTbuK oxidation experiments also show several minor channels, including β-scission of the initial radicals and cyclic ether formation.« less

Caffeine intake increases plasma ketones: an acute metabolic study in humans.

PubMed

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

2017-04-01

Brain glucose uptake declines during aging and is significantly impaired in Alzheimer's disease. Ketones are the main alternative brain fuel to glucose so they represent a potential approach to compensate for the brain glucose reduction. Caffeine is of interest as a potential ketogenic agent owing to its actions on lipolysis and lipid oxidation but whether it is ketogenic in humans is unknown. This study aimed to evaluate the acute ketogenic effect of 2 doses of caffeine (2.5; 5.0 mg/kg) in 10 healthy adults. Caffeine given at breakfast significantly stimulated ketone production in a dose-dependent manner (+88%; +116%) and also raised plasma free fatty acids. Whether caffeine has long-term ketogenic effects or could enhance the ketogenic effect of medium chain triglycerides remains to be determined.

Catecholamine, Corticosteroid and Ketone Excretion in Exercise and Hypoxia,

DTIC Science & Technology

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)

Two-Carbon Homologation of Ketones to 3-Methyl Unsaturated Aldehydes

USDA-ARS?s Scientific Manuscript database

The usual scheme of two-carbon homologation of ketones to 3-methyl unsaturated aldehydes by Horner-Wadsworth-Emmons condensations with phosphonate esters, such as triethyl-2-phosphonoacetate, involves three steps. The phosphonate condensation step results in extension of the carbon chain by two carb...

An Unconventional Redox Cross Claisen Condensation-Aromatization of 4-Hydroxyprolines with Ketones.

PubMed

Tang, Mi; Sun, Rengwei; Li, Hao; Yu, Xinhong; Wang, Wei

2017-08-18

Reaction of α-amino acids, particularly prolines and their derivatives with carbonyl compounds via decarboxylative redox process, is a viable strategy for synthesis of structurally diverse nitrogen centered heterocyclics. In these processes, the decarboxylation is the essential driving force for the processes. The realization of the redox process without decarboxylation may offer an opportunity to explore new reactions. Herein, we report the discovery of an unprecedented redox Claisen-type condensation aromatization cascade reaction of 4-substituted 4-hydroxyproline and its esters with unreactive ketones. We found that the use of propionic acid as a catalyst and a co-solvent can change the reaction course. The commonly observed redox decarboxylation and aldol condensation reactions are significantly minimized. Moreover, unreactive ketones can effectively participate in the Claisen condensation reaction. The new reactivity enables a redox cyclization via an unconventional Claisen-type condensation reaction of in situ formed enamine intermediates from ketone precursors with 4-substituted 4-hydroxyproline and its esters as electrophilic acylation partners. Under the reaction conditions, the cascade process proceeds highly regio- and stereoselectively to afford highly synthetically and biologically valued cis-2,3-dihydro-1H-pyrrolizin-1-ones with a broad substrate scope in efficient 'one-pot' operation, whereas such structures generally require multiple steps.

Preparation of unsymmetrical ketones from tosylhydrazones and aromatic aldehydes via formyl C-H bond insertion.

PubMed

Allwood, Daniel M; Blakemore, David C; Ley, Steven V

2014-06-06

Preparation of ketones by insertion of diazo compounds into the formyl C-H bond of an aldehyde is an attractive procedure, but use of structurally diverse diazo compounds is hampered by preparation and safety issues. A convenient procedure for the synthesis of unsymmetrical ketones from bench-stable tosylhydrazones and aryl aldehydes is reported. The procedure can be performed in one pot from the parent carbonyl compound and needs only a base, with no additional promoters being required.

N-Triflylthiophosphoramide Catalyzed Enantioselective Mukaiyama Aldol Reaction of Aldehydes with Silyl Enol Ethers of Ketones

PubMed Central

Cheon, Cheol Hong; Yamamoto, Hisashi

2010-01-01

The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to Brønsted acid itself depending on the reaction temperature. PMID:20465277

A modified Girard derivatizing reagent for universal profiling and trace analysis of aldehydes and ketones by electrospray ionization tandem mass spectrometry.

PubMed

Johnson, David W

2007-01-01

4-Hydrazino-N,N,N-trimethyl-4-oxobutanaminium iodide (HTMOB) is a modified Girard derivatizing reagent synthesized to improve the sensitivity of analysis of aldehydes and ketones with electrospray ionization tandem mass spectrometry. Compared with Girard T reagent the measured signal intensity increase is between 3.3 times (succinylacetone) and 7.0 times (17-hydroxyprogesterone). HTMOB is a universal profiling reagent for aldehydes and ketones. A neutral loss of 59 Da scan detects all aldehydes and ketones from acetone to corticosteroids. Applications described include the profiling of ketones, ketoacids and ketodiacids in the urine of children with ketosis and the profiling of long-chain aldehydes incorporated in plasma plasmalogens. Copyright (c) 2007 John Wiley & Sons, Ltd.

Body concentration of caesium-137 in patients from Western Isles of Scotland.

PubMed Central

Isles, C G; Robertson, I; Macleod, J A; Preston, T; East, B W; Hole, D J; Lever, A F

1991-01-01

OBJECTIVES--To compare caesium-137 concentrations in patients from the Western Isles Health Board, Glasgow area, and other parts of the Scottish mainland, and to investigate the source of 137Cs in patients from the Western Isles. DESIGN--Study of hypertensive patients having electrolyte concentrations measured, including 137Cs. Interview by questionnaire of island subjects about intake of foods likely to contain radiocaesium and the source of these foods. Measurement of 137Cs and 134Cs in food, urine, and vegetation. SETTING--Scottish mainland and Western Isles, 1979-86. All measurements before Chernobyl nuclear accident. PATIENTS--413 consecutive patients referred to the blood pressure unit for investigation of hypertension. 60 from the Western Isles, including 44 from North Uist; 32 from North Uist participated in the dietary analysis. MAIN OUTCOME MEASURES--Concentration of radiocaesium in the body, urine, food, and vegetation. Islanders' consumption of local produce. RESULTS--Patients from the Western Isles had five times higher body concentrations of 137Cs (median 2.54 (interquartile range 1.25-3.73)) Bq/gK) than did patients from around Glasgow (0.47 (0.26-0.66) Bq/gK) and other parts of the Scottish mainland (0.42 (0.24-0.71) Bq/gK). Islanders often consumed local milk and mutton, but ate local fish rarely. 137Cs and 134Cs were present in coastal (21.6 Bq/kg 137Cs, 0.25 Bq/kg 134Cs) and moorland (135.9, 0.65 Bq/kg) grasses and in islanders' urine (2.01, 0.013 Bq/l). Lower concentrations (0.336, 0.004 Bq/l), were found in the urine of Glasgow controls (p less than 0.001 for both isotopes). CONCLUSIONS--Islanders have excess body 137Cs concentrations, most of which probably comes from local milk and lamb. The radioactivity is not above the recommended safety limit. The presence of 134Cs suggests that nuclear reprocessing is the source of some of the radiocaesium. PMID:1906765

Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations.

PubMed

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.

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

PubMed

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.

Stability of proton-bound clusters of alkyl alcohols, aldehydes and ketones in Ion Mobility Spectrometry.

PubMed

Jurado-Campos, Natividad; Garrido-Delgado, Rocío; Martínez-Haya, Bruno; Eiceman, Gary A; Arce, Lourdes

2018-08-01

Significant substances in emerging applications of ion mobility spectrometry such as breath analysis for clinical diagnostics and headspace analysis for food purity include low molar mass alcohols, ketones, aldehydes and esters which produce mobility spectra containing protonated monomers and proton-bound dimers. Spectra for all n- alcohols, aldehydes and ketones from carbon number three to eight exhibited protonated monomers and proton-bound dimers with ion drift times of 6.5-13.3 ms at ambient pressure and from 35° to 80 °C in nitrogen. Only n-alcohols from 1-pentanol to 1-octanol produced proton-bound trimers which were sufficiently stable to be observed at these temperatures and drift times of 12.8-16.3 ms. Polar functional groups were protected in compact structures in ab initio models for proton-bound dimers of alcohols, ketones and aldehydes. Only alcohols formed a V-shaped arrangement for proton-bound trimers strengthening ion stability and lifetime. In contrast, models for proton-bound trimers of aldehydes and ketones showed association of the third neutral through weak, non-specific, long-range interactions consistent with ion dissociation in the ion mobility drift tube before arriving at the detector. Collision cross sections derived from reduced mobility coefficients in nitrogen gas atmosphere support the predicted ion structures and approximate degrees of hydration. Copyright © 2018 Elsevier B.V. All rights reserved.

Serum, tissue and body fluid concentrations of tigecycline after a single 100 mg dose.

PubMed

Rodvold, Keith A; Gotfried, Mark H; Cwik, Michael; Korth-Bradley, Joan M; Dukart, Gary; Ellis-Grosse, Evelyn J

2006-12-01

The purpose of this study was to determine the tissue and corresponding serum concentration of tigecycline at selected time points in gall bladder, bile, colon, bone, synovial fluid (SF), lung and CSF in subjects undergoing surgical or medical procedures. One hundred and four adult subjects (aged 24-83 years; 64 women, 40 men) received a single intravenous (i.v.) dose of tigecycline (100 mg infused over 30 min). Subjects were randomly assigned to one of four collection times at 4, 8, 12 and 24 h after the start of the infusion. For CSF, samples were collected at approximately 1.5 and 24 h after the start of the infusion. All subjects had serum samples collected before the administration of tigecycline, at the end of the infusion and at the time corresponding to tissue or body fluid collection. Drug concentrations in serum, tissues and body fluids were determined by LC/MS/MS. The area under the mean concentration-time curve from 0 to 24 h (AUC(0-24)) was determined for the comparison of systemic exposure between tissue or body fluid to serum. The mean serum concentrations of tigecycline were similar to those previously published. Tissue penetration, expressed as the ratio of AUC(0-24) in tissue or body fluid to serum, was 537 for bile, 23 for gall bladder, 2.6 for colon, 2.0 for lung, 0.41 for bone, 0.31 for SF and 0.11 for CSF. A single 100 mg dose of intravenous tigecycline produced considerably higher tissue/fluid concentrations in bile, gall bladder, colon and lung compared with simultaneous serum concentrations. On average, the systemic exposure of tigecycline in bone, SF and CSF ranged from 11% to 41% of serum concentrations. The results in bone are inconsistent with previous radiolabelled studies in animals and it is unclear if tight binding to bone (versus low bone uptake) or poor extraction of tigecycline for LC/MS/MS detection or both may have contributed to the differences we observed in humans.

Integrated quantification and identification of aldehydes and ketones in biological samples.

PubMed

Siegel, David; Meinema, Anne C; Permentier, Hjalmar; Hopfgartner, Gérard; Bischoff, Rainer

2014-05-20

The identification of unknown compounds remains to be a bottleneck of mass spectrometry (MS)-based metabolomics screening experiments. Here, we present a novel approach which facilitates the identification and quantification of analytes containing aldehyde and ketone groups in biological samples by adding chemical information to MS data. Our strategy is based on rapid autosampler-in-needle-derivatization with p-toluenesulfonylhydrazine (TSH). The resulting TSH-hydrazones are separated by ultrahigh-performance liquid chromatography (UHPLC) and detected by electrospray ionization-quadrupole-time-of-flight (ESI-QqTOF) mass spectrometry using a SWATH (Sequential Window Acquisition of all Theoretical Fragment-Ion Spectra) data-independent high-resolution mass spectrometry (HR-MS) approach. Derivatization makes small, poorly ionizable or retained analytes amenable to reversed phase chromatography and electrospray ionization in both polarities. Negatively charged TSH-hydrazone ions furthermore show a simple and predictable fragmentation pattern upon collision induced dissociation, which enables the chemo-selective screening for unknown aldehydes and ketones via a signature fragment ion (m/z 155.0172). By means of SWATH, targeted and nontargeted application scenarios of the suggested derivatization route are enabled in the frame of a single UHPLC-ESI-QqTOF-HR-MS workflow. The method's ability to simultaneously quantify and identify molecules containing aldehyde and ketone groups is demonstrated using 61 target analytes from various compound classes and a (13)C labeled yeast matrix. The identification of unknowns in biological samples is detailed using the example of indole-3-acetaldehyde.

Pyrrolidine-mediated direct preparation of (e)-monoarylidene derivatives of homo- and heterocyclic ketones with various aldehydes.

PubMed

Gu, Xin; Wang, Xiaoyan; Wang, Fengtian; Sun, Hongbao; Liu, Jie; Xie, Yongmei; Xiang, Mingli

2014-02-12

An efficient method for the facile synthesis of (E)-monoarylidene derivatives of homo- and heterocyclic ketones with various aldehydes in the presence of a pyrrolidine organocatalyst has been achieved. A range of α,β-unsaturated ketones were obtained in moderate to high yields (up to 99%). Unlike the Claisen-Schmidt condensation process, the formation of undesired bisarylidene byproducts is not observed. The possible reaction mechanism suggests that the reaction proceeds via a Mannich-elimination sequence.

Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ide, Matthew S.; Hao, Bing; Neurock, Matthew

The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Althoughmore » Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.« less

Trifluoromethylation of ketones and aldehydes with Bu₃SnCF₃.

PubMed

Sanhueza, Italo A; Bonney, Karl J; Nielsen, Mads C; Schoenebeck, Franziska

2013-08-02

The (trifluoromethyl)stannane reagent, Bu3SnCF3, was found to react under CsF activation with ketones and aldehydes to the corresponding trifluoromethylated stannane ether intermediates at room temperature in high yield. Only a mildly acidic extraction (aqueous NH4Cl) is required to release the corresponding trifluoromethyl alcohol products. The protocol is compatible with acid-sensitive functional groups.

Persistence assessment of cyclohexyl- and norbornyl-derived ketones and their degradation products in different OECD screening tests.

PubMed

Seyfried, M; van Ginkel, C G; Boschung, A; Miffon, F; Fantini, P; Tissot, E; Baroux, L; Merle, P; Chaintreau, A

2015-07-01

The persistence of synthetic cyclohexyl- and norbornyl-derived ketones was assessed by using OECD 301F and 301D biodegradation tests. While cyclohexyl-derived ketones either reached or came close to the pass level (60%) after 60 d, the corresponding norbornyl derivatives yielded significantly less biodegradation (<40%). By analyzing extracts at 60 d, the key degradation products of four norbornyl derivatives were identified. Consistently, 2-bicyclo[2.2.1]heptane carboxylic acid was found as a principal degradation product with minor quantities of bicyclo[2.2.1]heptan-2-one and 2-bicyclo[2.2.1]heptane acetic acid. When the three degradation products were re-synthesized and tested individually for biodegradability, the former two were found to be ultimately biodegradable after 60 d in OECD 301D tests, thus proving non-persistence. Similarly, 2-bicyclo[2.2.1]heptane acetic acid was found to be degraded significantly, albeit with long lag phases exceeding 60 d in the case of freshwater inoculum, then ultimately reaching the pass level. On the other hand, norbornyl ketones were still only partially biodegradable in the same test. We conclude that despite the potential for ultimate biodegradation of norbornyl-derived ketones, current screening tests yield an incomplete picture of their biodegradability, particularly when applying strict OECD criteria. The appearance of long lag phases when re-testing norbornyl ketone degradation products underlines the importance of extending tests to well beyond 28 and even 60 d in the case of freshwater inocula. Copyright © 2015 Elsevier Ltd. All rights reserved.

Organocatalytic Enantioselective Protonation for Photoreduction of Activated Ketones and Ketimines Induced by Visible Light.

PubMed

Lin, Lu; Bai, Xiangbin; Ye, Xinyi; Zhao, Xiaowei; Tan, Choon-Hong; Jiang, Zhiyong

2017-10-23

The first catalytic asymmetric photoreduction of 1,2-diketones and α-keto ketimines under visible light irradiation is reported. A transition-metal-free synergistic catalysis platform harnessing dicyanopyrazine-derived chromophore (DPZ) as the photoredox catalyst and a non-covalent chiral organocatalyst is effective for these transformations. With the flexible use of a chiral Brønsted acid or base in H + transfer interchange to control the elusive enantioselective protonation, a variety of chiral α-hydroxy ketones and α-amino ketones were obtained with high yields and enantioselectivities. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bicyclic tetrapeptide histone deacetylase inhibitors with methoxymethyl ketone and boronic acid zinc-binding groups.

PubMed

Islam, Md Nurul; Islam, Md Shahidul; Hoque, Md Ashraful; Kato, Tamaki; Nishino, Norikazu; Ito, Akihiro; Yoshida, Minoru

2014-12-01

Histone deacetylase (HDAC) inhibitors are a class of potential therapeutics for the treatment of cancer. Bicyclic tetrapeptides equipped with methoxymethyl ketone and boronic acid as zinc-binding group were designed and synthesized. The inhibitory activities of these compounds were evaluated against HDAC enzymes. The cell-free and cell-based assay data showed that both potency and selectivity changed with the change in zinc-binding group. Boronic acid-based compound showed poor activity whereas methoxymethyl ketone-based compound displayed impressive activity in both cell-free and cell-based conditions. Copyright © 2014 Elsevier Inc. All rights reserved.

Methamphetamine and amphetamine concentrations in survivors of body-packer syndrome in Japan.

PubMed

Uekusa, Kyoko; Hayashida, Makiko; Saito, Nobuyuki; Mashiko, Kunihiro; Hara, Kenji; Waters, Brian; Ohno, Youkichi

2013-04-10

There are few reports from Japan on the analysis of fluids in survivors of body-packer syndrome. We analyzed the concentrations of stimulants in the serum, plasma and urine collected from three patients suspected of being body packers at immigration that were referred to hospitals between 2010 and 2011. The drugs were extracted with solid-phase columns and analyzed by gas chromatography-mass spectrometry (GC-MS). In all cases, wrapped, cylindrical packets of foreign bodies were detected in the intestinal tract on plain X-ray (X-P) and computed tomography (CT), and they were eventually removed surgically. In case 1, the patient presented with convulsions and tachycardia at admission to the hospital and one of the packets was found to have ruptured. In case 2, although the subject appeared to have an intestinal obstruction caused by the packets on the third day, he exhibited no symptoms on arrival and the packets did not appear to have ruptured. In case 3, the patient exhibited restlessness on the first day and one of the removed packets had ruptured. In all cases, methamphetamine (MA) and amphetamine (AP) were detected in serum, plasma and urine. In this study, we report the variation in MA and AP concentrations in survivors of body-packer syndrome. The serum and plasma concentrations of MA were high in subjects that exhibited symptoms of MA intoxication. MA and AP were also detected in the case in which the patient exhibited no symptoms of intoxication and the packets had not ruptured. These results suggest either that the stimulants may have seeped through the wrap of the packets, or that the subject had been abusing the drugs. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Thermotolerant cyclamen with reduced acrolein and methyl vinyl ketone

PubMed Central

Kai, Hiroomi; Hirashima, Keita; Matsuda, Osamu; Ikegami, Hidetoshi; Winkelmann, Traud; Nakahara, Takao; Iba, Koh

2012-01-01

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. PMID:22511805

Benzoyl radicals from (hetero)aromatic aldehydes. Decatungstate photocatalyzed synthesis of substituted aromatic ketones.

PubMed

Ravelli, Davide; Zema, Michele; Mella, Mariella; Fagnoni, Maurizio; Albini, Angelo

2010-09-21

Benzoyl radicals are generated directly from (hetero)aromatic aldehydes upon tetrabutylammonium decatungstate ((n-Bu(4)N)(4)W(10)O(32)), TBADT) photocatalysis under mild conditions. In the presence of alpha,beta-unsaturated esters, ketones and nitriles radical conjugate addition ensues and gives the corresponding beta-functionalized aryl alkyl ketones in moderate to good yields (stereoselectively in the case of 3-methylene-2-norbornanone). Due to the mild reaction conditions the presence of various functional groups on the aromatic ring is tolerated (e.g. methyl, methoxy, chloro). The method can be applied to hetero-aromatic aldehydes whether electron-rich (e.g. thiophene-2-carbaldehyde) or electron-poor (e.g. pyridine-3-carbaldehyde).

Ketonization of Cuphea oil for the production of 2-undecanone

USDA-ARS?s Scientific Manuscript database

The objective of this work was to demonstrate the viability of the cross ketonization reaction with the triacylglycerol from Cuphea sp. and acetic acid in a fixed-bed plug-flow reactor. The seed oil from Cuphea sp. contains up to 71% decanoic acid and the reaction of this fatty acid residue with ac...

Formation of intermediate products during the resonance stepwise polarization of dibenzyl ketone and benzil molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polevoi, A.V.; Matyuk, V.M.; Grigor'eva, G.A.

1987-07-01

The processes resulting in the intramolecular redistribution of energy in electronically excited S/sub ..pi pi..*/ states of dibenzyl ketone and benzil molecules have been investigated by laser mass spectrometry. The decisive role of dissociation under the conditions of the resonance stepwise photoionization of these molecules upon excitation by radiation with lambda = 266 nm has been demonstrated. The ionization potentials of the molecules and the appearance potentials of fragment ions from dibenzyl ketone and benzil have been determined on the basis of an analysis of photoionization efficiency curves.

n-BuLi as a highly efficient precatalyst for hydrophosphonylation of aldehydes and unactivated ketones.

PubMed

Liu, Chengwei; Zhang, Yu; Qian, Qinqin; Yuan, Dan; Yao, Yingming

2014-12-05

It was found for the first time that organic alkali metal compounds serve as highly efficient precatalysts for the hydrophosphonylation reactions of aldehydes and unactivated ketones with dialkyl phosphite under mild conditions. For ketone substrates, a reversible reaction was observed, and the influence of catalyst loading and reaction temperature on the reaction equilibrium was studied in detail. Overall, the hydrophosphonylation reactions catalyzed by 0.1 mol % n-BuLi were completed within 5 min for a broad range of substrates and generated a series of α-hydroxy phosphonates in high yields.

Analysis of carbonaceous biomarkers with the Mars Organic Analyzer microchip capillary electrophoresis system: aldehydes and ketones.

PubMed

Stockton, Amanda M; Tjin, Caroline Chandra; Huang, Grace L; Benhabib, Merwan; Chiesl, Thomas N; Mathies, Richard A

2010-11-01

A microchip CE method is developed for the analysis of two oxidized forms of carbon, aldehydes and ketones, with the Mars Organic Analyzer (MOA). Fluorescent derivitization is achieved in ∼ 15 min by hydrazone formation with Cascade Blue hydrazide in 30 mM borate pH 5-6. The microchip CE separation and analysis method is optimized via separation in 30 mM borate buffer, pH 9.5, at 20°C. A carbonyl standard consisting of ten aldehydes and ketones found in extraterrestrial matter is successfully separated; the resulting LOD depends on the reactivity of the compound and range from 70 pM for formaldehyde to 2 μM for benzophenone. To explore the utility of this method for analyzing complex samples, analyses of several fermented beverages are conducted, identifying ten aldehydes and ketones ranging from 30 nM to 5 mM. A Martian regolith simulant sample, consisting of a basalt matrix spiked with soluble ions and acetone, is designed and analyzed, but acetone is found to have a limited detectable lifetime under simulant Martian conditions. This work establishes the capability of the MOA for studying aldehydes and ketones, a critical class of oxidized organic molecules of interest in planetary and in terrestrial environmental and health studies. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Whole-Body Insulin Sensitivity Rather than Body-Mass-Index Determines Fasting and Post-Glucose-Load Growth Hormone Concentrations

PubMed Central

Anderwald, Christian-Heinz; Tura, Andrea; Gessl, Alois; Smajis, Sabina; Bieglmayer, Christian; Marculescu, Rodrig; Luger, Anton; Pacini, Giovanni; Krebs, Michael

2014-01-01

Background Obese, non-acromegalic persons show lower growth hormone (GH) concentrations at fasting and reduced GH nadir during an oral glucose tolerance test (OGTT). However, this finding has never been studied with regard to whole-body insulin-sensitivity as a possible regulator. Methods In this retrospective analysis, non-acromegalic (NonACRO, n = 161) and acromegalic (ACRO, n = 35), non-diabetic subjects were subdivided into insulin-sensitive (IS) and –resistant (IR) groups according to the Clamp-like Index (CLIX)-threshold of 5 mg·kg−1·min−1 from the OGTT. Results Non-acromegalic IS (CLIX: 8.8±0.4 mg·kg−1·min−1) persons with similar age and sex distribution, but lower (p<0.001) body-mass-index (BMI = 25±0 kg/m2, 84% females, 56±1 years) had 59% and 70%, respectively, higher (p<0.03) fasting GH and OGTT GH area under the curve concentrations than IR (CLIX: 3.5±0.1 mg·kg−1·min−1, p<0.001) subjects (BMI = 29±1 kg/m2, 73% females, 58±1 years). When comparing on average overweight non-acromegalic IS and IR with similar anthropometry (IS: BMI: 27±0 kg/m2, 82% females, 58±2 years; IR: BMI: 27±0 kg/m2, 71% females, 60±1 years), but different CLIX (IS: 8.7±0.9 vs. IR: 3.8±0.1 mg·kg−1·min−1, p<0.001), the results remained almost the same. In addition, when adjusted for OGTT-mediated glucose rise, GH fall was less pronounced in IR. In contrast, in acromegalic subjects, no difference was found between IS and IR patients with regard to fasting and post-glucose-load GH concentrations. Conclusions Circulating GH concentrations at fasting and during the OGTT are lower in non-acromegalic insulin-resistant subjects. This study seems the first to demonstrate that insulin sensitivity rather than body-mass modulates fasting and post-glucose-load GH concentrations in non-diabetic non–acromegalic subjects. PMID:25517727

Synthesis of Trifluoromethylthiolated Alkenes and Ketones by Decarboxylative Functionalization of Cinnamic Acids.

PubMed

Pan, Shen; Huang, Yangen; Qing, Feng-Ling

2016-10-20

A tunable decarboxylative trifluoromethylthiolation of cinnamic acids with AgSCF 3 was developed to afford trifluoromethylthiolated alkenes or ketones by using transition metal-mediated conditions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Association between Serum Albumin Concentration and Ketosis Risk in Hospitalized Individuals with Type 2 Diabetes Mellitus.

PubMed

Cheng, Po-Chung; Hsu, Shang-Ren; Cheng, Yun-Chung

2016-01-01

Objective. This study examined the association between serum albumin concentration and ketosis risk in hospitalized individuals with type 2 diabetes mellitus (T2DM). Methods. A retrospective cross-sectional study was conducted at a medical center in Taiwan. Inclusion criteria were endocrinology ward inpatients exceeding 21 years of age, with preexisting diagnosis of T2DM, and blood glucose above 13.9 millimoles per liter (mmol/L) at admission. Individuals without measurement of serum albumin, urine ketone, or hemoglobin A1C, or harboring active infection, myocardial infarction, cerebrovascular event, cirrhosis, malignancy, or overt proteinuria were excluded. Using serum albumin concentration below 3.0 grams per deciliter to define hypoalbuminemia, 151 hypoalbuminemic cases and 104 normoalbuminemic controls were enrolled. The presence of ketones in urine established ketosis. Results. The prevalence of ketonuria was 48% in hypoalbuminemic subjects compared to 30% in normoalbuminemic controls (odds ratio (OR): 2.15; 95% confidence interval (CI): 1.26-3.57; P = 0.004). Moreover, among the 156 subjects with serum beta-hydroxybutyrate measurement in addition to urine ketone, 33% of the hypoalbuminemic individuals had ketonemia exceeding 3 mmol/L compared to 19% of those with normoalbuminemia (OR: 2.12, 95% CI: 0.99-4.48, P = 0.051). Conclusions. Serum albumin concentration is inversely associated with ketosis risk in hospitalized individuals with T2DM.

Association between Serum Albumin Concentration and Ketosis Risk in Hospitalized Individuals with Type 2 Diabetes Mellitus

PubMed Central

2016-01-01

Objective. This study examined the association between serum albumin concentration and ketosis risk in hospitalized individuals with type 2 diabetes mellitus (T2DM). Methods. A retrospective cross-sectional study was conducted at a medical center in Taiwan. Inclusion criteria were endocrinology ward inpatients exceeding 21 years of age, with preexisting diagnosis of T2DM, and blood glucose above 13.9 millimoles per liter (mmol/L) at admission. Individuals without measurement of serum albumin, urine ketone, or hemoglobin A1C, or harboring active infection, myocardial infarction, cerebrovascular event, cirrhosis, malignancy, or overt proteinuria were excluded. Using serum albumin concentration below 3.0 grams per deciliter to define hypoalbuminemia, 151 hypoalbuminemic cases and 104 normoalbuminemic controls were enrolled. The presence of ketones in urine established ketosis. Results. The prevalence of ketonuria was 48% in hypoalbuminemic subjects compared to 30% in normoalbuminemic controls (odds ratio (OR): 2.15; 95% confidence interval (CI): 1.26–3.57; P = 0.004). Moreover, among the 156 subjects with serum beta-hydroxybutyrate measurement in addition to urine ketone, 33% of the hypoalbuminemic individuals had ketonemia exceeding 3 mmol/L compared to 19% of those with normoalbuminemia (OR: 2.12, 95% CI: 0.99–4.48, P = 0.051). Conclusions. Serum albumin concentration is inversely associated with ketosis risk in hospitalized individuals with T2DM. PMID:27504458

Alcohol, Aldehyde, and Ketone Liberation and Intracellular Cargo Release through Peroxide-Mediated α-Boryl Ether Fragmentation.

PubMed

Hanna, Ramsey D; Naro, Yuta; Deiters, Alexander; Floreancig, Paul E

2016-10-12

α-Boryl ethers, carbonates, and acetals, readily prepared from the corresponding alcohols that are accessed through ketone diboration, react rapidly with hydrogen peroxide to release alcohols, aldehydes, and ketones through the collapse of hemiacetal intermediates. Experiments with α-boryl acetals containing a latent fluorophore clearly demonstrate that cargo can be released inside cells in the presence of exogenous or endogenous hydrogen peroxide. These experiments show that this protocol can be used for drug activation in an oxidative environment without generating toxic byproducts.

Activation of Acetone and Other Simple Ketones in Anaerobic Bacteria.

PubMed

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.

Diplogelasinospora grovesii IMI 171018 immobilized in polyurethane foam. An efficient biocatalyst for stereoselective reduction of ketones.

PubMed

Quezada, M A; Carballeira, J D; Sinisterra, J V

2012-05-01

Diplogelasinospora grovesii has been reported as a very active biocatalyst in the reduction of ketones. Along the text, the properties of this filamentous fungus as an immobilized catalyst are described. For this purpose, several immobilization supports as agar and polyurethane foam were tested. Experimental assays were also performed to test different co-substrates for the regeneration of the required enzyme cofactor. The fungus immobilized in polyurethane foam lead to the most stable and active catalyst. This derivative, using i-PrOH as co-substrate, could be reused at least 18 times without appreciable activity loss (>90% activity remains). Kinetic runs experiments shown that the reduction of cyclohexanone, selected as model substrate, followed a pseudo-first kinetic order and that the rate controlling step was the mass transfer through the cell wall. The deactivation kinetic constants were also determined. The reduction of different chiral ketones showed that the ketone reductase activity followed the Prelog's rule. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effect of hydrothermal carbonization on storage process of woody pellets: Pellets' properties and aldehydes/ketones emission.

PubMed

Li, Hui; Wang, Siyuan; Huang, Zhongliang; Yuan, Xingzhong; Wang, Ziliang; He, Rao; Xi, Yanni; Zhang, Xuan; Tan, Mengjiao; Huang, Jing; Mo, Dan; Li, Changzhu

2018-07-01

Effect of hydrothermal carbonization (HTC) on the hydrochar pelletization and the aldehydes/ketones emission from pellets during storage was investigated. Pellets made from the hydrochar were stored in sealed apparatuses for sampling. The energy consumption during pelletization and the pellets' properties before/after storage, including dimension, density, moisture content, hardness, aldehyde/ketones emission amount/rate and unsaturated fatty acid amount, were analyzed. Compared with untreated-sawdust-pellets, the hydrochar-pellets required more energy consumption for pelletization, and achieved the improved qualities, resulting in the higher stability degree during storage. The species and amount of unsaturated fatty acids in the hydrochar-pellets were higher than those in the untreated-sawdust-pellets. The unsaturated fatty acids content in the hydrochar-pellets was decreased with increasing HTC temperature. Higher aldehydes/ketones emission amount and rates with a longer emission period were found for the hydrochar-pellets, associated with variations of structure and unsaturated fatty acid composition in pellets. Copyright © 2018 Elsevier Ltd. All rights reserved.

Poor adherence to ketone testing in patients with Type 1 Diabetes

USDA-ARS?s Scientific Manuscript database

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 ...

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

PubMed

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.

Two-carbon homologation of aldehydes and ketones to a,ß-unsaturated aldehydes

USDA-ARS?s Scientific Manuscript database

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched a,ß-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a...

Ketonization of Model Pyrolysis Oil Solutions in a Plug Flow Reactor over a Composite Oxide of Fe, Ce, and Al

USDA-ARS?s Scientific Manuscript database

The stabilization and upgrading of pyrolysis oil requires the neutralization of the acidic components of the oil. The conversion of small organic acids, particularly acetic acid, to ketones is one approach to addressing the instability of the oils caused by low pH. In the ketonization reaction, acet...

Ketones and lactate increase cancer cell “stemness”, driving recurrence, metastasis and poor clinical outcome in breast cancer

PubMed Central

Tsirigos, Aristotelis; Lin, Zhao; Pavlides, Stephanos; Wang, Chengwang; Flomenberg, Neal; Knudsen, Erik S; Howell, Anthony; Pestell, Richard G

2011-01-01

Previously, we showed that high-energy metabolites (lactate and ketones) “fuel” tumor growth and experimental metastasis in an in vivo xenograft model, most likely by driving oxidative mitochondrial metabolism in breast cancer cells. To mechanistically understand how these metabolites affect tumor cell behavior, here we used genome-wide transcriptional profiling. Human breast cancer cells (MCF7) were cultured with lactate or ketones, and then subjected to transcriptional analysis (exon-array). Interestingly, our results show that treatment with these high-energy metabolites increases the transcriptional expression of gene profiles normally associated with “stemness”, including genes upregulated in embryonic stem (ES) cells. Similarly, we observe that lactate and ketones promote the growth of bonafide ES cells, providing functional validation. The lactate- and ketone-induced “gene signatures” were able to predict poor clinical outcome (including recurrence and metastasis) in human breast cancer patients. Taken together, our results are consistent with the idea that lactate and ketone utilization in cancer cells promotes the “cancer stem cell” phenotype, resulting in significant decreases in patient survival. One possible mechanism by which high-energy metabolites might induce stemness is by increasing the pool of Acetyl-CoA, leading to increased histone acetylation and elevated gene expression. Thus, our results mechanistically imply that clinical outcome in breast cancer could simply be determined by epigenetics and energy metabolism, rather than by the accumulation of specific “classical” gene mutations. We also suggest that high-risk cancer patients (identified by the lactate/ketone gene signatures) could be treated with new therapeutics that target oxidative mitochondrial metabolism, such as the anti-oxidant and “mitochondrial poison” metformin. Finally, we propose that this new approach to personalized cancer medicine be termed �

Synthesis of 2-acyl-1,4-diketones via the diacylation of {alpha},{beta}-unsaturated ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, N.S.; Yu, S.; Kabalka, G.W.

1998-08-17

The first example of a diacylation of the carbon-carbon double bond in {alpha},{beta}-unsaturated ketones is described. The reaction of acylcyanocuprate reagents with {alpha},{beta}-unsaturated ketones, followed by C-acylation, produces 2-acyl-1,4-diketones in good yields (50--89%). The 1,4-addition of organocuprate reagents to conjugated enones, followed by trapping of the enolate intermediates with various electrophiles, is one of the most useful synthetic reactions. However, to the best of the authors` knowledge, 1,4-acylation followed by trapping of the enolate intermediates with acid chloride has not been reported.

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

PubMed

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.

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: Synergetic effect of ligands and barium enolates

DOE PAGES

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

2014-10-22

Here, 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.

Antifungal activity of fused Mannich ketones triggers an oxidative stress response and is Cap1-dependent in Candida albicans.

PubMed

Rossignol, Tristan; Kocsis, Béla; Bouquet, Orsolya; Kustos, Ildikó; Kilár, Ferenc; Nyul, Adrien; Jakus, Péter B; Rajbhandari, Kshitij; Prókai, László; d'Enfert, Christophe; Lóránd, Tamás

2013-01-01

We investigated the antifungal activity of fused Mannich ketone (FMK) congeners and two of their aminoalcohol derivatives. In particular, FMKs with five-membered saturated rings were shown to have minimum inhibitory concentration (MIC90s) ranging from 0.8 to 6 µg/mL toward C. albicans and the closely related C. parapsilosis and C. krusei while having reduced efficacy toward C. glabrata and almost no efficacy against Aspergillus sp. Transcript profiling of C. albicans cells exposed for 30 or 60 min to 2-(morpholinomethyl)-1-indanone, a representative FMK with a five-membered saturated ring, revealed a transcriptional response typical of oxidative stress and similar to that of a C. albicans Cap1 transcriptional activator. Consistently, C. albicans lacking the CAP1 gene was hypersensitive to this FMK, while C. albicans strains overexpressing CAP1 had decreased sensitivity to 2-(morpholinomethyl)-1-indanone. Quantitative structure-activity relationship studies revealed a correlation of antifungal potency and the energy of the lowest unoccupied molecular orbital of FMKs and unsaturated Mannich ketones thereby implicating redox cycling-mediated oxidative stress as a mechanism of action. This conclusion was further supported by the loss of antifungal activity upon conversion of representative FMKs to aminoalcohols that were unable to participate in redox cycles.

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

PubMed Central

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

Microwave-assisted synthesis of 5-aminopyrazol-4-yl ketones and the p38(MAPK) inhibitor RO3201195 for study in Werner syndrome cells.

PubMed

Bagley, Mark C; Davis, Terence; Dix, Matthew C; Murziani, Paola G S; Rokicki, Michal J; Kipling, David

2008-07-01

5-Aminopyrazol-4-yl ketones are prepared rapidly and efficiently using microwave dielectric heating from beta-ketonitriles by treatment with N,N'-diphenylformamidine followed by heterocyclocondensation by irradiation with a hydrazine. The inhibitory activity of RO3201195 prepared by this methodology was confirmed in hTERT-immortalized HCA2 and WS dermal fibroblasts at 200nM concentration, both by ELISA and immunoblot assay, and displays excellent kinase selectivity for p38alpha MAPK over the related stress-activated kinase JNK.

Body mass index, neighborhood fast food and restaurant concentration, and car ownership.

PubMed

Inagami, Sanae; Cohen, Deborah A; Brown, Arleen F; Asch, Steven M

2009-09-01

Eating away from home and particularly fast food consumption have been shown to contribute to weight gain. Increased geographic access to fast food outlets and other restaurants may contribute to higher levels of obesity, especially in individuals who rely largely on the local environment for their food purchases. We examined whether fast food and restaurant concentrations are associated with body mass index and whether car ownership might moderate this association. We linked the 2000 US Census data and information on locations of fast food and other restaurants with the Los Angeles Family and Neighborhood Study database, which consists of 2,156 adults sampled from 63 neighborhoods in Los Angeles County. Multilevel modeling was used to estimate associations between body mass index (BMI), fast food and restaurant concentration, and car ownership after adjustment for individual-level factors and socioeconomic characteristics of residential neighborhoods. A high concentration of local restaurants is associated with BMI. Car owners have higher BMIs than non-car owners; however, individuals who do not own cars and reside in areas with a high concentration of fast food outlets have higher BMIs than non-car owners who live in areas with no fast food outlets, approximately 12 lb more (p = 0.02) for an individual with a height of 5 ft. 5 in. Higher restaurant density is associated with higher BMI among local residents. The local fast food environment has a stronger association with BMI for local residents who do not have access to cars.

Highly productive CNN pincer ruthenium catalysts for the asymmetric reduction of alkyl aryl ketones.

PubMed

Baratta, Walter; Chelucci, Giorgio; Magnolia, Santo; Siega, Katia; Rigo, Pierluigi

2009-01-01

Chiral pincer ruthenium complexes of formula [RuCl(CNN)(Josiphos)] (2-7; Josiphos = 1-[1-(dicyclohexylphosphano)ethyl]-2-(diarylphosphano)ferrocene) have been prepared by treating [RuCl(2)(PPh(3))(3)] with (S,R)-Josiphos diphosphanes and 1-substituted-1-(6-arylpyridin-2-yl)methanamines (HCNN; substituent = H (1 a), Me (1 b), and tBu (1 c)) with NEt(3). By using 1 b and 1 c as a racemic mixture, complexes 4-7 were obtained through a diastereoselective synthesis promoted by acetic acid. These pincer complexes, which display correctly matched chiral PP and CNN ligands, are remarkably active catalysts for the asymmetric reduction of alkyl aryl ketones in basic alcohol media by both transfer hydrogenation (TH) and hydrogenation (HY), achieving enantioselectivities of up to 99 %. In 2-propanol, the enantioselective TH of ketones was accomplished by using a catalyst loading as low as 0.002 mol % and afforded a turnover frequency (TOF) of 10(5)-10(6) h(-1) (60 and 82 degrees C). In methanol/ethanol mixtures, the CNN pincer complexes catalyzed the asymmetric HY of ketones with H(2) (5 atm) at 0.01 mol % relative to the complex with a TOF of approximately 10(4) h(-1) at 40 degrees C.

Effect of a transition diet on production performance and metabolism in periparturient dairy cows.

PubMed

Guo, J; Peters, R R; Kohn, R A

2007-11-01

The objectives of this study were to characterize the change in blood metabolites over time, and to evaluate the effect of dietary energy concentration on ketone body accumulation in periparturient cows. Twenty-eight multiparous Holstein cows were listed in order of their anticipated due dates and assigned randomly to 1 of 2 groups: with or without a transition diet. The control group received a nonlactating cow diet [1.54 Mcal/kg of net energy for lactation (NE(L)), 10.9% crude protein (CP), 53.1% neutral detergent fiber (NDF)] from 28 d before expected parturition, and a lactation diet (1.77 Mcal of NE(L)/kg, 16.8% CP, 29.9% NDF) after parturition. The treatment group received a transition diet (1.71 Mcal of NE(L)/kg, 16.8% CP, 35.2% NDF) from 17 d before parturition to 14 d after calving and was fed the same diets as cows in the control group during the third week of lactation. Blood from the coccygeal vein was sampled 3 times per week from 21 d before expected parturition to 21 d postpartum for analysis of glucose, nonesterified fatty acids (NEFA), beta-hydroxybutyrate, acetoacetate, acetone, and glycerol. There were no significant differences in dry matter intake, milk yield, milk components, body weight change, and body condition score change during the postcalving period. Plasma concentrations of different ketone bodies changed in parallel, stayed relatively constant precalving, peaked after parturition, and then decreased but remained high compared with concentrations late in gestation. Plasma concentrations of NEFA and glycerol changed in a pattern similar to those of the ketone bodies. Feeding a transition diet resulted in a greater area under the curve (AUC) for glucose in the last 17 d of gestation, but in no effect within the first 21 d in milk. Acetoacetate AUC was greater for treatment cows than for control cows across the first 21 d in milk. The AUC of NEFA and glycerol between d 15 and 21 postpartum were greater for treatment cows than for control

Direct asymmetric aldol reaction of aryl ketones with aryl aldehydes catalyzed by chiral BINOL-derived zincate catalyst.

PubMed

Li, Hong; Da, Chao-Shan; Xiao, Yu-Hua; Li, Xiao; Su, Ya-Ning

2008-09-19

Direct asymmetric aldol reaction of aryl ketones with aryl aldehydes catalyzed by chiral metal complex is reported for the first time herein. Two novel semicrown chiral ligands 1a and 1b were synthesized from (S)- and (R)-BINOL, respectively, and then employed to catalyze the direct asymmetric aldol addition of aryl ketones to aryl aldehydes. Introduced with 2.0 equiv of diethylzinc, 1b had higher enantioselectivity than 1a. Up to 97% yield and up to 80% enantioselectivity were achieved.

Season, molt, and body size influence mercury concentrations in grebes

USGS Publications Warehouse

Hartman, Christopher; Ackerman, Joshua T.; Herzog, Mark; Eagles-Smith, Collin A.

2017-01-01

We studied seasonal and physiological influences on mercury concentrations in western grebes (Aechmophorus occidentalis) and Clark's grebes (A. occidentalis) across 29 lakes and reservoirs in California, USA. Additionally, at three of these lakes, we conducted a time series study, in which we repeatedly sampled grebe blood mercury concentrations during the spring, summer, and early fall. Grebe blood mercury concentrations were higher among males (0.61 ± 0.12 μg/g ww) than females (0.52 ± 0.10 μg/g ww), higher among Clark's grebes (0.58 ± 0.12 μg/g ww) than western grebes (0.51 ± 0.10 μg/g ww), and exhibited a strong seasonal pattern (decreasing by 60% from spring to fall). Grebe blood THg concentrations exhibited a shallow, inverse U-shaped pattern with body size, and was lowest among the smallest and largest grebes. Further, the relationship between grebe blood mercury concentrations and wing primary feather molt exhibited a shallow U-shaped pattern, where mercury concentrations were highest among birds that had not yet begun molting, decreased approximately 24% between pre-molt and late molt, and increased approximately 19% from late molt to post-molt. Because grebes did not begin molting until mid-summer, lower grebe blood mercury concentrations observed in late summer and early fall were consistent with the onset of primary feather molt. However, because sampling date was a much stronger predictor of grebe mercury concentrations than molt, other seasonally changing environmental factors likely played a larger role than molt in the seasonal variation in grebe mercury concentrations. In the time series study, we found that seasonal trends in grebe mercury concentrations were not consistent among lakes, indicating that lake-specific variation in mercury dynamics influence the overall seasonal decline in grebe blood mercury concentrations. These results highlight the importance of accounting for sampling date, as well as ecological processes that may

Preparation and Characterization of Various Poly(ether ether ketone) Containing Imidazolium Moiety for Anion Exchange Membrane Fuel Cell Application.

PubMed

Lee, Byeol-Nim; Son, Tae Yang; Park, Chi Hoon; Kim, Tae Hyun; Nam, Sang Yong

2018-09-01

In this study, various poly(ether ether ketone) were synthesized using three different monomers and the imidazolium group was introduced into synthesized poly(ether ether ketone)s by using substitution reaction. Synthesized polymers were used to prepare anion exchange membranes and to evaluate its properties. Thermal, chemical and structural properties were carried out using thermogravimetric analysis, nuclear magnetic resonance. The anion exchange membranes with different imidazolium moieties were characterized by several different analytical techniques such as water up take, ion exchange capacity, hydroxide conductivity for checking the possibility to apply the anion exchange membrane fuel cell. Consequently, results of characterization were studied to understand the correlation between stabilities of the membrane and functional group and polymer backbone structures. And we confirm membrane performance was improved by increasing imidazolium cation groups.

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

PubMed

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.

Forging C-C Bonds Through Decarbonylation of Aryl Ketones.

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

Study of sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups as ion conductive binder in lithium-ion batteries

NASA Astrophysics Data System (ADS)

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.

Determination of hydride affinities of various aldehydes and ketones in acetonitrile.

PubMed

Zhu, Xiao-Qing; Chen, Xi; Mei, Lian-Rui

2011-05-06

The hydride affinities of 21 typical aldehydes and ketones in acetonitrile were determined by using an experimental method, which is valuable for chemists choosing suitable reducing agents to reduce them. The focus of this paper is to introduce a very facile experimental method, which can be used to determine the hydride affinities of various carbonyl compounds in solution.

Synthesis of a ketone analogue of biotin via the intramolecular Pauson-Khand reaction.

PubMed

McNeill, Eric; Chen, Irwin; Ting, Alice Y

2006-09-28

We report an improved synthesis of 5-(5-oxohexahydrocyclopenta[c]thiophen-1-yl)pentanoic acid (ketone biotin, 1) based on the intramolecular Pauson-Khand cyclization. The synthesis proceeds in eight steps and in 2.7% overall yield from cyclohexene.

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

PubMed

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.

Acetoacetate protects hippocampal neurons against glutamate-mediated neuronal damage during glycolysis inhibition.

PubMed

Massieu, L; Haces, M L; Montiel, T; Hernández-Fonseca, K

2003-01-01

Glucose is the main substrate that fulfills energy brain demands. However, in some circumstances, such as diabetes, starvation, during the suckling period and the ketogenic diet, brain uses the ketone bodies, acetoacetate and beta-hydroxybutyrate, as energy sources. Ketone body utilization in brain depends directly on its blood concentration, which is normally very low, but increases substantially during the conditions mentioned above. Glutamate neurotoxicity has been implicated in neurodegeneration associated with brain ischemia, hypoglycemia and cerebral trauma, conditions related to energy failure, and to elevation of glutamate extracellular levels in brain. In recent years substantial evidence favoring a close relation between glutamate neurotoxic potentiality and cellular energy levels, has been compiled. We have previously demonstrated that accumulation of extracellular glutamate after inhibition of its transporters, induces neuronal death in vivo during energy impairment induced by glycolysis inhibition. In the present study we have assessed the protective potentiality of the ketone body, acetoacetate, against glutamate-mediated neuronal damage in the hippocampus of rats chronically treated with the glycolysis inhibitor, iodoacetate, and in hippocampal cultured neurons exposed to a toxic concentration of iodoacetate. Results show that acetoacetate efficiently protects against glutamate neurotoxicity both in vivo and in vitro probably by a mechanism involving its role as an energy substrate.

Drude polarizable force field for aliphatic ketones and aldehydes, and their associated acyclic carbohydrates

NASA Astrophysics Data System (ADS)

Small, Meagan C.; Aytenfisu, Asaminew H.; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D.

2017-04-01

The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars ( d-allose and d-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars d-allose and d-psicose, thereby extending the available biomolecules in the Drude polarizable FF.

Drude polarizable force field for aliphatic ketones and aldehydes, and their associated acyclic carbohydrates.

PubMed

Small, Meagan C; Aytenfisu, Asaminew H; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D

2017-04-01

The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars (D-allose and D-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars D-allose and D-psicose, thereby extending the available biomolecules in the Drude polarizable FF.

Benzofuran ketone dosage-dependent rayless goldenrod (Isocoma pluriflora) toxicosis in a caprine model

USDA-ARS?s Scientific Manuscript database

The objectives of this study were to determine the dosage of benzofuran ketone compounds (tremetone, 3-hydroxytremetone, dehydrotremetone, and 3-oxyangeloyltremetone) and the duration of exposure to these compounds required to produce clinical signs and the associated pathological changes of rayles ...

Synthesis of a ketone analog of biotin via the intramolecular Pauson-Khand reaction

PubMed Central

McNeill, Eric; Chen, Irwin; Ting, Alice Y.

2008-01-01

We report an improved synthesis of 5-(5-oxohexahydrocyclopenta[c]thiophen-1-yl)pentanoic acid (ketone biotin, 1) based on the intramolecular Pauson-Khand cyclization. The synthesis proceeds in 8 steps and in 2.7% overall yield from cyclohexene. PMID:16986958

Enantioselective, Organocatalytic Reduction of Ketones using Bifunctional Thiourea-Amine Catalysts

PubMed Central

Li, De Run; He, Anyu; Falck, J. R.

2010-01-01

Prochiral ketones are reduced to enantioenriched, secondary alcohols using catecholborane and a family of air-stable, bifunctional thiourea-amine organocatalysts. Asymmetric induction is proposed to arise from the in situ complexation between the borane and chiral thiourea-amine organocatalyst resulting in a stereochemically biased boronate-amine complex. The hydride in the complex is endowed with enhanced nucleophilicity while the thiourea concomitantly embraces and activates the carbonyl. PMID:20334398

Distributions of Polycyclic Aromatic Hydrocarbons, Aromatic Ketones, Carboxylic Acids, and Trace Metals in Arctic Aerosols: Long-Range Atmospheric Transport, Photochemical Degradation/Production at Polar Sunrise.

PubMed

Singh, Dharmendra Kumar; Kawamura, Kimitaka; Yanase, Ayako; Barrie, Leonard A

2017-08-15

The distributions, correlations, and source apportionment of aromatic acids, aromatic ketones, polycyclic aromatic hydrocarbons (PAHs), and trace metals were studied in Canadian high Arctic aerosols. Nineteen PAHs including minor sulfur-containing heterocyclic PAH (dibenzothiophene) and major 6 carcinogenic PAHs were detected with a high proportion of fluoranthene followed by benzo[k]fluoranthene, pyrene, and chrysene. However, in the sunlit period of spring, their concentrations significantly declined likely due to photochemical decomposition. During the polar sunrise from mid-March to mid-April, benzo[a]pyrene to benzo[e]pyrene ratios significantly dropped, and the ratios diminished further from late April to May onward. These results suggest that PAHs transported over the Arctic are subjected to strong photochemical degradation at polar sunrise. Although aromatic ketones decreased in spring, concentrations of some aromatic acids such as benzoic and phthalic acids increased during the course of polar sunrise, suggesting that aromatic hydrocarbons are oxidized to result in aromatic acids. However, PAHs do not act as the major source for low molecular weight (LMW) diacids such as oxalic acid that are largely formed at polar sunrise in the arctic atmosphere because PAHs are 1 to 2 orders of magnitude less abundant than LMW diacids. Correlations of trace metals with organics, their sources, and the possible role of trace transition metals are explained.

EVALUATION OF METHODS FOR THE ISOLATION OR CONCENTRATION OF ORGANIC SUBSTANCES FROM WATER USING XAD-4 QUATERNARY RESIN

EPA Science Inventory

A synthetic resin (Amberlite XAD-4 Quaternary in the OH- form) was evaluated as an adsorption medium for the concentration/isolation of acids, amines, aldehydes, carbohydrates, chlorobiphenyls, esters, hydrocarbons, ketones, phenols, polynuclear aromatic hydrocarbons, and trihalo...

Changes in Oxygen Partial Pressure in the Vitreous Body and Arterial Blood of Rabbits Depending on Oxygen Concentration in Inspired Mixture.

PubMed

Amkhanitskaya, L I; Nikolaeva, G V; Sokolova, N A

2015-07-01

We demonstrated that the vitreous body of one-month-old rabbits becomes a "reservoir" for storage and accumulation of oxygen after exposure to additional oxygenation of the organism (O2 concentrations in inspired gas mixture were 40, 60, 85, and 99%). The higher was O2 concentration in inspired mixture, the higher was oxygen saturation of the blood and vitreous body. O2 concentration of 40% was relatively safe for eye tissues. O2 concentration >60% induced oxygen accumulation in the vitreous body, which can be a provoking factor for the development of oxygen-induced pathologies.

Post-exercise ketosis.

PubMed Central

Koeslag, J H; Noakes, T D; Sloan, A W

1980-01-01

1. The effect of exercise on blood ketone body concentrations was studied in trained athletes and in sedentary subjects pedalling a bicycle ergometer. 2. Although the untrained subjects had higher heart rates and blood lactate concentrations at the same work load as the athletes, neither group developed ketonaemia even after intense or prolonged exercise. 3. Older subjects developed post-exercise ketonaemia, reaching maximum about 3 hr after exercise. 4. A high-carbohydrate diet before the exercise could prevent the onset of post-exercise ketonaemia and a low-carbohydrate diet enhanced it. The highest post-exercise blood ketone levels were recorded in marathon runners after a "glycogen-stripping' regimen. 5. Concentrations of free fatty acids, glucose, growth hormone and insulin in blood after exercise followed different patterns from that of ketones. 6. Post-exercise ketosis, when it occurs in untrained subjects, may be due to a lower carbohydrate intake than that of athletes. PMID:6997456

Season, molt, and body size influence mercury concentrations in grebes.

PubMed

Hartman, C Alex; Ackerman, Joshua T; Herzog, Mark P; Eagles-Smith, Collin A

2017-10-01

We studied seasonal and physiological influences on mercury concentrations in western grebes (Aechmophorus occidentalis) and Clark's grebes (A. occidentalis) across 29 lakes and reservoirs in California, USA. Additionally, at three of these lakes, we conducted a time series study, in which we repeatedly sampled grebe blood mercury concentrations during the spring, summer, and early fall. Grebe blood mercury concentrations were higher among males (0.61 ± 0.12 μg/g ww) than females (0.52 ± 0.10 μg/g ww), higher among Clark's grebes (0.58 ± 0.12 μg/g ww) than western grebes (0.51 ± 0.10 μg/g ww), and exhibited a strong seasonal pattern (decreasing by 60% from spring to fall). Grebe blood THg concentrations exhibited a shallow, inverse U-shaped pattern with body size, and was lowest among the smallest and largest grebes. Further, the relationship between grebe blood mercury concentrations and wing primary feather molt exhibited a shallow U-shaped pattern, where mercury concentrations were highest among birds that had not yet begun molting, decreased approximately 24% between pre-molt and late molt, and increased approximately 19% from late molt to post-molt. Because grebes did not begin molting until mid-summer, lower grebe blood mercury concentrations observed in late summer and early fall were consistent with the onset of primary feather molt. However, because sampling date was a much stronger predictor of grebe mercury concentrations than molt, other seasonally changing environmental factors likely played a larger role than molt in the seasonal variation in grebe mercury concentrations. In the time series study, we found that seasonal trends in grebe mercury concentrations were not consistent among lakes, indicating that lake-specific variation in mercury dynamics influence the overall seasonal decline in grebe blood mercury concentrations. These results highlight the importance of accounting for sampling date, as well as ecological processes

Comparison of mercury concentrations in liver, muscle, whole bodies, and composites of fish from the Red River of the North

USGS Publications Warehouse

Goldstein, Robert M.; Brigham, Mark E.; Stauffer, Joseph C.

1996-01-01

Carp (Cyprinus carpio) from four sites and channel catfish (Ictalurus punctatus) from one site in the Red River of the North in 1994 were analyzed for total mercury content. In carp, mercury concentrations differed among liver, muscle, and whole bodies (0.11, 0.31, and 0.18 µg/g wet weight, respectively), between large and small size groups, but not location. Mercury distribution in channel catfish tissues differed from that in carp. Liver and muscle tissue had similar mean concentrations; each was higher than whole-body concentrations (0.16, 0.18, and 0.11 µg/g, respectively). Mercury concentrations were not significantly different between the two size groups of channel catfish. Weighted-mean mercury concentrations from seven individual fish agreed closely (usually within 10%) with concentrations determined on physical composites of the same fish. The ratio of mercury in whole bodies to mercury in muscle was similar for both carp and channel catfish. Historical data indicate that this ratio may be applicable to other species and locations. The ratio of mercury in livers to whole bodies and muscle differed between carp and channel catfish, which may reflect physiological differences between different trophic groups.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

High Leucine Diets Stimulate Cerebral Branched-Chain Amino Acid Degradation and Modify Serotonin and Ketone Body Concentrations in a Pig Model

PubMed Central

Wessels, Anna G.; Kluge, Holger; Hirche, Frank; Kiowski, Andreas; Schutkowski, Alexandra; Corrent, Etienne; Bartelt, Jörg; König, Bettina; Stangl, Gabriele I.

2016-01-01

In addition to its role as an essential protein component, leucine (Leu) displays several other metabolic functions such as activation of protein synthesis. This property makes it an interesting amino acid for the therapy of human muscle atrophy and for livestock production. However, Leu can stimulate its own degradation via the branched-chain keto acid dehydrogenase complex (BCKDH). To examine the response of several tissues to excessive Leu, pigs were fed diets containing two- (L2) and four-fold (L4) higher Leu contents than the recommended amount (control). We found that the L4 diet led to a pronounced increase in BCKDH activity in the brain (2.5-fold, P < 0.05), liver (1.8-fold, P < 0.05) and cardiac muscle (1.7-fold, P < 0.05), whereas we found no changes in enzyme activity in the pancreas, skeletal muscle, adipose tissue and intestinal mucosa. The L2 diet had only weak effects on BCKDH activity. Both high Leu diets reduced the concentrations of free valine and isoleucine in nearly all tissues. In the brain, high Leu diets modified the amount of tryptophan available: for serotonin synthesis. Compared to the controls, pigs treated with the high Leu diets consumed less food, showed increased plasma concentrations of 3-hydroxybutyrate and reduced levels of circulating serotonin. In conclusion, excessive Leu can stimulate BCKDH activity in several tissues, including the brain. Changes in cerebral tryptophan, along with the changes in amino acid-derived metabolites in the plasma may limit the use of high Leu diets to treat muscle atrophy or to increase muscle growth. PMID:26930301

Inorganic Contaminant Concentrations and Body Condition in Wintering Waterfowl from Great Salt Lake, Utah

NASA Astrophysics Data System (ADS)

Vest, J.; Conover, M.; Perschon, C.; Luft, J.

2006-12-01

The Great Salt Lake (GSL) is the fourth largest terminal lake in the world and is an important region for migratory and breeding waterbirds. Because the GSL is a closed basin, contaminants associated with industrial and urban development may accumulate in this system. Recently, water and sediment samples from the GSL revealed high concentrations of Hg and Se and methylmercury concentrations in GSL water samples were among the highest ever recorded in surface water by the USGS Mercury Laboratory. Thus, GSL waterbirds are likely exposed to these contaminants and elevated contaminant concentrations may adversely affect survival and reproduction in waterfowl. Our objectives were to 1) estimate mercury (Hg), selenium (Se), cadmium (Cd), copper (Cu), and zinc (Zn) concentrations in wintering waterfowl from GSL and, 2) evaluate relationships between measures of waterfowl body condition and internal organ masses (hereafter body condition) with trace metal concentrations. We collected common goldeneye (COGO), northern shoveler (NSHO), and American green-winged teal (AGWT) from the GSL during early winter. We used ICP-MS to analyze liver and muscle tissue samples for contaminant concentrations. We developed species specific regression models for each of 5 condition indices, including ingesta-free plucked body mass (IFPBM), abdominal fat mass, spleen, liver, and pancreas masses. Independent variables were comprised of Hg, Se, Cd, Cu, and Zn and we included sex and age as covariates in each regression. We used Akaike's Information Criterion adjusted for small sample size to select best and competing models. Subsequently, we used partial correlations to depict inverse relationships identified in competing models. Hg concentrations in COGO and NSHO muscle tissue generally exceeded or approached the 1 ppm wet weight (ww) threshold considered unsafe for human consumption in fish and game. Hg concentrations in liver tissue exceeded or were among the highest reported in published

Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide.

PubMed

Dong, Jia Jia; Unjaroen, Duenpen; Mecozzi, Francesco; Harvey, Emma C; Saisaha, Pattama; Pijper, Dirk; de Boer, Johannes W; Alsters, Paul; Feringa, Ben L; Browne, Wesley R

2013-09-01

An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2 O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Compound-Specific Carbon Isotope Compositions of Aldehydes and Ketones in the Tagish Lake Meteorite

NASA Astrophysics Data System (ADS)

Simkus, D. N.; Aponte, J. C.; Hilts, R. W.; Elsila, J. E.; Herd, C. D. K.

2016-08-01

Aldehydes and ketones detected in the Tagish Lake meteorite are highly depleted in 13C, indicating that they are unlikely relic Strecker synthesis precursors. Potential sources for these compounds and the effects of aqueous alteration are discussed.

Bioreduction of α,β-unsaturated ketones and aldehydes by non-conventional yeast (NCY) whole-cells.

PubMed

Goretti, Marta; Ponzoni, Chiara; Caselli, Elisa; Marchegiani, Elisabetta; Cramarossa, Maria Rita; Turchetti, Benedetta; Forti, Luca; Buzzini, Pietro

2011-03-01

The bioreduction of α,β-unsaturated ketones (ketoisophorone, 2-methyl- and 3-methyl-cyclopentenone) and aldehydes [(S)-(-)-perillaldehyde and α-methyl-cinnamaldehyde] by 23 "non-conventional" yeasts (NCYs) belonging to 21 species of the genera Candida, Cryptococcus, Debaryomyces, Hanseniaspora, Kazachstania, Kluyveromyces, Lindnera, Nakaseomyces, Vanderwaltozyma, and Wickerhamomyces was reported. The results highlight the potential of NCYs as whole-cell biocatalysts for selective biotransformation of electron-poor alkenes. A few NCYs exhibited extremely high (>90%) or even total ketoisophorone and 2-methyl-cyclopentenone bioconversion yields via asymmetric reduction of the conjugated CC bond catalyzed by enoate reductases. Catalytic efficiency declined after switching from ketones to aldehydes. High chemoselectivity due to low competing carbonyl reductases was also sometimes observed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Influence of animal age on body concentrations of minerals in Japanese quail (Coturnix japonica).

PubMed

Sales, J; Skřivan, M; Englmaierová, M

2014-12-01

Mathematical modelling of the relationships between mineral inputs and outputs would enable the prediction of mineral requirements of poultry under a wide range of conditions. To establish the feasibility of possible modelling of mineral requirements, the current study aimed to describe the individual mineral concentrations of whole bodies of quail over the life cycle from hatching to 70 days of age. Quail were reared indoors without any restrictions that could limit growth. Sampling of birds (n = 6-18) was carried out at 0, 3, 7, 14, 21, 35, 49 and 70 days after hatching. Freeze-dried samples of whole bodies (digestive contents removed) were analysed for ash, and macrominerals (calcium, magnesium, phosphorus, potassium, sodium) and microminerals (copper, iron, manganese, nickel, selenium, zinc). Ash concentration followed a curvilinear trend, with a maximum of 101.7 g/kg dry matter at 32.77 days. Individual mineral concentrations, expressed as a proportion of ash, were fluctuating over time, with the most prominent changes at 3 days and again at either 14 or 21 days. Dissimilar patterns in individual mineral concentrations resulted that ratios between minerals followed inconsistent patterns over time. Although mineral contents in absolute quantities can be described through modelling over the entire life cycle of the bird, it can be concluded that variable concentrations of individual minerals could complicate further model development. Journal of Animal Physiology and Animal Nutrition © 2014 Blackwell Verlag GmbH.

Drude Polarizable Force Field for Aliphatic Ketones and Aldehydes, and their Associated Acyclic Carbohydrates

PubMed Central

Small, Meagan C.; Aytenfisu, Asaminew H.; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D.

2017-01-01

The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars (D-allose and D-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars D-allose and D-psicose, thereby extending the available biomolecules in the Drude polarizable FF. PMID:28190218

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

PubMed

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.

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.

PubMed

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.

The (non)sense of routinely analysing beta-hydroxybutyric acid in forensic toxicology casework.

PubMed

Sadones, Nele; Lambert, Willy E; Stove, Christophe P

2017-05-01

Beta-hydroxybutyric acid (BHB) is a ketone body which is generated from fatty acids as an alternative energy source when glucose is not available. Determination of this compound may be relevant in the forensic laboratory as ketoacidosis - an elevated level of ketone bodies - may contribute to the cause of death. In this study, we aimed at determining the relevance of routinely implementing BHB analysis in the forensic toxicological laboratory, as BHB analysis typically requires an additional workload. We therefore performed an unbiased retrospective analysis of BHB in 599 cases, comprising 553 blood, 232 urine and 62 vitreous humour samples. Cases with BHB concentrations above 100mg/L (in blood, urine and/or vitreous humour) were invariably associated with elevated levels of acetone, another ketone body, the detection of which is already implemented in most forensic laboratories using the gas chromatographic procedure for ethanol quantification. Our retrospective analysis did not reveal any positive case that had been missed initially and confirms that BHB analysis can be limited to acetone positive cases. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly efficient and direct heterocyclization of dipyridyl ketone to N,N-bidentate ligands

NASA Technical Reports Server (NTRS)

Wang, Jie; Dyers, Leon Jr; Mason, Richard Jr; Amoyaw, Prince; Bu, Xiu R.

2005-01-01

[reaction: see text] Reaction of various aromatic aldehydes with 2,2'-dipyridyl ketone and ammonium acetate in hot acetic acid provides ready access to a series of substituted 1-pyridylimidazo[1,5-a]pyridines, a class of ligands possessing an N,N-bidentate feature, in good yields.

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

PubMed

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.

The mechanism of enantioselective ketone reduction with Noyori and Noyori–Ikariya bifunctional catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dub, Pavel A.; Gordon, John C.

2016-03-21

The catalytic hydrogenation of prochiral ketones with second and third-row transition metal complexes bearing chelating chiral ligands containing at least one N–H functionality has achieved unparalleled performance, delivering, in the best cases, chiral alcohols with up to 99.9% ee using extremely small catalyst loadings (~10 -5 mol%). Hence the efficacy of this reaction has closely approached that of natural enzymatic systems and the reaction itself has become one of the most efficient artificial catalytic reactions developed to date. This paper describes the current level of understanding of the mechanism of enantioselective hydrogenation and transfer hydrogenation of aromatic ketones with pioneeringmore » prototypes of bifunctional catalysts, the Noyori and Noyori–Ikariya complexes. Finally, analysis presented herein expands the concept of “metal–ligand cooperation”, redefines the term “cooperative ligand” and introduces “H –/H + outer-sphere hydrogenation” as a novel paradigm in outer-sphere hydrogenation.« less

Tandem nucleophilic addition-Oppenauer oxidation of aromatic aldehydes to aryl ketones with triorganoaluminium reagents.

PubMed

Fu, Ying; Yang, Yanshou; Hügel, Helmut M; Du, Zhengyin; Wang, Kehu; Huang, Danfeng; Hu, Yulai

2013-07-21

In the presence of pinacolone, the in situ prepared triorganoaluminium reagents reacted with aromatic aldehydes to give ketones in moderate to high yield. We propose that the products are formed via a tandem organoaluminium reagents addition-Oppenauer oxidation sequence.

Allyl transfer to aldehydes and ketones by Brønsted acid activation of allyl and crotyl 1,3,2-dioxazaborolidines.

PubMed

Reilly, Maureen K; Rychnovsky, Scott D

2010-11-05

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism).

[Determination of methyl nonyl ketone in volatile oil from herbs of Houttuynia cordata by GC-MS].

PubMed

Yang, Lixin; Zhang, Yongxin; Yi, Hong; Yang, Hua; Zhang, Qiwei

2010-08-01

To develop a GC-MS method for the determination of methyl nonyl ketone in the volatile oil from the herbs of Houttuynia cordata. The sample was split in the 240 degrees C injection port, with 20:1 split ratio, and separated on a DB-5 (30 m x 0.25 mm, 0.25 microm film thickness) fused silica column with helium as the carrier gas. The temperature program was as follows: 100 degrees C for 2 min, the 5 degrees C x min(-1) to 150 degrees C, then 15 degrees C x min(-1) to 200 degrees C, and kept for 10 min. The MS transfer line temperature was set to 250 degrees C, the MS source temperature was set to 200 degrees C. The ionization mode was electron ionization (EI) and the selective ion monitor mode was used. A good linear relationship was constructed over the injection amount range of 5.5-110 ng of methyl nonyl ketone. The average recovery was 98.9%, and RSD was 2. 2%. The developed method was sensitive, accurate, and can be used for the determination of methyl nonyl ketone in the volatile oil and for the quality control of H. cordata.

Aminosilica materials as adsorbents for the selective removal of aldehydes and ketones from simulated bio-oil.

PubMed

Drese, Jeffrey H; Talley, Anne D; Jones, Christopher W

2011-03-21

The fast pyrolysis of biomass is a potential route to the production of liquid biorenewable fuel sources. However, degradation of the bio-oil mixtures due to reaction of oxygenates, such as aldehydes and ketones, reduces the stability of the liquids and can impact long-term storage and shipping. Herein, solid aminosilica adsorbents are described for the selective adsorptive removal of reactive aldehyde and ketone species. Three aminosilica adsorbents are prepared through the reaction of amine-containing silanes with pore-expanded mesoporous silica. A fourth aminosilica adsorbent is prepared through the ring-opening polymerization of aziridine from pore-expanded mesoporous silica. Adsorption experiments with a representative mixture of bio-oil model compounds are presented using each adsorbent at room temperature and 45 °C. The adsorbent comprising only primary amines adsorbs the largest amount of aldehydes and ketones. The overall reactivity of this adsorbent increases with increasing temperature. Additional aldehyde screening experiments show that the reactivity of aldehydes with aminosilicas varies depending on their chemical functionality. Initial attempts to regenerate an aminosilica adsorbent by acid hydrolysis show that they can be at least partially regenerated for further use. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Indium-mediated asymmetric Barbier-type propargylations: additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents.

PubMed

Haddad, Terra D; Hirayama, Lacie C; Buckley, Jannise J; Singaram, Bakthan

2012-01-20

We report a simple, efficient, and general method for the indium-mediated enantioselective propargylation of aromatic and aliphatic aldehydes under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 90%) and enantiomeric excess (up to 95%). The extension of this methodology to ketones demonstrated the need for electrophilic ketones more reactive than acetophenone as the reaction would not proceed with just acetophenone. Using the Lewis acid indium triflate [In(OTf)(3)] induced regioselective formation of the corresponding homoallenic alcohol product from acetophenone. However, this methodology demonstrated excellent chemoselectivity in formation of only the corresponding secondary homopropargylic alcohol product in the presence of a ketone functionality. Investigation of the organoindium intermediates under our reaction conditions shows the formation of allenylindium species, and we suggest that these species contain an indium(III) center. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.

Relationship of ultrasound signal intensity with SonoVue concentration at body temperature in vitro

NASA Astrophysics Data System (ADS)

Yang, Xin; Li, Jing; He, Xiaoling; Wu, Kaizhi; Yuan, Yun; Ding, Mingyue

2014-04-01

In this paper, the relationship between image intensity and ultrasound contrast agent (UCA) concentration is investigated. Experiments are conducted in water bath using a silicon tube filled with UCA (SonoVue) at different concentrations (100μl/l to 6000μl/l) at around 37 °C to simulate the temperature in human body. The mean gray-scale intensity within the region of interest (ROI) is calculated to obtain the plot of signal intensity to UCA concentration. The results show that the intensity firstly exhibits a linear increase to the peak at approximately 1500μl/l then appears a downward trend due to the multiple scattering (MS) effects.

The effects of low and moderate doses of caffeine supplementation on upper and lower body maximal voluntary concentric and eccentric muscle force.

PubMed

Tallis, Jason; Yavuz, Harley C M

2018-03-01

Despite the growing quantity of literature exploring the effect of caffeine on muscular strength, there is a dearth of data that directly explores differences in erogenicity between upper and lower body musculature and the dose-response effect. The present study sought to investigate the effects of low and moderate doses of caffeine on the maximal voluntary strength of the elbow flexors and knee extensors. Ten nonspecifically strength-trained, recreationally active participants (aged 21 ± 0.3 years) completed the study. Using a randomised, counterbalanced, and double-blind approach, isokinetic concentric and eccentric strength was measured at 60 and 180°/s following administration of a placebo, 3 mg·kg -1 body mass caffeine, and 6 mg·kg -1 body mass caffeine. There was no effect of caffeine on the maximal voluntary concentric and eccentric strength of the elbow flexors, or the eccentric strength of the knee extensors. Both 3 and 6 mg·kg -1 body mass caffeine caused a significant increase in peak concentric force of the knee extensors at 180°/s. No difference was apparent between the 2 concentrations. Only 6 mg·kg -1 body mass caused an increase in peak concentric force during repeated contractions. The results infer that the effective caffeine concentration to evoke improved muscle performance may be related to muscle mass and contraction type. The present work indicates that a relatively low dose of caffeine treatment may be effective for improving lower body muscular strength, but may have little benefit for the strength of major muscular groups of the upper body.

Ca(OH)2-Catalyzed Condensation of Aldehydes with Methyl ketones in Dilute Aqueous Ethanol: A Comprehensive Access to α,β-Unsaturated Ketones

NASA Astrophysics Data System (ADS)

Yu, Lei; Han, Mengting; Luan, Jie; Xu, Lin; Ding, Yuanhua; Xu, Qing

2016-07-01

Cheap, abundant but seldom-employed Ca(OH)2 was found to be an excellent low-loading (5-10 mol%) catalyst for Claisen-Schmidt condensation of aldehydes with methyl ketones under mild conditions. It was interesting that dilute aqueous ethanol (20 v/v%) was unexpectedly discovered to be the optimal solvent. The reaction was scalable at least to 100 mmol and calcium could be precipitated by CO2 and removed by filtration. Evaporation of solvent directly afforded the product in the excellent 96% yield with high purity, as confirmed by its 1H NMR spectrum.

Development of many-body polarizable force fields for Li-battery components: 1. Ether, alkane, and carbonate-based solvents.

PubMed

Borodin, Oleg; Smith, Grant D

2006-03-30

Classical many-body polarizable force fields were developed for n-alkanes, perflouroalkanes, polyethers, ketones, and linear and cyclic carbonates on the basis of quantum chemistry dimer energies of model compounds and empirical thermodynamic liquid-state properties. The dependence of the electron correlation contribution to the dimer binding energy on basis-set size and level of theory was investigated as a function of molecular separation for a number of alkane, ether, and ketone dimers. Molecular dynamics (MD) simulations of the force fields accurately predicted structural, dynamic, and transport properties of liquids and unentangled polymer melts. On average, gas-phase dimer binding energies predicted with the force field were between those from MP2/aug-cc-pvDz and MP2/aug-cc-pvTz quantum chemistry calculations.

Allyl Transfer to Aldehydes and Ketones by Brønsted Acid Activation of Allyl and Crotyl 1,3,2-Dioxazaborolidines

PubMed Central

Reilly, Maureen K.; Rychnovsky, Scott D.

2010-01-01

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (Type I mechanism). PMID:20942379

Iridium Catalysts with f-Amphox Ligands: Asymmetric Hydrogenation of Simple Ketones.

PubMed

Wu, Weilong; Liu, Shaodong; Duan, Meng; Tan, Xuefeng; Chen, Caiyou; Xie, Yun; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu

2016-06-17

A series of modular and rich electronic tridentate ferrocene aminophosphoxazoline ligands (f-amphox) have been successfully developed and used in iridium-catalytic asymmetric hydrogenation of simple ketones to afford corresponding enantiomerically enriched alcohols under mild conditions with superb activities and excellent enantioselectivities (up to 1 000 000 TON, almost all products up to >99% ee, full conversion). The resulting chiral alcohols and their derivatives are important intermediates in pharmaceuticals.

Doubly Vinylogous Aldol Reaction of Furoate Esters with Aldehydes and Ketones.

PubMed

Hartwig, William T; Sammakia, Tarek

2017-01-06

The use of bulky Lewis acids, aluminum tris(2,6-diphenylphenoxide) (ATPH) and aluminum tris(2,6-di-2-naphthylphenoxide) (ATNP), in the doubly vinylogous aldol reaction between methyl-5-methyl-2-furoate and aldehydes or ketones is described. These reactions proceed smoothly and in high yields with both enolizable and non-enolizable substrates. This C-C bond-forming reaction enables a new bond construction for the synthesis of functionalized furans.

How Cinchona Alkaloid-Derived Primary Amines Control Asymmetric Electrophilic Fluorination of Cyclic Ketones

PubMed Central

2015-01-01

The origin of selectivity in the α-fluorination of cyclic ketones catalyzed by cinchona alkaloid-derived primary amines is determined with density functional calculations. The chair preference of a seven-membered ring at the fluorine transfer transition state is key in determining the sense and level of enantiofacial selectivity. PMID:24967514

Simple one-pot conversion of aldehydes and ketones to enals.

PubMed

Valenta, Petr; Drucker, Natalie A; Bode, Jeffrey W; Walsh, Patrick J

2009-05-21

A simple and efficient method to convert aldehydes into alpha,beta-unsaturated aldehydes with a two-carbon homologation is presented. Hydroboration of ethoxy acetylene with BH(3).SMe(2) generates tris(ethoxyvinyl) borane. Transmetalation with diethylzinc, addition to aldehydes or ketones, and acidic workup affords enals. When the addition is quenched with anilinium hydrochloride, 1,2-dithioglycol, or acetic anhydride, the unsaturated imine, dithiolane, or 1,1-diacetate is isolated in high yield. These transformations can be performed in a one-pot procedure.

Decreased carbon shunting from glucose towards oxidative metabolism in diet-induced ketotic rat brain

PubMed Central

Zhang, Yifan; Zhang, Shenghui; Marin-Valencia, Isaac; Puchowicz, Michelle A.

2014-01-01

The mechanistic link of ketosis to neuroprotection under certain pathological conditions continues to be explored. We investigated whether chronic ketosis induced by ketogenic diet results in the partitioning of ketone bodies towards oxidative metabolism in brain. We hypothesized that diet-induced ketosis results in increased shunting of ketone bodies towards citric acid cycle (CAC) and amino acids with decreased carbon shunting from glucose. Rats were fed standard (STD) or ketogenic (KG) diets for 3.5 weeks and then infused with [U-13C]glucose or [U-13C]acetoacetate tracers. Concentrations and 13C-labeling pattern of CAC intermediates and amino acids were analyzed from brain homogenates using stable isotopomer mass spectrometry analysis. The contribution of [U-13C]glucose to acetyl-CoA and amino acids decreased by ~30% in the KG group vs STD, whereas [U-13C]acetoacetate contributions were more than 2-fold higher. The concentration of GABA remained constant across all groups; however, the 13C-labeling of GABA was markedly increased in the KG group infused with [U-13C]acetoacetate compared to STD. This study reveals that there is a significant contribution of ketone bodies to oxidative metabolism and GABA in diet-induced ketosis. We propose that this represents a fundamental mechanism of neuroprotection under pathological conditions. PMID:25314677

Fe-Catalyzed Cycloisomerization of Aryl Allenyl Ketones: Access to 3-Arylidene-indan-1-ones.

PubMed

Teske, Johannes; Plietker, Bernd

2018-04-20

A cycloisomerization of aryl allenyl ketones to 3-arylidene-indan-1-ones using a cationic Fe-complex as a catalyst is reported. The catalyst opens a synthetically interesting reaction pathway to this surprisingly underrepresented class of indanones that are not accessible using alternative catalytic systems.

Difluoromethyl 2-pyridyl sulfone: a new gem-difluoroolefination reagent for aldehydes and ketones.

PubMed

Zhao, Yanchuan; Huang, Weizhou; Zhu, Lingui; Hu, Jinbo

2010-04-02

Difluoromethyl 2-pyridyl sulfone, a previously unknown compound, was found to act as a novel and efficient gem-difluoroolefination reagent for both aldehydes and ketones. It was found that the fluorinated sulfinate intermediate in the reaction is relatively stable, which can be observed by (19)F NMR and trapped with CH(3)I.

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

PubMed

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.

Regulation of body fluid volume and electrolyte concentrations in spaceflight.

PubMed

Smith, S M; Krauhs, J M; Leach, C S

1997-01-01

Despite a number of difficulties in performing experiments during weightlessness, a great deal of information has been obtained concerning the effects of spaceflight on the regulation of body fluid and electrolytes. Many paradoxes and questions remain, however. Although body mass, extracellular fluid volume, and plasma volume are reduced during spaceflight and remain so at landing, the changes in total body water are comparatively small. Serum or plasma sodium and osmolality have generally been unchanged or reduced during the spaceflight, and fluid intake is substantially reduced, especially during the first of flight. The diuresis that was predicted to be caused by weightlessness, has only rarely been observed as an increased urine volume. What has been well established by now, is the occurrence of a relative diuresis, where fluid intake decreases more than urine volume does. Urinary excretion of electrolytes has been variable during spaceflight, but retention of fluid and electrolytes at landing has been consistently observed. The glomerular filtration rate was significantly elevated during the SLS missions, and water and electrolyte loading tests have indicated that renal function is altered during readaptation to Earth's gravity. Endocrine control of fluid volumes and electrolyte concentrations may be altered during weightlessness, but levels of hormones in body fluids do not conform to predictions based on early hypotheses. Antidiuretic hormone is not suppressed, though its level is highly variable and its secretion may be affected by space motion sickness and environmental factors. Plasma renin activity and aldosterone are generally elevated at landing, consistent with sodium retention, but inflight levels have been variable. Salt intake may be an important factor influencing the levels of these hormones. The circadian rhythm of cortisol has undoubtedly contributed to its variability, and little is known yet about the influence of spaceflight on circadian

Regulation of body fluid volume and electrolyte concentrations in spaceflight

NASA Technical Reports Server (NTRS)

Smith, S. M.; Krauhs, J. M.; Leach, C. S.

1997-01-01

Despite a number of difficulties in performing experiments during weightlessness, a great deal of information has been obtained concerning the effects of spaceflight on the regulation of body fluid and electrolytes. Many paradoxes and questions remain, however. Although body mass, extracellular fluid volume, and plasma volume are reduced during spaceflight and remain so at landing, the changes in total body water are comparatively small. Serum or plasma sodium and osmolality have generally been unchanged or reduced during the spaceflight, and fluid intake is substantially reduced, especially during the first of flight. The diuresis that was predicted to be caused by weightlessness, has only rarely been observed as an increased urine volume. What has been well established by now, is the occurrence of a relative diuresis, where fluid intake decreases more than urine volume does. Urinary excretion of electrolytes has been variable during spaceflight, but retention of fluid and electrolytes at landing has been consistently observed. The glomerular filtration rate was significantly elevated during the SLS missions, and water and electrolyte loading tests have indicated that renal function is altered during readaptation to Earth's gravity. Endocrine control of fluid volumes and electrolyte concentrations may be altered during weightlessness, but levels of hormones in body fluids do not conform to predictions based on early hypotheses. Antidiuretic hormone is not suppressed, though its level is highly variable and its secretion may be affected by space motion sickness and environmental factors. Plasma renin activity and aldosterone are generally elevated at landing, consistent with sodium retention, but inflight levels have been variable. Salt intake may be an important factor influencing the levels of these hormones. The circadian rhythm of cortisol has undoubtedly contributed to its variability, and little is known yet about the influence of spaceflight on circadian

Environmental and Body Concentrations of Heavy Metals at Sites Near and Distant from Industrial Complexes in Ulsan, Korea.

PubMed

Sung, Joo Hyun; Oh, Inbo; Kim, Ahra; Lee, Jiho; Sim, Chang Sun; Yoo, Cheolin; Park, Sang Jin; Kim, Geun Bae; Kim, Yangho

2018-01-29

Industrial pollution may affect the heavy metal body burden of people living near industrial complexes. We determined the average concentrations of atmospheric heavy metals in areas close to and distant from industrial complexes in Korea, and the body concentrations of these heavy metals in residents living near and distant from these facilities. The atmospheric data of heavy metals (lead and cadmium) were from the Regional Air Monitoring Network in Ulsan. We recruited 1,148 participants, 872 who lived near an industrial complex ("exposed" group) and 276 who lived distant from industrial complexes ("non-exposed" group), and measured their concentrations of blood lead, urinary cadmium, and urinary total mercury. The results showed that atmospheric and human concentrations of heavy metals were higher in areas near industrial complexes. In addition, residents living near industrial complexes had higher individual and combined concentrations (cadmium + lead + mercury) of heavy metals. We conclude that residents living near industrial complexes are exposed to high concentrations of heavy metals, and should be carefully monitored. © 2018 The Korean Academy of Medical Sciences.

Environmental and Body Concentrations of Heavy Metals at Sites Near and Distant from Industrial Complexes in Ulsan, Korea

PubMed Central

2017-01-01

Background Industrial pollution may affect the heavy metal body burden of people living near industrial complexes. We determined the average concentrations of atmospheric heavy metals in areas close to and distant from industrial complexes in Korea, and the body concentrations of these heavy metals in residents living near and distant from these facilities. Methods The atmospheric data of heavy metals (lead and cadmium) were from the Regional Air Monitoring Network in Ulsan. We recruited 1,148 participants, 872 who lived near an industrial complex (“exposed” group) and 276 who lived distant from industrial complexes (“non-exposed” group), and measured their concentrations of blood lead, urinary cadmium, and urinary total mercury. Results The results showed that atmospheric and human concentrations of heavy metals were higher in areas near industrial complexes. In addition, residents living near industrial complexes had higher individual and combined concentrations (cadmium + lead + mercury) of heavy metals. Conclusion We conclude that residents living near industrial complexes are exposed to high concentrations of heavy metals, and should be carefully monitored. PMID:29349943

Genetic parameter estimation for milk β-hydroxybutyrate and acetone in early lactation and its association with fat to protein ratio and energy balance in Korean Holstein cattle.

PubMed

Ranaraja, Umanthi; Cho, KwangHyun; Park, MiNa; Kim, SiDong; Lee, SeokHyun; Do, ChangHee

2018-06-01

The objective of this study was to estimate the genetic parameters for milk β-hydroxybutyrate (BHBA), acetone (Ac), fat protein ratio (FPR), and energy balance (EB) using milk test day records and investigate the effect of early lactation FPR and EB on milk ketone body concentrations. Total 262,940 test-day records collected from Korea Animal Improvement Association during the period of 2012 to 2016 were used in this study. BHBA and Ac concentrations in milk were measured by Fourier transform infrared spectroscopy (FTIR). FPR values were obtained using test day records of fat and protein percentage. EB was calculated using previously developed equation based on parity, lactation week, and milk composition data. Genetic parameters were estimated by restricted maximum likelihood procedure based on repeatability model using Wombat program. Elevated milk BHBA and Ac concentrations were observed during the early lactation under the negative energy balance. Milk FPR tends to decrease with the decreasing ketone body concentrations. Heritability estimates for milk BHBA, Ac, EB, and FPR ranged from 0.09 to 0.14, 0.23 to 0.31, 0.19 to 0.52, and 0.16 to 0.42 respectively at parity 1, 2, 3, and 4. The overall heritability for BHBA, Ac, EB and FPR were 0.29, 0.32, 0.58, and 0.38 respectively. A common pattern was observed in heritability of EB and FPR along with parities. FPR and EB can be suggested as potential predictors for risk of hyperketonemia. The heritability estimates of milk BHBA, Ac, EB, and FPR indicate that the selective breeding may contribute to maintaining the milk ketone bodies at optimum level during early lactation.

Triacetin: a potential parenteral nutrient.

PubMed

Bailey, J W; Haymond, M W; Miles, J M

1991-01-01

Triacetin, the water-soluble triglyceride of acetate, was infused in mongrel dogs at isocaloric (N = 6) or hypercaloric (approximately 1.5 REE, N = 7) rates in mongrel dogs for 3 hr. Ketone body and glucose production rates were quantified with [13C2] acetoacetate and [3H]glucose, respectively. Four additional animals were infused with glycerol to serve as controls for the hypercaloric triacetin infusion. Energy expenditure was determined in the isocaloric experiments. no evidence of acute toxicity was observed during triacetin infusion at either rate. Plasma acetate concentrations increased from basal levels to approximately 1 and approximately 13 mmol/liter in the isocaloric and hypercaloric experiments, respectively. Plasma lactate and pyruvate concentrations decreased dramatically after 30 min of both isocaloric and hypercaloric triacetin infusions. Glucose production rates did not increase in either group, but glucose clearance decreased significantly in both groups (p less than 0.05) over the last hour of triacetin infusion. Plasma ketone body concentrations increased from 1.4 to 3.5 and 1.8 to 13.5 mumol/kg.min, respectively, during isocaloric and hypercaloric triacetin infusion. Resting energy expenditure increased from 3.0 +/- 0.3 to 4.0 +/- 0.5 kcal/kg.hr during isocaloric triacetin infusion (p less than 0.05). These studies indicate that triacetin can be administered to dogs at high rates without overt toxicity. The decrease in glucose clearance may represent competition between carbohydrate (glucose) and lipid (acetate). Triacetin infusion resulted in significant increases in ketone body production and concentration. These preliminary data indicate that triacetin may have a future role as a parenteral nutrient, and that further studies of its use are warranted.

The Microwave Spectrum of Methyl Vinyl Ketone Revisited

NASA Astrophysics Data System (ADS)

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.

N-heterocyclic carbene catalysed asymmetric cross-benzoin reactions of heteroaromatic aldehydes with trifluoromethyl ketones.

PubMed

Enders, Dieter; Grossmann, André; Fronert, Jeanne; Raabe, Gerhard

2010-09-14

A new triazolium salt derived N-heterocyclic carbene catalyses an asymmetric cross-benzoin-type reaction of heteroaromatic aldehydes and various trifluoromethyl ketones in good to excellent yields (69-96%) and moderate to good enantioselectivities (ee = 39-85%). Up to 99% ee can be achieved by recrystallisation.

Synthesis of functionalized chromenes from Meldrum's acid, 4-hydroxycoumarin, and ketones or aldehydes.

PubMed

Sabbaghan, Maryam; Yavari, Issa; Hossaini, Zinatossadat

2010-11-01

An efficient synthesis of 4-alkyl-4-methyl-3,4-dihydro-2H,5H-pyrano[3,2-c]chromene-2,5-dione or 4-aryl-3,4-dihydro-2H,5H-pyrano[3,2-c]chromene-2,5-diones via reaction 4-hydroxycoumarin with Meldrum's acid and ketones or aldehydes is described.

Determination of linear short chain aliphatic aldehyde and ketone vapors in air using a polystyrene-coated quartz crystal nanobalance sensor.

PubMed

Mirmohseni, Abdolreza; Olad, Ali

2010-01-01

A polystyrene coated quartz crystal nanobalance (QCN) sensor was developed for use in the determination of a number of linear short-chain aliphatic aldehyde and ketone vapors contained in air. The quartz crystal was modified by a thin-layer coating of a commercial grade general purpose polystyrene (GPPS) from Tabriz petrochemical company using a solution casting method. Determination was based on frequency shifts of the modified quartz crystal due to the adsorption of analytes at the surface of modified electrode in exposure to various concentrations of analytes. The frequency shift was found to have a linear relation to the concentration of analytes. Linear calibration curves were obtained for 7-70 mg l(-1) of analytes with correlation coefficients in the range of 0.9935-0.9989 and sensitivity factors in the range of 2.07-6.74 Hz/mg l(-1). A storage period of over three months showed no loss in the sensitivity and performance of the sensor.

Evaluation of silica-gel cartridges coated in situ with acidified 2,4-dinitrophenylhydrazine for sampling aldehydes and ketones in air

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tejada, S.B.

1986-01-01

A procedure for coating in-situ silica in commercially available prepacked cartridges with 2,4-dinitrophenylhydrazine (DNPH) acidified with hydrochloric acid is described. The coated cartridge was compared with a validated DNPH impinger method for sampling organic carbonyl compounds (aldehydes and ketones) in diluted automotive exhaust emissions and in ambient air for subsequent analysis of the DNPH derivatives by high performance liquid chromatography. Qualitative and quantitative results show that the two sampling devices are equivalent. An unknown degradation product of acrolein has been tentatively identified as x-acrolein. The disappearance of acrolein in the analytical sample matrix correlated quantitatively almost on a mole-for-mole basismore » with the growth of x-acrolein. The sum of the concentration of acrolein and x-acrolein appears to be invariant with time. This sum could possibly be used as a more-accurate value of the concentration of acrolein in the integratated sample.« less

Chemoselective synthesis of ketones and ketimines by addition of organometallic reagents to secondary amides

NASA Astrophysics Data System (ADS)

Bechara, William S.; Pelletier, Guillaume; Charette, André B.

2012-03-01

The development of efficient and selective transformations is crucial in synthetic chemistry as it opens new possibilities in the total synthesis of complex molecules. Applying such reactions to the synthesis of ketones is of great importance, as this motif serves as a synthetic handle for the elaboration of numerous organic functionalities. In this context, we report a general and chemoselective method based on an activation/addition sequence on secondary amides allowing the controlled isolation of structurally diverse ketones and ketimines. The generation of a highly electrophilic imidoyl triflate intermediate was found to be pivotal in the observed exceptional functional group tolerance, allowing the facile addition of readily available Grignard and diorganozinc reagents to amides, and avoiding commonly observed over-addition or reduction side reactions. The methodology has been applied to the formal synthesis of analogues of the antineoplastic agent Bexarotene and to the rapid and efficient synthesis of unsymmetrical diketones in a one-pot procedure.

The effect of power-law body forces on a thermally driven flow between concentric rotating spheres

NASA Technical Reports Server (NTRS)

Macaraeg, M. G.

1986-01-01

A numerical study is conducted to determine the effect of power-law body forces on a thermally-driven axisymmetric flow field confined between concentric co-rotating spheres. This study is motivated by Spacelab geophysical fluid-flow experiments, which use an electrostatic force on a dielectric fluid to simulate gravity; this force exhibits a (1/r)sup 5 distribution. Meridional velocity is found to increase when the electrostatic body force is imposed, relative to when the body force is uniform. Correlation among flow fields with uniform, inverse-square, and inverse-quintic force fields is obtained using a modified Grashof number.

The effect of power law body forces on a thermally-driven flow between concentric rotating spheres

NASA Technical Reports Server (NTRS)

Macaraeg, M. G.

1985-01-01

A numerical study is conducted to determine the effect of power-law body forces on a thermally-driven axisymmetric flow field confined between concentric co-rotating spheres. This study is motivated by Spacelab geophysical fluid-flow experiments, which use an electrostatic force on a dielectric fluid to simulate gravity; this force exhibits a (1/r)sup 5 distribution. Meridional velocity is found to increase when the electrostatic body force is imposed, relative to when the body force is uniform. Correlation among flow fields with uniform, inverse-square, and inverse-quintic force fields is obtained using a modified Grashof number.

Preoperative carbohydrate-rich beverage reduces hypothermia during general anesthesia in rats.

PubMed

Yatabe, Tomoaki; Kawano, Takashi; Yamashita, Koichi; Yokoyama, Masataka

2011-08-01

Intraoperative hypothermia is associated with several unfavorable events; therefore, it is important to prevent the development of hypothermia. Amino acid consumption and/or infusion have been reported to prevent hypothermia. We hypothesized that preoperative carbohydrate-rich beverage (Arginaid Water™) loading can reduce intraoperative hypothermia in rats under general anesthesia. We divided 18 rats into 3 groups (group A, 8 mL/kg of saline; group B, 8 mL/kg of a carbohydrate-rich beverage; and group C, 21 mL/kg of the carbohydrate-rich beverage). The rats were administered each beverage at the above mentioned doses via an oral gastric tube 30 min before the induction of anesthesia. During the 2-h general anesthesia, rectal temperature was measured at 20-min intervals. Serum ketone body concentration was measured at 0 and 120 min. The baseline temperature was not significantly different among the groups. At the end of the experiment, group A showed a significantly greater decrease in temperature from the baseline (5.4 ± 0.8°C) than group B (3.9 ± 0.7°C, P = 0.01) and group C (3.8 ± 0.8°C, P = 0.01). The temperatures in groups B and C were not significantly different. There was no significant change in the serum ketone body concentration from the baseline at the end of the experiment in group A. However, the serum ketone body concentrations in group B and group C were significantly decreased from the baseline. Preoperative carbohydrate loading reduces hypothermia in rats under general anesthesia.

Metabolic organization of the spotted ratfish, Hydrolagus colliei (Holocephali: Chimaeriformes): insight into the evolution of energy metabolism in the chondrichthyan fishes.

PubMed

Speers-Roesch, Ben; Robinson, Jacob William; Ballantyne, James Stuart

2006-08-01

The metabolic organization of a holocephalan, the spotted ratfish (Hydrolagus colliei), was assessed using measurements of key enzymes of several metabolic pathways in four tissues and plasma concentrations of free amino acids (FAA) and non-esterified fatty acids (NEFA) to ascertain if the Holocephali differ metabolically from the Elasmobranchii since these groups diverged ca. 400 Mya. Activities of carnitine palmitoyl transferase indicate that fatty acid oxidation occurs in liver and kidney but not in heart or white muscle. This result mirrors the well-established absence of lipid oxidation in elasmobranch muscle, and more recent studies showing that elasmobranch kidney possesses a capacity for lipid oxidation. High activities in oxidative tissues of enzymes of ketone body metabolism, including D-beta-hydroxybutyrate dehydrogenase, indicate that, like elasmobranchs, ketone bodies are of central importance in spotted ratfish. Like many carnivorous fishes, enzyme activities demonstrate that amino acids are metabolically important, although the concentration of plasma FAA was relatively low. NEFA concentrations are lower than in teleosts, but higher than in most elasmobranchs and similar to that in some "primitive" ray-finned fishes. NEFA composition is comparable to other marine temperate fishes, including high levels of n-6 and especially n-3 polyunsaturated fatty acids. The metabolic organization of the spotted ratfish is similar to that of elasmobranchs: a reduced capacity for lipid oxidation in muscle, lower plasma NEFA levels, and an emphasis on ketone bodies as oxidative fuel. This metabolic strategy was likely present in the common chondrichthyan ancestor, and may be similar to the ancestral metabolic state of fishes. Copyright 2006 Wiley-Liss, Inc.

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

PubMed

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.

Ambient Temperature Synthesis of High Enantiopurity N-Protected Peptidyl Ketones by Peptidyl Thiol Ester–Boronic Acid Cross-Coupling

PubMed Central

Yang, Hao; Li, Hao; Wittenberg, Rüdiger; Egi, Masahiro; Huang, Wenwei; Liebeskind, Lanny S.

2009-01-01

α-Amino acid thiol esters derived from N-protected mono-, di-, and tripeptides couple with aryl, π-electron-rich heteroaryl, or alkenyl boronic acids in the presence of stoichiometric Cu(I) thiophene-2-carboxylate (CuTC) and catalytic Pd2(dba)3/triethylphosphite to generate the corresponding N-protected peptidyl ketones in good to excellent yields and in high enantiopurity. Triethylphosphite plays a key role as a supporting ligand by mitigating an undesired palladium-catalyzed decarbonylation-β-elimination of the α-amino thiol esters. The peptidyl ketone synthesis proceeds at room temperature under non-basic conditions and demonstrates a high tolerance to functionality. PMID:17263394

High anion gap metabolic acidosis induced by cumulation of ketones, L- and D-lactate, 5-oxoproline and acute renal failure.

PubMed

Heireman, Laura; Mahieu, Boris; Helbert, Mark; Uyttenbroeck, Wim; Stroobants, Jan; Piqueur, Marian

2017-07-27

Frequent causes of high anion gap metabolic acidosis (HAGMA) are lactic acidosis, ketoacidosis and impaired renal function. In this case report, a HAGMA caused by ketones, L- and D-lactate, acute renal failure as well as 5-oxoproline is discussed. A 69-year-old woman was admitted to the emergency department with lowered consciousness, hyperventilation, diarrhoea and vomiting. The patient had suffered uncontrolled type 2 diabetes mellitus, underwent gastric bypass surgery in the past and was chronically treated with high doses of paracetamol and fosfomycin. Urosepsis was diagnosed, whilst laboratory analysis of serum bicarbonate concentration and calculation of the anion gap indicated a  HAGMA. L-lactate, D-lactate, β-hydroxybutyric acid, acetone and 5-oxoproline serum levels were markedly elevated and renal function was impaired. We concluded that this case of HAGMA was induced by a variety of underlying conditions: sepsis, hyperglycaemia, prior gastric bypass surgery, decreased renal perfusion and paracetamol intake. Risk factors for 5-oxoproline intoxication present in this case are female gender, sepsis, impaired renal function and uncontrolled type 2 diabetes mellitus. Furthermore, chronic antibiotic treatment with fosfomycin might have played a role in the increased production of 5-oxoproline. Paracetamol-induced 5-oxoproline intoxication should be considered as a cause of HAGMA in patients with female gender, sepsis, impaired renal function or uncontrolled type 2 diabetes mellitus, even when other more obvious causes of HAGMA such as lactate, ketones or renal failure can be identified.

Synthesis and insect antifeedant activities of some substituted styryl 3,4-dichlorophenyl ketones

NASA Astrophysics Data System (ADS)

Thirunarayanan, G.; Surya, S.; Srinivasan, S.; Vanangamudi, G.; Sathiyendiran, V.

2010-01-01

Sixteen substituted styryl 3,4-dichlorophenyl ketones [ (2E)-1-(3,4-dichlorophenyl)-3-phenyl-2-propen-1-ones] were synthesized using eco-friendly benign stereoselective crossed-aldol reaction. They are characterized by their analytical, infrared, NMR and mass spectral data. The insect antifeedant activities of these chalcones were evaluated using Caster semilooper and Achoea janata L.

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

PubMed

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 < or =98% have been achieved with acetophenone as the substrate. Several other substrates were tested, among them 2-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.

Serum Adiponectin and Leptin Concentrations in Relation to Body Fat Distribution, Hematological Indices and Lipid Profile in Humans.

PubMed

Lubkowska, Anna; Radecka, Aleksandra; Bryczkowska, Iwona; Rotter, Iwona; Laszczyńska, Maria; Dudzińska, Wioleta

2015-09-14

The purpose of the study was to evaluate the relationship between serum adiponectin and leptin concentrations and body composition, hematological indices and lipid profile parameters in adults. The study involved 95 volunteers (BMI from 23.3 to 53 kg/m²). Anthropometric parameters were measured: body weight and height, waist and hip circumference, waist-to-hip ratio, body fat mass (BMF), subcutaneous and visceral fat mass (SFM, VFM), lean body mass (LBM), skeletal muscle mass (SMM). In serum we determined adiponectin and leptin concentrations, extracellular hemoglobin, total bilirubin, as well as lipid metabolism (TCh, HDL-Ch, LDL-Ch, TG). Mean adipokine levels were significantly higher in women (p ≤ 0.01), adiponectin significantly negatively correlated with body height and weight, systolic blood pressure and absolute LBM and SMM values. The same relation was observed for erythroid system indicators and lipid indicators. A positive correlation was exceptionally found between adiponectin and HDL-Ch. LEP negatively correlated with some percentage rates (%LBM, %SMM). Only in women, we observed a positive correlation between LEP and body weight, BMI and WHR. Studies on ADPN and the ADPN/LEP ratio as a valuable complementary diagnostic element in the prediction and prevention of cardiovascular diseases need to be continued.

Kinetic study of the reaction of the hydroxyl radical (OH) with methyl ethyl ketone (2-butanone) and its deuterated isotopomers at low pressure

NASA Astrophysics Data System (ADS)

Liljegren, J. A.; Stevens, P. S.

2012-12-01

Methyl ethyl ketone (2-butanone) in the atmosphere comes from a variety of sources. It is produced commercially as an industrial ketone. It can be formed as a result of the OH or Cl-initiated oxidation of C4-C6 alkanes, primarily n-butane, or from the reaction of some alkenes with OH or O3. Biogenic sources include direct emissions from certain plants as well as emissions from decaying plant matter. Methyl ethyl ketone is removed from the atmosphere primarily by its reaction with OH. A product of this reaction includes acetaldehyde, which is a hazardous air pollutant, can further react to produce peroxy acetyl nitrate (PAN), and can be a significant source of free radicals to the atmosphere. The absolute rate constant for the reaction of OH with methyl ethyl ketone has been measured as a function of temperature at low pressure using discharge-flow techniques coupled with laser induced fluorescence (LIF) detection of OH. In addition, measurements of the rate constants for the reactions of OH with two deuterated isotopomers of methyl ethyl ketone, including CD3C(O)CH2CH3 and CH3C(O)CD2CD3, will be presented to gain a better understanding of the mechanism for this reaction. Theoretical studies of the potential energy surface for this reaction suggest that the reaction proceeds through the formation of a hydrogen-bonded pre-reactive complex, similar to that of several other atmospherically relevant oxygenated VOCs such as acetone, acetic acid, and hydroxyacetone.

Advanced emissions-speciation methodologies for the auto/oil air-quality improvement research program. 2. Aldehydes, ketones, and alcohols. SAE technical paper series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swarin, S.J.; Loo, J.F.; Chladek, E.

1992-01-01

Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air Quality Improvement Research Program to provide emission data for comparison of individual reformulated fuels, individual vehicles, and for air modeling studies. The emission samples are collected in impingers which contain either 2,4-dinitrophenylhydrazine solution for the aldehydes and ketones or deionized water for the alcohols. Subsequent analyses by liquid chromatography for the aldehydes and ketones and gas chromatography for the alcohols utilized auto injectors and computerized data systems which permit high sample throughput with minimalmore » operator intervention. The quality control procedures developed and interlaboratory comparisons conducted as part of the program are also described. (Copyright (c) 1992 Society of Automotive Engineers, Inc.)« less

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

PubMed

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 (< or = 40 g carbohydrate/day) or a healthy-eating 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.

Stereogenic phosphorus-induced diastereoselective formation of chiral carbon during nucleophilic addition of chiral H-P species to aldehydes or ketones.

PubMed

Zhang, He; Sun, Yong-Ming; Yao, Lan; Ji, Si-Yu; Zhao, Chang-Qiu; Han, Li-Biao

2014-05-01

P,C-stereogenic α-hydroxyl phosphinates or phosphine oxides were prepared from the additions of (RP)-phosphinate to ketones or (RP)-phosphine oxide to aldehydes, respectively, catalyzed by bases at room temperature in up to >99:1 diasteromeric ratio (d.r.P/d.r.C) and 99 % yields. The diastereoselectivity was induced by reversible equilibrium and different stabilities between two diastereomers of adduct, which was caused by the spatial interaction between menthoxyl or menthyl to alkyl groups of aldehydes or ketones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

ULTRASOUND-ASSISTED EPOXIDATION OF OLEFINS AND A,B-UNSATURATED KETONES OVER HYDROTALCITES USING HYDROGEN PEROXIDE

EPA Science Inventory

An efficient ultrasound-assisted epoxidation of olefins and a,B-unsaturated ketones over hydrotacite catalysts in the presence of hydrogen peroxide and acetonitrile is described. This general and selective protocol is relatively fast and is applicable to a wide variety of substra...

Efficient purification and concentration of viruses from a large body of high turbidity seawater.

PubMed

Sun, Guowei; Xiao, Jinzhou; Wang, Hongming; Gong, Chaowen; Pan, Yingjie; Yan, Shuling; Wang, Yongjie

2014-01-01

Marine viruses are the most abundant entities in the ocean and play crucial roles in the marine ecological system. However, understanding of viral diversity on large scale depends on efficient and reliable viral purification and concentration techniques. Here, we report on developing an efficient method to purify and concentrate viruses from large body of high turbidity seawater. The developed method characterizes with high viral recovery efficiency, high concentration factor, high viral particle densities and high-throughput, and is reliable for viral concentration from high turbidity seawater. Recovered viral particles were used directly for subsequent analysis by epifluorescence microscopy, transmission electron microscopy and metagenomic sequencing. Three points are essential for this method:•The sampled seawater (>150 L) was initially divided into two parts, water fraction and settled matter fraction, after natural sedimentation.•Both viruses in the water fraction concentrated by tangential flow filtration (TFF) and viruses isolated from the settled matter fraction were considered as the whole viral community in high turbidity seawater.•The viral concentrates were re-concentrated by using centrifugal filter device in order to obtain high density of viral particles.

Can whole body vibration exercises affect growth hormone concentration? A systematic review.

PubMed

Paineiras-Domingos, Laisa Liane; Sá-Caputo, Danúbia da Cunha de; Moreira-Marconi, Eloá; Morel, Danielle Soares; da Fontoura Dionello, Carla; Sousa-Gonçalves, Cintia Renata; Frederico, Éric Heleno Freire Ferreira; Marín, Pedro Jesus; Tamini, Sofia; Sartorio, Alessandro; Bernardo-Filho, Mario

2017-10-01

Whole body vibration (WBV) has been recognized as an effective alternative exercise modality to resistance exercise for its ability in enhancing force and power, generating capacity in skeletal muscle, increasing bone mass and improving cardiovascular function. Since the effect of WBV exercises on growth hormone (GH) levels has been never compared and discussed, the aim of this study was to review systematically the literature to verify the WBV effects on GH concentration. By using PubMed, Scopus and PEDRo databases with the keywords 'growth hormone' or GH and 'whole body vibration' or WBV, we found and analysed 12 papers (182 subjects recruited), verifying their level of evidence (National Health and Medical Research Council hierarchy of evidence) and the methodological quality (PEDRo scale). Although WBV induced GH responses in nine out of 12 publications, caution should be however taken when considering the results due to the markedly different methodologies among these publications.

Resonance stabilization effects on ketone autoxidation: Isomer-specific cyclic ether and ketohydroperoxide formation in the low-temperature (400–625 K) oxidation of diethyl ketone

DOE PAGES

Scheer, Adam M.; Eskola, Arkke J.; Osborn, David L.; ...

2016-10-11

Here, the pulsed photolytic chlorine-initiated oxidation of diethyl ketone [DEK; (CH 3CH 2) 2C=O], 2,2,4,4- d 4-DEK [ d 4-DEK; (CH 3CD 2) 2C=O], and 1,1,1,5,5,5-d 6-DEK [ d 6-DEK; (CD 3CH 2) 2C=O] is studied at 8 torr and 1–2 atm and from 400–625 K. Cl atoms produced by laser photolysis react with diethyl ketone to form either primary (3-pentan-on-1-yl, R P) or secondary (3-pentan-on-2-yl, R S) radicals, which in turn react with O 2. Multiplexed time-of-flight mass spectrometry, coupled to either a hydrogen discharge lamp or tunable synchrotron photoionizing radiation, is used to detect products as a functionmore » of mass, time, and photon energy. At 8 torr, the nature of the chain propagating cyclic ether + OH channel changes as a function of temperature. At 450 K, the production of OH is mainly in conjunction with formation of 2,4-dimethyloxetan-3-one, resulting from reaction of the resonance-stabilized secondary R S with O 2. In contrast, at 550 K and 8 torr, 2-methyl-tetrahydrofuran-3-one, originating from oxidation of the primary radical (RP), is observed as the dominant cyclic ether product. Formation of both of these cyclic ether production channels proceeds via a resonance-stabilized hydroperoxy alkyl (QOOH) intermediate. Little or no ketohydroperoxide (KHP) is observed under the low-pressure conditions. At higher O 2 concentrations and higher pressures (1–2 atm), a strong KHP signal appears as the temperature is increased above 450 K. Definitive isomeric identification from measurements on the deuterated DEK isotopologues indicates the favored pathway produces a γ-KHP via resonance-stabilized alkyl, QOOH, and HOOPOOH radicals. Time-resolved measurements reveal the KHP formation becomes faster and signal more intense upon increasing temperature from 450 to 575 K before intensity drops significantly at 625 K. The KHP time profile also shows a peak followed by a gradual depletion for the extent of experiment. Several tertiary products exhibit a slow

Relationship Not Found Between Blood and Urine Concentrations and Body Mass Index in Humans With Apparently Adequate Boron Status.

PubMed

Koc, Fulya; Aysan, Erhan; Hasbahceci, Mustafa; Arpaci, Beyza; Gecer, Salih; Demirci, Selami; Sahin, Fikrettin

2016-06-01

The impact of boron on the development of obesity remains controversial in the analysis of experimental and clinical data. The objective of this study was to investigate the relationship between blood and urine boron concentrations and obesity in normal, overweight, obese, and morbidly obese subjects in different age groups. A total of 105 subjects were categorized into 12 groups based on body mass index and three different age levels: as young adult (18 to 34 years old), adult (35 to 54 years old), and older adult (greater than 55 years old). Age, gender, body mass index, and blood and urine boron concentrations were recorded for each subject. There were 50 women and 55 men, with a mean age of 44.63 ± 17.9 years. Blood and urine boron concentrations were similar among the groups (p = 0.510 and p = 0.228, respectively). However, a positive correlation between age and blood boron concentration (p = 0.001) was detected in contrast to the presence of a negative correlation between age and urine boron concentration (p = 0.027). Multiple linear regression analysis showed that there was no significant relationship between gender, age, and quantitative values of body mass index for each subject, and blood and urine boron concentrations. Although the relationship between boron and obesity has not been confirmed, changes of blood and urine boron concentrations with age may have some physiologic sequences to cause obesity.

Does Long-Term High Fat Diet Always Lead to Smaller Hippocampi Volumes, Metabolite Concentrations, and Worse Learning and Memory? A Magnetic Resonance and Behavioral Study in Wistar Rats.

PubMed

Setkowicz, Zuzanna; Gaździńska, Agata; Osoba, Joanna J; Karwowska, Karolina; Majka, Piotr; Orzeł, Jarosław; Kossowski, Bartosz; Bogorodzki, Piotr; Janeczko, Krzysztof; Wyleżoł, Mariusz; Gazdzinski, Stefan P

2015-01-01

Obesity is a worldwide epidemic with more than 600 million affected individuals. Human studies have demonstrated some alterations in brains of otherwise healthy obese individuals and elevated risk of neurodegenerative disease of old age; these studies have also pointed to slightly diminished memory and executive functions among healthy obese individuals. Similar findings were obtained in animal models of obesity induced by high fat diet. On the other hand, low carbohydrate high fat diets are currently promoted for losing weight (e.g., Atkin's style diets). However, the long-term effects of such diets are not known. Additionally, high fat diets leading to (mild) ketonemia were shown to improve brain function in elderly humans and in some animal models. To evaluate the hypothesis that long-term use of a high fat diet was associated with decreases in spatial memory, smaller hippocampi and hippocampi metabolite concentrations in Wistar rats. Twenty five male Wistar rats were put on high fat diet (HFD; 60% calories from fat, 30% from carbohydrates) on their 55th day of life, while 25 control male rats (CONs) remained on chow. Adequate levels of essential nutrients were provided. Both groups underwent memory tests in 8-arm radial maze at 3rd, 6th, 9th, and 12th month. 1H magnetic resonance spectroscopy was employed to measure concentrations of tNAA (marker of neuronal integrity) at one month and one year, whereas MRI was used to evaluate hippocampal volumes. Obese rats (OBRs) consumed similar amount of calories as CONs, but less proteins. However, their protein intake was within recommended amounts. Throughout the experiment OBRs had statistically higher concentrations of blood ketone bodies than CONs, but still within normal values. At post-mortem assessment, OBRs had 38% larger fat deposits than CONs (p<0.05), as evaluated by volume of epididymis fat, an acknowledged marker of fat deposits in rats. Contrary to our expectations, OBRs had better scores of memory

Syntheses of calix[4]pyrroles by amberlyst-15 catalyzed cyclocondensations of pyrrole with selected ketones.

PubMed

Chauhan, Shive Murat Singh; Garg, Bhaskar; Bisht, Tanuja

2007-11-09

A facile and efficient protocol is reported for the synthesis of calix[4]pyrroles and N-confused calix[4]pyrroles in moderate to excellent yields by reaction of dialkyl or cycloalkyl ketones with pyrrole catalyzed by reusable Amberlyst(TM)-15 under eco-friendly conditions.

Electrosynthesis of enaminones directly from methyl ketones and amines with nitromethane as a carbon source.

PubMed

Xu, Kun; Zhang, Zhenlei; Qian, Peng; Zha, Zhenggen; Wang, Zhiyong

2015-07-14

An efficient and mechanistically different method for the electrosynthesis of enaminone directly from methyl ketones, amines and nitromethane was developed. This transition-metal-free method proceeded at room temperature to give a wide array of enaminones in one step, utilizing nitromethane as the carbon source.

A FACILE ONE-POT SYNTHESIS OF β-KETO SULFONES FROM KETONES UNDER SOLVENT-FREE CONDITIONS

EPA Science Inventory

An easy solvent-free method is described for the conversion of ketones into β-keto sulfones in high yields that involves in situ generation of α-tosyloxyketones followed by nucleophilic substitution with sodium arene sulfinate in presence of tetra-butylammonium bromide at ...

β-Keto esters from ketones and ethyl chloroformate: a rapid, general, efficient synthesis of pyrazolones and their antimicrobial, in silico and in vitro cytotoxicity studies

PubMed Central

2013-01-01

Background Pyrazolones are traditionally synthesized by the reaction of β-keto esters with hydrazine and its derivatives. There are methods to synthesize β-keto esters from esters and aldehydes, but these methods have main limitation in varying the substituents. Often, there are a number of methods such as acylation of enolates in which a chelating effect has been employed to lock the enolate anion using lithium and magnesium salts; however, these methods suffer from inconsistent yields in the case of aliphatic acylation. There are methods to synthesize β-keto esters from ketones like caboxylation of ketone enolates using carbon dioxide and carbon monoxide sources in the presence of palladium or transition metal catalysts. Currently, the most general and simple method to synthesize β-keto ester is the reaction of dimethyl or ethyl carbonate with ketone in the presence of strong bases which also requires long reaction time, use of excessive amount of reagent and inconsistent yield. These factors lead us to develop a simple method to synthesize β-keto esters by changing the base and reagent. Results A series of β-keto esters were synthesized from ketones and ethyl chloroformate in the presence of base which in turn are converted to pyrazolones and then subjected to cytotoxicity studies towards various cancer cell lines and antimicrobial activity studies towards various bacterial and fungal strains. Conclusion The β-keto esters from ethyl chloroformate was successfully attempted, and the developed method is simple, fast and applicable to the ketones having the alkyl halogens, protecting groups like Boc and Cbz that were tolerated and proved to be useful in the synthesis of fused bicyclic and tricyclic pyrazolones efficiently using cyclic ketones. Since this method is successful for different ketones, it can be useful for the synthesis of pharmaceutically important pyrazolones also. The synthesized pyrazolones were subjected to antimicrobial, docking and

Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

PubMed Central

Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

Effect of carbonates/phosphates as nucleophilic catalysts in dimethylformamide for efficient cyanosilylation of aldehydes and ketones

PubMed Central

Prakash, G. K. Surya; Vaghoo, Habiba; Panja, Chiradeep; Surampudi, Vijayalakshmi; Kultyshev, Roman; Mathew, Thomas; Olah, George A.

2007-01-01

Cyanosilylation of aldehydes and aliphatic ketones can be carried out in dimethylformamide even without the use of any catalyst. In the presence of nucleophilic catalysts such as carbonate and phosphate salts, the reaction rate is significantly enhanced. PMID:17360603

Studies of Azetidin-2-one as a Reactive Enolate Synthon of β-Alanine for Condensations with Aldehydes and Ketones.

PubMed

Williams, David R; Donnell, Andrew F; Kammler, David C; Ward, Sarah A; Taylor, Levin

2016-11-04

Studies describe formation of the lithium enolate of N-(4-methoxybenzyloxy)azetidin-2-one (1) and characterization of representative aldol reactions with aldehydes and ketones. Diastereoselectivity features the production of anti-aldol adducts from α,β-unsaturated ketones and α-branched aliphatic aldehydes. The stereoselectivity is rationalized via closed, six-membered transition-state arrangements leading to the formation of Felkin-Anh and anti-Felkin products. Examples illustrate the direct incorporation of monocyclic β-lactams into a variety of molecular architectures. The utility of 1 as an enolate synthon of homoglycine (β-alanine) is illustrated by the efficient synthesis of novel β-amino acid derivatives, including complex 4-hydroxy-2-pyridinones.

A Cu(I)-Catalyzed C-H α-Amination of Aryl Ketones. Direct Synthesis of Imidazolinones

PubMed Central

Zhao, Baoguo; Du, Haifeng; Shi, Yian

2009-01-01

This paper describes an α-amination process of aryl ketones using CuCl as catalyst and di-tert-butyldiaziridinone as the nitrogen source. A variety of imidazolinone derivatives are prepared in moderate yields under mild conditions. A possible catalytic cycle is proposed for this reaction. PMID:19402696

Predictive comparisons of procalcitonin (PCT) level, arterial ketone body ratio (AKBR), APACHE III score and multiple organ dysfunction score (MODS) in systemic inflammatory response syndrome (SIRS).

PubMed

Lee, Young-Joo; Park, Chan-Hee; Yun, Jang-Woon; Lee, Young-Suk

2004-02-29

Procalcitonin (PCT) is a newly introduced marker of systemic inflammation and bacterial infection. A marked increase in circulating PCT level in critically ill patients has been related with the severity of illness and poor survival. The goal of this study was to compare the prognostic power of PCT and three other parameters, the arterial ketone body ratio (AKBR), the acute physiology, age, chronic health evaluation (APACHE) III score and the multiple organ dysfunction score (MODS), in the differentiation between survivors and nonsurvivors of systemic inflammatory response syndrome (SIRS). The study was performed in 95 patients over 16 years of age who met the criteria of SIRS. PCT and AKBR were assayed in arterial blood samples. The APACHE III score and MODS were recorded after the first 24 hours of surgical ICU (SICU) admission and then daily for two weeks or until either discharge or death. The patients were divided into two groups, survivors (n=71) and nonsurvivors (n=24), in accordance with the ICU outcome. They were also divided into three groups according to the trend of PCT level: declining, increasing or no change. Significant differences between survivors and nonsurvivors were found in APACHE III score and MODS throughout the study period, but in PCT value only up to the 7th day and in AKBR only up to the 3rd day. PCT values of the three groups were not significantly different on the first day between survivors and nonsurvivors. Receiver operating characteristic (ROC) curves for prediction of mortality by PCT, AKBR, APACHE III score and MODS were 0.690, 0.320, 0.915 and 0.913, respectively, on the admission day. In conclusion, PCT could have some use as a mortality predictor in SIRS patients but was less reliable than APACHE III score or MODS.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davidson, Stephen D.; Spies, Kurt A.; Mei, Donghai

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, andmore » 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.« less

Association Between Maternal Prepregnancy Body Mass Index and Plasma Folate Concentrations With Child Metabolic Health.

PubMed

Wang, Guoying; Hu, Frank B; Mistry, Kamila B; Zhang, Cuilin; Ren, Fazheng; Huo, Yong; Paige, David; Bartell, Tami; Hong, Xiumei; Caruso, Deanna; Ji, Zhicheng; Chen, Zhu; Ji, Yuelong; Pearson, Colleen; Ji, Hongkai; Zuckerman, Barry; Cheng, Tina L; Wang, Xiaobin

2016-08-01

Previous reports have linked maternal prepregnancy obesity with low folate concentrations and child overweight or obesity (OWO) in separate studies. To our knowledge, the role of maternal folate concentrations, alone or in combination with maternal OWO, in child metabolic health has not been examined in a prospective birth cohort. To test the hypotheses that maternal folate concentrations can significantly affect child metabolic health and that sufficient maternal folate concentrations can mitigate prepregnancy obesity-induced child metabolic risk. This prospective birth cohort study was conducted at the Boston Medical Center, Boston, Massachusetts. It included 1517 mother-child dyads recruited at birth from 1998 to 2012 and followed up prospectively up to 9 years from 2003 to 2014. Child body mass index z score calculated according to US reference data, OWO defined as a body mass index in the 85th percentile or greater for age and sex, and metabolic biomarkers (leptin, insulin, and adiponectin). The mean (SD) age was 28.6 (6.5) years for mothers and 6.2 (2.4) years for the children. An L-shaped association between maternal folate concentrations and child OWO was observed: the risk for OWO was higher among those in the lowest quartile (Q1) as compared with those in Q2 through Q4, with an odds ratio of 1.45 (95% CI, 1.13-1.87). The highest risk for child OWO was found among children of obese mothers with low folate concentrations (odds ratio, 3.05; 95% CI, 1.91-4.86) compared with children of normal-weight mothers with folate concentrations in Q2 through Q4 after accounting for multiple covariables. Among children of obese mothers, their risk for OWO was associated with a 43% reduction (odds ratio, 0.57; 95% CI, 0.34-0.95) if their mothers had folate concentrations in Q2 through Q4 compared with Q1. Similar patterns were observed for child metabolic biomarkers. In this urban low-income prospective birth cohort, we demonstrated an L-shaped association between

Normative data for regional sweat sodium concentration and whole-body sweating rate in athletes.

PubMed

Baker, Lindsay B; Barnes, Kelly A; Anderson, Melissa L; Passe, Dennis H; Stofan, John R

2016-01-01

The purpose of this study was to establish normative data for regional sweat sodium concentration ([Na+]) and whole-body sweating rate in athletes. Data from 506 athletes (367 adults, 139 youth; 404 male, 102 female) were compiled from observational athlete testing for a retrospective analysis. The participants were skill/team-sport (including American football, baseball, basketball, soccer and tennis) and endurance (including cycling, running and triathlon) athletes exercising in cool to hot environmental conditions (15-50 °C) during training or competition in the laboratory or field. A standardised regional absorbent patch technique was used to determine sweat [Na+] on the dorsal mid-forearm. Whole-body sweat [Na+] was predicted using a published regression equation (y = 0.57x+11.05). Whole-body sweating rate was calculated from pre- to post-exercise change in body mass, corrected for fluid/food intake (ad libitum) and urine output. Data are expressed as mean ± SD (range). Forearm sweat [Na+] and predicted whole-body sweat [Na+] were 43.6 ± 18.2 (12.6-104.8) mmol · L(-1) and 35.9 ± 10.4 (18.2-70.8) mmol · L(-1), respectively. Absolute and relative whole-body sweating rates were 1.21 ± 0.68 (0.26-5.73) L · h(-1) and 15.3 ± 6.8 (3.3-69.7) ml · kg(-1) · h(-1), respectively. This retrospective analysis provides normative data for athletes' forearm and predicted whole-body sweat [Na+] as well as absolute and relative whole-body sweating rate across a range of sports and environmental conditions.

Considerations of the Effects of Naphthalene Moieties on the Design of Proton-Conductive Poly(arylene ether ketone) Membranes for Direct Methanol Fuel Cells.

PubMed

Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Wei, Yuxue; Zhao, Chengji; Na, Hui

2016-09-14

Novel sulfonated poly(arylene ether ketones) (SDN-PAEK-x), consisting of dual naphthalene and flexible sulfoalkyl groups, were prepared via polycondensation, demethylation, and sulfobutylation grafting reaction. Among them, SDN-PAEK-1.94 membrane with the highest ion exchange capacity (IEC = 2.46 mequiv·g(-1)) exhibited the highest proton conductivity, which was 0.147 S· cm(-1) at 25 °C and 0.271 S·cm(-1) at 80 °C, respectively. The introduction of dual naphthalene moieties is expected to achieve much enhanced properties compared to those of sulfonated poly(arylene ether ketones) (SNPAEK-x), consisting of single naphthalene and flexible sulfoalkyl groups. Compared with SNPAEK-1.60 with a similar IEC, SDN-PAEK-1.74 membrane showed higher proton conductivity, higher IEC normalized conductivity, and higher effective proton mobility, although it had lower analytical acid concentration. The SDN-PAEK-x membranes with IECs higher than 1.96 mequiv·g(-1) also exhibited higher proton conductivity than that of recast Nafion membrane. Furthermore, SDN-PAEK-1.94 displayed a better single cell performance with a maximum power density of 60 mW·cm(-2) at 80 °C. Considering its high proton conductivity, excellent single cell performance, good mechanical stabilities, low membrane swelling, and methanol permeability, SDN-PAEK-x membranes are promising candidates as alternative polymer electrolyte membranes to Nafion for direct methanol fuel cell applications.

Determination of silver, antimony, bismuth, copper, cadmium and indium in ores, concentrates and related materials by atomic-absorption spectrophotometry after methyl isobutyl ketone extraction as iodides.

PubMed

Donaldson, E M; Wang, M

1986-03-01

Methods for determining ~ 0.2 mug g or more of silver and cadmium, ~ 0.5 mug g or more of copper and ~ 5 mug g or more of antimony, bismuth and indium in ores, concentrates and related materials are described. After sample decomposition and recovery of antimony and bismuth retained by lead and calcium sulphates, by co-precipitation with hydrous ferric oxide at pH 6.20 +/- 0.05, iron(III) is reduced to iron(II) with ascorbic acid, and antimony, bismuth, copper, cadmium and indium are separated from the remaining matrix elements by a single methyl isobutyl ketone extraction of their iodides from ~2M sulphuric acid-0.1M potassium iodide. The extract is washed with a sulphuric acid-potassium iodide solution of the same composition to remove residual iron and co-extracted zinc, and the extracted elements are stripped from the extract with 20% v v nitric acid-20% v v hydrogen peroxide. Alternatively, after the removal of lead sulphate by filtration, silver, copper, cadmium and indium can be extracted under the same conditions and stripped with 40% v v nitric acid-25% v v hydrochloric acid. The strip solutions are treated with sulphuric and perchloric acids and ultimately evaporated to dry ness. The individual elements are determined in a 24% v v hydrochloric acid medium containing 1000 mug of potassium per ml by atomic-absorption spectrophotometry with an air-acetylene flame. Tin, arsenic and molybdenum are not co-extracted under the conditions above. Results obtained for silver, antimony, bismuth and indium in some Canadian certified reference materials by these methods are compared with those obtained earlier by previously published methods.

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

PubMed

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.

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

PubMed Central

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-01-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions. PMID:27671606

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

NASA Astrophysics Data System (ADS)

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-09-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

Optical activities of steroid ketones - Elucidation of the octant rule

NASA Astrophysics Data System (ADS)

Hatanaka, Masashi; Sayama, Daisuke; Miyasaka, Makoto

2018-07-01

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.

A Simple One-pot Conversion of Aldehydes and Ketones to Enals

PubMed Central

Valenta, Petr; Drucker, Natalie A.; Bode, Jeffrey W.; Walsh, Patrick J.

2009-01-01

A simple and efficient method to convert aldehydes into α,β-unsaturated aldehydes with a two-carbon homologation is presented. Hydroboration of ethoxy acetylene with BH3•SMe2 generates tris(ethoxyvinyl) borane. Transmetallation with diethylzinc, addition to aldehydes or ketones, and acidic workup affords enals. When the addition is quenched with anilinium hydrochloride, 1,2-dithioglycol, or acetic anhydride the unsaturated imine, dithiolane, or 1,1-diacetate is isolated in high yield. These transformations can be performed in a one-pot procedure. PMID:19419211

Bioactive constituents of Chinese natural medicines. I. New sesquiterpene ketones with vasorelaxant effect from Chinese moxa, the processed leaves of Artemisia argyi Levl. et Vant.: moxartenone and moxartenolide.

PubMed

Yoshikawa, M; Shimada, H; Matsuda, H; Yamahara, J; Murakami, N

1996-09-01

Two new sesquiterpene ketones, moxartenone and moxartenolide, and three octadecadienoic acids were isolated from Chinese moxa, the processed leaves of Artemisia argyi LEVL. et VANT., together with two sesquiterpenes, five triterpenes, two phenyl propanoids and three polyoxyflavones. The chemical structures of new sesquiterpenes, moxartenone, moxartenolide, and octadecadienoic acids were determined on the basis of chemical and physiochemical evidence. Moxartenolide was found to inhibit the contractions induced by a high concentration of K+, by norepinephrine, and by serotonin in isolated aortic strips of rat, while moxartenone showed little activity.

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

PubMed Central

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

The allylation reactions of aromatic aldehydes and ketones with tin dichloride in water.

PubMed

Bian, Yan-Jiang; Xue, Wei-Li; Yu, Xu-Guang

2010-01-01

The allylation reactions of aromatic aldehydes and ketones were carried out in 31-86% yield using SnCl(2)-H(2)O system under ultrasound irradiation at r.t. for 5h. The reactions in the same system gave homoallyl alcohols in 21-84% yield with stirring at r.t. for 24h. Compared with traditional stirring methods, ultrasonic irradiation is more convenient and efficient.

Synthesis of 2-Ethenylcyclopropyl Aryl Ketones via Intramolecular SN2-like Displacement of an Ester.

PubMed

Jung, Michael E; Sun, Daniel L; Dwight, Timothy A; Yu, Peiyuan; Li, Wei; Houk, K N

2016-10-07

The efficient synthesis of trans-2-ethenylcyclopropyl aryl ketones via an intramolecular S N 2-like displacement of an allylic ester is reported. A novel 1,5-acyl shift process is also observed that contributes to the product mixture. Theoretical calculations provide a rationale for the observed product ratio.

Highly Enantioselective Three-Component Direct Mannich Reactions of Unfunctionalized Ketones Catalyzed by Bifunctional Organocatalysts

PubMed Central

Guo, Qunsheng; Zhao, John Cong-Gui

2013-01-01

A highly stereoselective three-component direct Mannich reaction between aromatic aldehydes, p-toluenesulfonamide, and unfunctionalized ketones was achieved through an enolate mechanism for the first time with a bifunctional quinidine thiourea catalyst. The corresponding N-tosylated β-aminoketones were obtained in high yields and excellent diastereo- and enantioselectivities (up to >99:1 dr and >99% ee). PMID:23343472

Biaxial deformation behaviour of poly-ether-ether-ketone

NASA Astrophysics Data System (ADS)

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).

Electron impact ionization of cycloalkanes, aldehydes, and ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Dhanoj; Antony, Bobby, E-mail: bka.ism@gmail.com

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 crossmore » 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.« less

Electron Impact Ion Fragmentation Pathways of Peracetylated C-glycoside Ketones Derived from Cyclic 1,3-diketones

USDA-ARS?s Scientific Manuscript database

Monosaccharide C-glycoside ketones have been prepared by aqueous-based Knoevenagel condensation of isotopically-labeled and unlabeled aldoses with cyclic diketones, 5,5-dimethyl-1,3-cyclohexanedione (dimedone) and 1,3-cyclohexanedione (1,3-CHD). The reaction products and their corresponding acetyla...

Selective synthesis of secondary amines by Pt nanowire catalyzed reductive amination of aldehydes and ketones with ammonia.

PubMed

Qi, Fenqiang; Hu, Lei; Lu, Shuanglong; Cao, Xueqin; Gu, Hongwei

2012-10-07

The process of the reductive amination of aldehydes or ketones in the presence of ammonia using unsupported ultra-thin Pt nanowires has been developed. This catalytic system shows high activity and selectivity under mild reaction conditions.

Acid-base and hormonal abnormalities in dogs with naturally occurring diabetes mellitus.

PubMed

Durocher, Lawren L; Hinchcliff, Kenneth W; DiBartola, Stephen P; Johnson, Susan E

2008-05-01

To examine acid-base and hormonal abnormalities in dogs with diabetes mellitus. Cross-sectional study. 48 dogs with diabetes mellitus and 17 healthy dogs. Blood was collected and serum ketone, glucose, lactate, electrolytes, insulin, glucagon, cortisol, epinephrine, norepinephrine, nonesterified fatty acid, and triglyceride concentrations were measured. Indicators of acid-base status were calculated and compared between groups. Serum ketone and glucose concentrations were significantly higher in diabetic than in healthy dogs, but there was no difference in venous blood pH or base excess between groups. Anion gap and strong ion difference were significantly higher and strong ion gap and serum bicarbonate concentration were significantly lower in the diabetic dogs. There were significant linear relationships between measures of acid-base status and serum ketone concentration, but not between measures of acid-base status and serum lactate concentration. Serum insulin concentration did not differ significantly between groups, but diabetic dogs had a wider range of values. All diabetic dogs with a serum ketone concentration > 1,000 micromol/L had a serum insulin concentration < 5 microU/mL. There were strong relationships between serum ketone concentration and serum glucagon-insulin ratio, serum cortisol concentration, and plasma norepinephrine concentration. Serum beta-hydroxybutyrate concentration, expressed as a percentage of serum ketone concentration, decreased as serum ketone concentration increased. Results suggested that ketosis in diabetic dogs was related to the glucagon-insulin ratio with only low concentrations of insulin required to prevent ketosis. Acidosis in ketotic dogs was attributable largely to high serum ketone concentrations.

A high-fat diet increases body weight and circulating estradiol concentrations but does not improve bone structural properties in ovariectomized mice.

PubMed

Cao, Jay J; Gregoire, Brian R

2016-04-01

Bone health is influenced by body mass and estrogen. The objective of the study was to determine whether high-fat diet-induced obesity affects bone structure and alters markers of bone turnover in ovariectomized (OVX) mice. We hypothesized that a high-fat diet would increase body weight gain and serum estradiol levels in OVX mice but would not improve bone structural parameter in OVX mice. Thirty-five C57BL/6 mice were either sham operated or OVX at the age of 4 months and then fed either a normal-fat diet (10% energy as fat) or a high-fat diet (45% energy as fat with extra fat from lard) ad libitum for 11 weeks. Ovariectomy increased body weight, serum tartrate-resistant acid phosphatase concentration, and expression of cathepsin K in bone; decreased serum estradiol concentration; and induced significant bone loss manifested by decreased bone volume/total volume (BV/TV), connectivity density (Conn.D), trabecular number, and trabecular thickness with increased trabecular separation and structural model index (P < .01). The high-fat diet increased body weight (P < .01) in OVX mice and nonsignificantly decreased BV/TV (P = .08) and Conn.D (P = .10). Despite having similar serum estradiol concentrations and higher body weight, OVX mice consuming the high-fat diet had lower BV/TV, Conn.D, trabecular number, trabecular thickness, and higher structural model index and trabecular separation than did sham mice fed the normal-fat diet. These findings indicate that increased body weight and elevated serum estradiol concentration induced by a high-fat diet do not mitigate ovariectomy-induced bone loss in mice. Published by Elsevier Inc.

(CF3CO)2O/CF3SO3H-mediated synthesis of 1,3-diketones from carboxylic acids and aromatic ketones

PubMed Central

Kim, JungKeun; Shokova, Elvira; Tafeenko, Victor

2014-01-01

Summary A very simple and convenient reaction for 1,3-diketone preparation from carboxylic acids and aromatic ketones in TFAA/TfOH system is described. When the β-phenylpropionic acids were used as starting materials, they initially gave 1-indanones and then underwent further acylation with the formation of 2-(β-phenylpropionyl)-1-indanones as the main reaction products. In addition, the application of the proposed protocol allowed for the synthesis of selected polysubstituted pyrazoles in a one-pot procedure directly from acids and ketones. PMID:25298794

Effects of body region and time on hair cortisol concentrations in chimpanzees (Pan troglodytes).

PubMed

Carlitz, Esther H D; Kirschbaum, Clemens; Miller, Robert; Rukundo, Joshua; van Schaik, Carel P

2015-11-01

Hair cortisol concentrations (HCC) are increasingly recognized as an integrated measure of the systemic cortisol secretion. Yet, we still know very little about confounding effects on HCC in animals. The present study therefore used hair from semi-wild and zoo living chimpanzees to investigate (1) intra-individual variability of HCC (body-region effect), and (2) the stability of HCC along the hair shaft (traditionally called the washout effect). Our results indicate that absolute HCC varied substantially between certain body regions, but a factor analysis revealed that these HCC differences were mainly attributable to one common source of variance. Thus, hair from all body regions provides similar biological signals and can be mixed, albeit at the cost of a lower signal-to-noise ratio. With regard to potential underlying mechanisms, we studied skin blood flow, as observed through thermal images from one chimpanzee. We found the general HCC pattern was reflected in differences in surface body temperature observed in this individual in three out of four body regions. In a separate set of samples, we found first evidence to suggest that the systematic cortisol decrease along the hair shaft, as observed in humans, is also present in chimpanzee hair. The effect was more pronounced in semi-wild than in zoo chimpanzees presumably due to more exposure to ambient weather conditions. Copyright © 2015 Elsevier Inc. All rights reserved.

Effects of Plyometric Versus Concentric and Eccentric Conditioning Contractions on Upper-Body Postactivation Potentiation.

PubMed

Ulrich, Gert; Parstorfer, Mario

2017-07-01

There are limited data on postactivation potentiation's (PAP) effects after plyometric conditioning contractions (CCs), especially in the upper body. This study compared plyometric CCs with concentric-eccentric and eccentric CCs aiming to improve upper-body power performance due to a PAP effect. Sixteen resistance-trained males completed 3 experimental trials in a randomized order that comprised either a plyometric (PLY), a concentric-eccentric (CON), or an eccentric-only (ECC) CC. Maximal muscle performance, as determined by a ballistic bench-press throw, was measured before (baseline) and 1, 4, 8, 12, and 16 min after each CC. Compared with baseline, bench-press power was significantly enhanced only in CON (P = .046, ES = 0.21) after 8 min of recovery. However, the results obtained from the comparisons between baseline power performance and the individual best power performance for each subject after each CC stimulus showed significant increases in PLY (P < .001, ES = 0.31) and CON (P < .001, ES = 0.38). There was no significant improvement in ECC (P = .106, ES = 0.11). The results indicate that only CON CCs generated increases in bench-press power after 8 min of rest. However, considering an individual rest interval, PLY CCs led to an enhanced power performance in the bench-press exercise, and this increase was comparable to that induced by CON CCs. Due to the easy practical application before a competition, PLY CCs might be an interesting part of warm-up strategies aiming to improve upper-body power performance by reason of PAP.

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

PubMed

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 < acetophenone < benzophenone. The Mulliken charges of the three solutes and CO2 molecules obtained by using quantum chemistry calculations described the order of the magnitude of the 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

Valproate causes metabolic disturbance in normal man.

PubMed Central

Turnbull, D M; Dick, D J; Wilson, L; Sherratt, H S; Alberti, K G

1986-01-01

Valproate is an important anticonvulsant which is rarely associated with fatal hepatotoxicity. Previous experiments have shown that valproate inhibits several metabolic processes in isolated rat hepatocytes and when administered to starved rats causes a fall in the blood concentrations of glucose and ketone bodies. Since these changes may be related to the hepatotoxicity, the effect of valproate administration on intermediary metabolism in man was studied. One gram of valproate given orally to fasted normal humans caused a 78% fall in the concentration of 3-hydroxybutyrate and a 60% fall in total ketones. Also the concentrations of lactate, pyruvate, alanine and glycerol increased after valproate administration. Similar changes were observed after intravenous administration of 400 mg of valproate. Valproate clearly has a significant effect on intermediary metabolism in the liver and this is probably related to the mechanism of the hepatotoxicity. PMID:3084712

The influence of sex, body composition, and nonesterified fatty acids on serum adipokine concentrations.

PubMed

Plaisance, Eric P; Grandjean, Peter W; Judd, Robert L; Jones, Kathy W; Taylor, J Kyle

2009-11-01

Serum adiponectin concentrations are higher in women than men. The sexual dimorphism for adiponectin has been attributed to the direct effects of testosterone on adipose tissue adiponectin secretion. However, serum testosterone and adiponectin concentrations are generally lower in obese men than lean men, suggesting that sex steroids may not be the only factor that contributes to sex differences in serum adiponectin. The primary objective of this study was to examine the influence of sex, body composition, and nonesterified fatty acids (NEFAs) on serum adiponectin concentrations. Women and men between the ages of 18 and 35 years were consecutively accrued into the study. Sixty-one participants were partitioned into normal-weight (15 female and 16 male) or obese (14 female and 16 male) groups. Blood samples were obtained after a 12-hour fast. Differences between groups were determined by analysis of variance with Tukey-Kramer post hoc testing. Serum adiponectin was 26% higher in women compared with men. Body mass index was associated with total serum adiponectin in men (r = -0.63, P < .05) but not women. Adiponectin was correlated with the homeostasis model assessment index in women (r = -0.56, P < .05) and men (r = -0.58, P < .05) and with NEFAs (r = -0.68, P < .05) in men only. After partitioning men and women into normal-weight and obese groups, serum adiponectin was lower and NEFAs were higher in obese men only. Homeostasis model assessment was similar between obese women and men despite higher NEFAs in the obese men. Leptin and plasminogen activator inhibitor-1 were higher in obese participants but were not associated with serum NEFAs. These results suggest that serum NEFAs may reduce adiponectin concentrations independent of their effects on insulin sensitivity in obese young men.

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

NASA Astrophysics Data System (ADS)

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.

A Lower Olfactory Capacity Is Related to Higher Circulating Concentrations of Endocannabinoid 2-Arachidonoylglycerol and Higher Body Mass Index in Women.

PubMed

Pastor, Antoni; Fernández-Aranda, Fernando; Fitó, Montserrat; Jiménez-Murcia, Susana; Botella, Cristina; Fernández-Real, Jose M; Frühbeck, Gema; Tinahones, Francisco J; Fagundo, Ana B; Rodriguez, Joan; Agüera, Zaida; Langohr, Klaus; Casanueva, Felipe F; de la Torre, Rafael

2016-01-01

The endocannabinoid (eCB) system can promote food intake by increasing odor detection in mice. The eCB system is over-active in human obesity. Our aim is to measure circulating eCB concentrations and olfactory capacity in a human sample that includes people with obesity and explore the possible interaction between olfaction, obesity and the eCB system. The study sample was made up of 161 females with five groups of body mass index sub-categories ranging from under-weight to morbidly obese. We assessed olfactory capacity with the "Sniffin´Sticks" test, which measures olfactory threshold-discrimination-identification (TDI) capacity. We measured plasma concentrations of the eCBs 2-arachidonoylglycerol (2-AG) and N-arachidonoylethanolamine or anandamide (AEA), and several eCB-related compounds, 2-acylglycerols and N-acylethanolamines. 2-AG and other 2-acylglycerols fasting plasma circulating plasma concentrations were higher in obese and morbidly obese subjects. AEA and other N-acylethanolamine circulating concentrations were lower in under-weight subjects. Olfactory TDI scores were lower in obese and morbidly obese subjects. Lower TDI scores were independently associated with higher 2-AG fasting plasma circulating concentrations, higher %body fat, and higher body mass index, after controlling for age, smoking, menstruation, and use of contraceptives. Our results show that obese subjects have a lower olfactory capacity than non-obese ones and that elevated fasting plasma circulating 2-AG concentrations in obesity are linked to a lower olfactory capacity. In agreement with previous studies we show that eCBs AEA and 2-AG, and their respective congeners have a distinct profile in relation to body mass index. The present report is the first study in humans in which olfactory capacity and circulating eCB concentrations have been measured in the same subjects.

Synthesis of ketones from biomass-derived feedstock.

PubMed

Meng, Qinglei; Hou, Minqiang; Liu, Huizhen; Song, Jinliang; Han, Buxing

2017-01-31

Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H 2 O/CH 2 Cl 2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H 2 O/CH 2 Cl 2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass.

Influence of sulfur oxidation state and steric bulk upon trifluoromethyl ketone (TFK) binding kinetics to carboxylesterases and fatty acid amide hydrolase (FAAH)

PubMed Central

Wheelock, Craig E.; Nishi, Kosuke; Ying, Andy; Jones, Paul D.; Colvin, Michael E.; Olmstead, Marilyn M.; Hammock, Bruce D.

2009-01-01

Carboxylesterases metabolize numerous exogenous and endogenous ester-containing compounds including the chemotherapeutic agent CPT-11, anti-influenza viral agent oseltamivir and many agrochemicals. Trifluoromethyl ketone (TFK)-containing compounds with a sulfur atom beta to the ketone moiety are some of the most potent carboxylesterase and amidase inhibitors identified to date. This study examined the effects of alkyl chain length (i.e., steric effects) and sulfur oxidation state upon TFK inhibitor potency (IC50) and binding kinetics (ki). The selective carboxylesterase inhibitor benzil was used as a non-TFK containing control. These effects were examined using two commercial esterases (porcine and rabbit liver esterase) and two human recombinant esterases (hCE-1 and hCE-2) as well as human recombinant fatty acid amide hydrolase (FAAH). In addition, the inhibition mechanism was examined using a combination of 1H NMR, X-ray crystallography and ab initio calculations. Overall, the data show that while sulfur oxidation state profoundly affects both inhibitor potency and binding kinetics, the steric effects dominate and override the contributions of sulfur oxidation. In addition, the data suggest that inclusion of a sulfur atom beta to the ketone contributes an increase (~5-fold) in inhibitor potency due to effects upon ketone hydration and/or intramolecular hydrogen bond formation. These results provide further information on the nature of the TFK binding interaction and will be useful in increasing our understanding of this basic biochemical process. PMID:18023188

Ethanol concentration in food and body condition affect foraging behavior in Egyptian fruit bats ( Rousettus aegyptiacus)

NASA Astrophysics Data System (ADS)

Sánchez, Francisco; Korine, Carmi; Kotler, Burt P.; Pinshow, Berry

2008-06-01

Ethanol occurs in fleshy fruit as a result of sugar fermentation by both microorganisms and the plant itself; its concentration [EtOH] increases as fruit ripens. At low concentrations, ethanol is a nutrient, whereas at high concentrations, it is toxic. We hypothesized that the effects of ethanol on the foraging behavior of frugivorous vertebrates depend on its concentration in food and the body condition of the forager. We predicted that ethanol stimulates food consumption when its concentration is similar to that found in ripe fruit, whereas [EtOH] below or above that of ripe fruit has either no effect, or else deters foragers, respectively. Moreover, we expected that the amount of food ingested on a particular day of feeding influences the toxic effects of ethanol on a forager, and consequently shapes its feeding decisions on the following day. We therefore predicted that for a food-restricted forager, ethanol-rich food is of lower value than ethanol-free food. We used Egyptian fruit bats ( Rousettus aegyptiacus) as a model to test our hypotheses, and found that ethanol did not increase the value of food for the bats. High [EtOH] reduced the value of food for well-fed bats. However, for food-restricted bats, there was no difference between the value of ethanol-rich and ethanol-free food. Thus, microorganisms, via their production of ethanol, may affect the patterns of feeding of seed-dispersing frugivores. However, these patterns could be modified by the body condition of the animals because they might trade-off the costs of intoxication against the value of nutrients acquired.

Efficient Three-Component Strecker Reaction of Aldehydes/Ketones via NHC-Amidate Palladium(II) Complex Catalysis

PubMed Central

Jarusiewicz, Jamie; Choe, Yvonne; Yoo, Kyung Soo; Park, Chan Pil

2009-01-01

A simple and efficient one-pot three-component method has been developed for the synthesis of α-aminonitriles. This Strecker reaction is applicable for aldehydes and ketones with aliphatic or aromatic amines and trimethyl siliyl cyanide in the presence of a palladium Lewis aid catalyst in dichloromethane solvent at room temperature. PMID:19265413

Asymmetric hydrogenation of aromatic ketones by new recyclable ionic tagged ferrocene-ruthenium catalyst system.

PubMed

Xu, Di; Zhou, Zhi-Ming; Dai, Li; Tang, Li-Wei; Zhang, Jun

2015-05-01

Newly developed ferrocene-oxazoline-phosphine ligands containing quaternary ammonium ionic groups exhibited excellent catalytic performance for the ruthenium-catalyzed hydrogenation of aromatic ketonic substrates to give chiral secondary alcohols with high levels of conversions and enantioselectivities. Simple manipulation process, water tolerance, high activity and good recyclable property make this catalysis practical and appealing. Copyright © 2015 Elsevier Ltd. All rights reserved.

Loss of body weight and fat and improved lipid profiles in obese rats fed apple pomace or apple juice concentrate.

PubMed

Cho, Kyung-Dong; Han, Chan-Kyu; Lee, Bog-Hieu

2013-09-01

The purpose of this study was to investigate the influence of apple pomace (AP) and apple juice concentrate (AC) supplementation on body weight and fat loss as well as lipid metabolism in obese rats fed a high-fat diet. Diet-induced obese rats were assigned to three groups (n=8 for each group): high fat diet (HFD) control, HFD containing 10% (w/w) AP, and HFD containing 10% (w/w) AC. There was also a normal diet group (n=8). After 5 weeks, body weight gain, adipose tissue weight, serum and hepatic lipid profiles, liver morphology, and adipocyte size were measured. Body weight gain, white adipose tissue (WAT) weight, serum total cholesterol, low-density lipoprotein cholesterol and triglyceride concentrations, epididymal adipocyte size, and lesion scores were significantly lower and serum high-density lipoprotein cholesterol concentration and brown adipose tissue weights were significantly higher in the AP and AC groups compared with the HFD group. In addition, atherogenic indices in the AP and AC groups were significantly lower than in the HFD group. These results indicate that supplementing apple products such as AP and AC may help suppress body weight and WAT gain, as well as improve lipid profiles in diet-induced obese rats.

Loss of Body Weight and Fat and Improved Lipid Profiles in Obese Rats Fed Apple Pomace or Apple Juice Concentrate

PubMed Central

Cho, Kyung-Dong; Han, Chan-Kyu

2013-01-01

Abstract The purpose of this study was to investigate the influence of apple pomace (AP) and apple juice concentrate (AC) supplementation on body weight and fat loss as well as lipid metabolism in obese rats fed a high-fat diet. Diet-induced obese rats were assigned to three groups (n=8 for each group): high fat diet (HFD) control, HFD containing 10% (w/w) AP, and HFD containing 10% (w/w) AC. There was also a normal diet group (n=8). After 5 weeks, body weight gain, adipose tissue weight, serum and hepatic lipid profiles, liver morphology, and adipocyte size were measured. Body weight gain, white adipose tissue (WAT) weight, serum total cholesterol, low-density lipoprotein cholesterol and triglyceride concentrations, epididymal adipocyte size, and lesion scores were significantly lower and serum high-density lipoprotein cholesterol concentration and brown adipose tissue weights were significantly higher in the AP and AC groups compared with the HFD group. In addition, atherogenic indices in the AP and AC groups were significantly lower than in the HFD group. These results indicate that supplementing apple products such as AP and AC may help suppress body weight and WAT gain, as well as improve lipid profiles in diet-induced obese rats. PMID:23909905

Highly efficient hydrophosphonylation of aldehydes and unactivated ketones catalyzed by methylene-linked pyrrolyl rare earth metal amido complexes.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Rong, Jiewei; Wang, Shaowu; Yang, Gaosheng; Zhu, Xiancui; Zhang, Lijun

2012-02-27

A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aqueous phase oligomerization of methyl vinyl ketone through photooxidation - Part 1: Aging processes of oligomers

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Salque, G.; Smaani, A.; Demelas, C.; Coulomb, B.; Vassalo, L.; Ravier, S.; Temime-Roussel, B.; Voisin, D.; Monod, A.

2014-06-01

Secondary organic aerosol (SOA) represents a substantial part of organic aerosol, which affects climate and human health. It is now accepted that one of the important pathways of SOA formation occurs via aqueous phase chemistry in the atmosphere. Recently, we have shown in a previous study (Renard et al., 2013) the mechanism of oligomerization of MVK (methyl vinyl ketone), and suggested that unsaturated water soluble organic compounds (UWSOC) might efficiently form SOA in wet aerosol particles, even for weakly soluble ones like MVK. The atmospheric relevance of these processes is explored by means of process model studies (in a companion paper). In the present study we investigate the aging of these aqueous phase MVK-oligomers (Part 1). We compared aqueous phase composition and SOA composition after nebulization, mainly by means of UPLC-ESI-MS and AMS, respectively. Both instruments match and show similar trend of oligomer formation and aging. The SMPS analysis performed on the nebulized solutions allow to quantify these SOA and to measure their mass yields. We have highlighted in the current study that MVK •OH-oxidation undergoes kinetic competition between functionalization and oligomerization. The SOA composition and its evolution highly depend on the precursor initial concentration. We determined the threshold of MVK concentration, i.e. 2 mM, from which oligomerization prevails over functionalization. Hence, at these concentrations, •OH-oxidation of MVK forms oligomers that are SV-OOA, with low O / C and high f43. Oligomers are then fragmented, via unidentified intermediates that have the properties of LV-OOA which then end into succinic, malonic and oxalic diacids. For lower initial MVK concentrations, the oligomerization is not the major process, and functionalization dominates, resulting in small carbonyls, dicarbonyls and mainly monoacids. The aging of these oligomers could be an explanation for the presence of a part of the diacids observed in aerosol.

Serum Beta Hydroxybutyrate Concentrations in Cats with Chronic Kidney Disease, Hyperthyroidism, or Hepatic Lipidosis.

PubMed

Gorman, L; Sharkey, L C; Armstrong, P J; Little, K; Rendahl, A

2016-01-01

Ketones, including beta hydroxybutyrate (BHB), are produced in conditions of negative energy balance and decreased glucose utilization. Serum BHB concentrations in cats are poorly characterized in diseases other than diabetes mellitus. Serum BHB concentrations will be increased in cats with chronic kidney disease (CKD), hyperthyroidism (HT), or hepatic lipidosis (HL). Twenty-eight client-owned cats with CKD, 34 cats with HT, and 15 cats with HL; 43 healthy cats. Prospective observational study. Serum BHB concentrations were measured at admission in cats with CKD, HT, and HL, for comparison with a reference interval established using healthy cats. Results of dipstick urine ketone measurement, when available, were compared to BHB measurement. Beta hydroxybutyrate was above the reference interval (<0.11 mmol/L) in 6/28 cats (21%) with CKD, 7/34 cats (20%) with HT, and 11/15 cats (73%) with HL, significantly exceeding the expected 2.5% above the reference interval for healthy cats (P < .001 for all groups). Elevations were mild in CKD and HT groups (median BHB 0.1 mmol/L for both groups, 80th percentile 0.12 and 0.11 mmol/L, respectively), but more marked in HL cats (median BHB 0.2 mmol/L, 80th percentile 0.84 mmol/L). None of 11 cats with increased serum BHB concentration having urine dipstick analysis performed within 24 h of sampling for BHB were ketonuric. Increases in serum BHB concentrations occur in cats with CKD, HT, and HL, and might provide an useful index of catabolism. Copyright © 2016 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

Design, synthesis, and bioactivities screening of a diaryl ketone-inspired pesticide molecular library as derived from natural products.

PubMed

Zhang, Hong; Jin, Hong; Ji, Lan-zhu; Tao, Ke; Liu, Wei; Zhao, Hao-yu; Hou, Tai-ping

2011-07-01

Three natural products, 1,5-diphenylpentan-1-one, 1,5-diphenylpent-2-en-1-one, and 3-hydroxy-1,5-diphenylpentan-1-one, with good insecticidal activities were extracted from Stellera chamaejasme L. Based on their shared diaryl ketone moiety as 'pharmacophores', a series of diaryl ketones were synthesized and tested for insecticidal activity, acetylcholinesterase inhibitory activity, and antifungal activity. All synthesized compounds showed poor insecticidal and acetylcholinesterase inhibitory activities. Compound III with a furyl ring showed strong activities against plant pathogenic fungi. The IC(50) of compound (E)-1-(2,4-dichlorophenyl)-3-(furan-2-yl)- -prop-2-en-1-one (III(2) ) was 1.20 mg/L against Rhizoctonia solani, suggesting its strong potential as a novel antifungal drug. © 2011 John Wiley & Sons A/S.

Rise and Fall: Poly(phenyl vinyl ketone) Photopolymerization and Photodegradation under Visible and UV Radiation.