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Sample records for anion gap metabolic

  1. Metabolic alkalosis from unsuspected ingestion: use of urine pH and anion gap.

    PubMed

    Yi, Joo-Hark; Han, Sang-Woong; Song, June-Seok; Kim, Ho-Jung

    2012-04-01

    Underlying causes of metabolic alkalosis may be evident from history, evaluation of effective circulatory volume, and measurement of urine chloride concentration. However, identification of causes may be difficult for certain conditions associated with clandestine behaviors, such as surreptitious vomiting, use of drugs or herbal supplements with mineralocorticoid activity, abuse of laxatives or diuretics, and long-term use of alkalis. In these circumstances, clinicians often are bewildered by unexplained metabolic alkalosis from an incomplete history or persistent deception by the patient, leading to misdiagnosis and poor outcome. We present a case of severe metabolic alkalosis and hypokalemia with a borderline urine chloride concentration in an alcoholic patient treated with a thiazide. The cause of the patient's metabolic alkalosis eventually was linked to surreptitious ingestion of baking soda. This case highlights the necessity of a high index of suspicion for the diverse clandestine behaviors that can cause metabolic alkalosis and the usefulness of urine pH and anion gap in its differential diagnosis.

  2. High Anion Gap Metabolic Acidosis after a Suicide Attempt with Cyanide: The Rebirth of Cyanide Poisoning.

    PubMed

    Hsiao, Po-Jen; Chang, Che-Fu; Chiu, Chih-Chien; Chan, Jenq-Shyong; Chiang, Wen-Fang; Wu, Chia-Chao; Lin, Shih-Hua; Chen, Jin-Shuen

    2015-01-01

    A 33-year-old woman was admitted to our emergency department in a state of unconsciousness after attempting suicide with unknown substances. Severe metabolic acidosis (pH: 6.81), with a high anion gap (36.2) and high lactate level (20.2 mmol/L), was observed. After four hours of intensive medical treatment, the patient regained consciousness, with a return of the arterial pH to 7.42. Finally, cyanide intoxication was diagnosed based on the detection of a serum cyanide level of 3.5 mg/L. The presence of a high anion gap associated with severe lactic acidosis is a clue for making a rapid differential diagnosis of acute cyanide intoxication. Providing intensive and immediate supportive management is also crucial, even in cases without obtainable specific antidotes.

  3. Closing the gap on unmeasured anions

    PubMed Central

    Kellum, John A

    2003-01-01

    Many critically ill and injured patients, especially those with metabolic acidosis, have abnormally high levels of unmeasured anions in their blood. At the same time, such patients are prone to hypoalbuminemia, which makes the traditional anion gap calculation inaccurate. Thus, little is known about the epidemiology and clinical consequences of an excess in unmeasured anions in the blood. Indeed, even the etiology of these "missing ions" is often unclear. Unfortunately, more precise means of quantifying unmeasured anions, such as the strong ion gap (SIG), are cumbersome to use clinically. However, a simple means of correcting the anion gap can be used to estimate SIG and may provide additional insight into this common clinical problem. PMID:12793870

  4. Krebs cycle anions in metabolic acidosis.

    PubMed

    Bowling, Francis G; Morgan, Thomas J

    2005-10-05

    For many years it has been apparent from estimates of the anion gap and the strong ion gap that anions of unknown identity can be generated in sepsis and shock states. Evidence is emerging that at least some of these are intermediates of the citric acid cycle. The exact source of this disturbance remains unclear, because a great many metabolic blocks and bottlenecks can disturb the anaplerotic and cataplerotic pathways that enter and leave the cycle. These mechanisms require clarification with the use of tools such as gas chromatography-mass spectrometry.

  5. Unmeasured anions in metabolic acidosis: unravelling the mystery.

    PubMed

    Forni, Lui G; McKinnon, William; Hilton, Philip J

    2006-01-01

    In the critically ill, metabolic acidosis is a common observation and, in clinical practice, the cause of this derangement is often multi-factorial. Various measures are often employed to try and characterise the aetiology of metabolic acidosis, the most popular of which is the anion gap. The purpose of the anion gap can be perceived as a means by which the physician is alerted to the presence of unmeasured anions in plasma that contribute to the observed acidosis. In many cases, the causative ion may be easily identified, such as lactate, but often the causative ion(s) remain unidentified, even after exclusion of the 'classic' causes. We describe here the various attempts in the literature that have been made to address this observation and highlight recent studies that reveal potential sources of such hitherto unmeasured anions.

  6. The Anion Gap is a Predictive Clinical Marker for Death in Patients with Acute Pesticide Intoxication.

    PubMed

    Lee, Sun-Hyo; Park, Samel; Lee, Jung-Won; Hwang, Il-Woong; Moon, Hyung-Jun; Kim, Ki-Hwan; Park, Su-Yeon; Gil, Hyo-Wook; Hong, Sae-Yong

    2016-07-01

    Pesticide formulation includes solvents (methanol and xylene) and antifreeze (ethylene glycol) whose metabolites are anions such as formic acid, hippuric acid, and oxalate. However, the effect of the anion gap on clinical outcome in acute pesticide intoxication requires clarification. In this prospective study, we compared the anion gap and other parameters between surviving versus deceased patients with acute pesticide intoxication. The following parameters were assessed in 1,058 patients with acute pesticide intoxication: blood chemistry (blood urea nitrogen, creatinine, glucose, lactic acid, liver enzymes, albumin, globulin, and urate), urinalysis (ketone bodies), arterial blood gas analysis, electrolytes (Na(+), K(+), Cl(-) HCO3 (-), Ca(++)), pesticide field of use, class, and ingestion amount, clinical outcome (death rate, length of hospital stay, length of intensive care unit stay, and seriousness of toxic symptoms), and the calculated anion gap. Among the 481 patients with a high anion gap, 52.2% had a blood pH in the physiologic range, 35.8% had metabolic acidosis, and 12.1% had acidemia. Age, anion gap, pesticide field of use, pesticide class, seriousness of symptoms (all P < 0.001), and time lag after ingestion (P = 0.048) were significant risk factors for death in univariate analyses. Among these, age, anion gap, and pesticide class were significant risk factors for death in a multiple logistic regression analysis (P < 0.001). In conclusions, high anion gap is a significant risk factor for death, regardless of the accompanying acid-base balance status in patients with acute pesticide intoxication.

  7. The Anion Gap is a Predictive Clinical Marker for Death in Patients with Acute Pesticide Intoxication

    PubMed Central

    2016-01-01

    Pesticide formulation includes solvents (methanol and xylene) and antifreeze (ethylene glycol) whose metabolites are anions such as formic acid, hippuric acid, and oxalate. However, the effect of the anion gap on clinical outcome in acute pesticide intoxication requires clarification. In this prospective study, we compared the anion gap and other parameters between surviving versus deceased patients with acute pesticide intoxication. The following parameters were assessed in 1,058 patients with acute pesticide intoxication: blood chemistry (blood urea nitrogen, creatinine, glucose, lactic acid, liver enzymes, albumin, globulin, and urate), urinalysis (ketone bodies), arterial blood gas analysis, electrolytes (Na+, K+, Cl- HCO3-, Ca++), pesticide field of use, class, and ingestion amount, clinical outcome (death rate, length of hospital stay, length of intensive care unit stay, and seriousness of toxic symptoms), and the calculated anion gap. Among the 481 patients with a high anion gap, 52.2% had a blood pH in the physiologic range, 35.8% had metabolic acidosis, and 12.1% had acidemia. Age, anion gap, pesticide field of use, pesticide class, seriousness of symptoms (all P < 0.001), and time lag after ingestion (P = 0.048) were significant risk factors for death in univariate analyses. Among these, age, anion gap, and pesticide class were significant risk factors for death in a multiple logistic regression analysis (P < 0.001). In conclusions, high anion gap is a significant risk factor for death, regardless of the accompanying acid-base balance status in patients with acute pesticide intoxication. PMID:27366016

  8. Anion gap corrected for albumin, phosphate and lactate is a good predictor of strong ion gap in critically ill patients: a nested cohort study

    PubMed Central

    Zampieri, Fernando Godinho; Park, Marcelo; Ranzani, Otavio Tavares; Maciel, Alexandre Toledo; de Souza, Heraldo Possolo; da Cruz Neto, Luiz Monteiro; da Silva, Fabiano Pinheiro

    2013-01-01

    Objective Corrected anion gap and strong ion gap are commonly used to estimate unmeasured anions. We evaluated the performance of the anion gap corrected for albumin, phosphate and lactate in predicting strong ion gap in a mixed population of critically ill patients. We hypothesized that anion gap corrected for albumin, phosphate and lactate would be a good predictor of strong ion gap, independent of the presence of metabolic acidosis. In addition, we evaluated the impact of strong ion gap at admission on hospital mortality. Methods We included 84 critically ill patients. Correlation and agreement between the anion gap corrected for albumin, phosphate and lactate and strong ion gap was evaluated by the Pearson correlation test, linear regression, a Bland-Altman plot and calculating interclass correlation coefficient. Two subgroup analyses were performed: one in patients with base-excess <-2mEq/L (low BE group - lBE) and the other in patients with base-excess >-2mEq/L (high BE group - hBE). A logistic regression was performed to evaluate the association between admission strong ion gap levels and hospital mortality. Results There was a very strong correlation and a good agreement between anion gap corrected for albumin, phosphate and lactate and strong ion gap in the general population (r2=0.94; bias 1.40; limits of agreement -0.75 to 3.57). Correlation was also high in the lBE group (r2=0.94) and in the hBE group (r2=0.92). High levels of strong ion gap were present in 66% of the whole population and 42% of the cases in the hBE group. Strong ion gap was not associated with hospital mortality by logistic regression. Conclusion Anion gap corrected for albumin, phosphate and lactate and strong ion gap have an excellent correlation. Unmeasured anions are frequently elevated in critically ill patients with normal base-excess. However, there was no association between unmeasured anions and hospital mortality. PMID:24213083

  9. Sheathless capillary electrophoresis‐mass spectrometry for anionic metabolic profiling

    PubMed Central

    Gulersonmez, Mehmet Can; Lock, Stephen; Hankemeier, Thomas

    2015-01-01

    The performance of CE coupled on‐line to MS via a sheathless porous tip sprayer was evaluated for anionic metabolic profiling. A representative metabolite mixture and biological samples were used for the evaluation of various analytical parameters, such as peak efficiency (plate numbers), migration time and peak area repeatability, and LODs. The BGE, i.e. 10% acetic acid (pH 2.2), previously used for cationic metabolic profiling was now assessed for anionic metabolic profiling by using MS detection in negative ion mode. For test compounds, RSDs for migration times and peak areas were below 2 and 11%, respectively, and plate numbers ranged from 60 000 to 40 0000 demonstrating a high separation efficiency. Critical metabolites with low or no retention on reversed‐phase LC could be efficiently separated and selectively analyzed by the sheathless CE‐MS method. An injection volume of only circa 20 nL resulted in LODs between 10 and 200 nM (corresponding to an amount of 0.4–4 fmol), which was an at least tenfold improvement as compared to LODs obtained by conventional CE‐MS approaches for these analytes. The methodology was applied to anionic metabolic profiling of glioblastoma cell line extracts. Overall, a sheathless CE‐MS method has been developed for highly efficient and sensitive anionic metabolic profiling studies, which can also be used for cationic metabolic profiling studies by only switching the MS detection and separation voltage polarity. PMID:26593113

  10. Do anionic titanium dioxide nano-clusters reach bulk band gap? A density functional theory study.

    PubMed

    Qu, Zheng-Wang; Zhu, Hui

    2010-07-30

    The electronic properties of both neutral and anionic (TiO(2))(n) (n = 1-10) clusters are investigated by extensive density functional theory calculations. The predicted electron detachment energies and excitation gaps of anionic clusters agree well with the original experimental anion photoelectron spectra (APES). It is shown that the old way to analyze APES tends to overestimate vertical excitation gaps (VGA) of large anionic clusters, due to the nature of multiple electronic origins for the higher APES bands. Moreover, the VGA of anionic TiO(2) clusters are evidently smaller than those of neutral clusters, which may also be the case for other metal oxide clusters with high electron affinity.

  11. Clinical significance of the fractional excretion of anions in metabolic acidosis.

    PubMed

    Kim, H Y; Han, J S; Jeon, U S; Joo, K W; Earm, J H; Ahn, C; Kim, S; Lee, J S; Kim, G H

    2001-06-01

    The fractional excretion of anions has been proposed as a new index for the differential diagnosis of metabolic acidosis, identifying the properties of the conjugate base by examining the renal handling of the anion. Here, we investigated clinical significance of the fractional excretion of anions in pathophysiologic diagnosis of metabolic acidosis by measuring urine ammonium (NH4+) excretion, the ratio of A plasma anion gap/delta plasma HCO3- concentration (deltaAG/deltaHCO3-), and fractional excretion of anions in three different groups of metabolic acidosis: acid overproduction (8 patients with lactic acidosis, 8 with diabetic ketoacidosis, 3 with hippuric acidosis following glue sniffing), acid underexcretion (10 patients with chronic renal failure) and normal controls (10 normal volunteers who underwent 3-day NH4Cl loading). As expected, urine NH4+ excretion was higher in overproduction acidosis than in acid-loaded normal controls (88.1 +/- 12.3 vs. 54.0 +/- 3.7 mmol/day, p < 0.05), and it was lower in chronic renal failure than in acid-loaded normal controls (12.8 +/- 1.7 vs. 54.0 +/- 3.7 mmol/day, p < 0.05). The fractional excretion of anions had no difference between overproduction acidosis and chronic renal failure (41.2 +/- 42.8% vs. 41.0 +/- 8.1%). However, the fractional excretion of anions showed significant differences between the subgroups in acid overproduction (lactic acidosis, 4.7 +/- 0.3%; diabetic ketoacidosis, 45.8 +/- 3.1%; hippuric acidosis, 126.0 +/- 14.4%; p < 0.05). The ratio of plasma deltaAG/deltaHCO3- also exhibited significant differences between the subgroups in acid overproduction (lactic acidosis, 1.5 +/- 0.1; diabetic ketoacidosis, 1.0 +/- 0.1; hippuric acidosis, 0.3 +/- 0.1; p < 0.05). There was an inverse linear correlation between the fractional excretion of anions and the ratio of plasma deltaAG/deltaHCO3- (r2 =-0.89, p < 0.05). In conclusion, determination of the fractional excretion of anions may provide a useful clue to the

  12. Serum anion gap, bicarbonate and biomarkers of inflammation in healthy individuals in a national survey

    PubMed Central

    Farwell, Wildon R.; Taylor, Eric N.

    2010-01-01

    Background In vitro data suggest that lower extracellular pH activates the immune system. We conducted a population-based study of the relation between serum acid–base status and inflammation. Methods We examined the serum anion gap and serum levels of bicarbonate and inflammatory biomarkers in 4525 healthy adults who participated in the National Health and Nutrition Examination Survey during 1999–2006. We excluded participants who had chronic disease, recent infection and an estimated glomerular filtration rate of less than 60 mL/min per 1.73 m2. Results The mean values of serum anion gap, bicarbonate level, leukocyte count and C-reactive protein level were all within normal limits. After adjustment for age, sex, ethnic background, body mass index, serum albumin level and other factors, we found that a higher anion gap and lower bicarbonate level were associated with a higher leukocyte count and higher C-reactive protein level. Compared with participants in the lowest quartile of anion gap, those in the highest quartile had a leukocyte count that was 1.0 × 09/L higher and a C-reactive protein level that was 10.9 nmol/L higher (p < 0.01). Compared with participants in the highest quartile of bicarbonate level, those in the lowest quartile had a leukocyte count that was 0.7 × 109/L higher and a C-reactive protein level that was 4.0 nmol/L higher (p ≤ 0.02). A higher anion gap and lower bicarbonate level were also associated with a higher platelet count, a larger mean platelet volume and a higher ferritin level. Interpretation A higher serum anion gap and lower bicarbonate level were associated with higher levels of inflammatory biomarkers in a healthy sample of the general population. Further studies are needed to elucidate the relation between acid–base status and inflammation. PMID:20008503

  13. Propylene Glycol Poisoning From Excess Whiskey Ingestion: A Case of High Osmolal Gap Metabolic Acidosis.

    PubMed

    Cunningham, Courtney A; Ku, Kevin; Sue, Gloria R

    2015-01-01

    In this report, we describe a case of high anion gap metabolic acidosis with a significant osmolal gap attributed to the ingestion of liquor containing propylene glycol. Recently, several reports have characterized severe lactic acidosis occurring in the setting of iatrogenic unintentional overdosing of medications that use propylene glycol as a diluent, including lorazepam and diazepam. To date, no studies have explored potential effects of excess propylene glycol in the setting of alcohol intoxication. Our patient endorsed drinking large volumes of cinnamon flavored whiskey, which was likely Fireball Cinnamon Whisky. To our knowledge, this is the first case of propylene glycol toxicity from an intentional ingestion of liquor containing propylene glycol.

  14. Anion Gap Toxicity in Alloxan Induced Type 2 Diabetic Rats Treated with Antidiabetic Noncytotoxic Bioactive Compounds of Ethanolic Extract of Moringa oleifera

    PubMed Central

    2014-01-01

    Moringa oleifera (MO) is used for a number of therapeutic purposes. This raises the question of safety and possible toxicity. The objective of the study was to ascertain the safety and possible metabolic toxicity in comparison with metformin, a known drug associated with acidosis. Animals confirmed with diabetes were grouped into 2 groups. The control group only received oral dose of PBS while the test group was treated with ethanolic extract of MO orally twice daily for 5-6 days. Data showed that the extract significantly lowered glucose level to normal values and did not cause any significant cytotoxicity compared to the control group (P = 0.0698); there was no gain in weight between the MO treated and the control groups (P > 0.8115). However, data showed that treatment with an ethanolic extract of MO caused a decrease in bicarbonate (P < 0.0001), and more than twofold increase in anion gap (P < 0.0001); metformin treatment also decreased bicarbonate (P < 0.0001) and resulted in a threefold increase in anion gap (P < 0.0001). Conclusively, these data show that while MO appears to have antidiabetic and noncytotoxic properties, it is associated with statistically significant anion gap acidosis in alloxan induced type 2 diabetic rats. PMID:25548560

  15. Anion Gap Toxicity in Alloxan Induced Type 2 Diabetic Rats Treated with Antidiabetic Noncytotoxic Bioactive Compounds of Ethanolic Extract of Moringa oleifera.

    PubMed

    Omabe, Maxwell; Nwudele, Chibueze; Omabe, Kenneth Nwobini; Okorocha, Albert Egwu

    2014-01-01

    Moringa oleifera (MO) is used for a number of therapeutic purposes. This raises the question of safety and possible toxicity. The objective of the study was to ascertain the safety and possible metabolic toxicity in comparison with metformin, a known drug associated with acidosis. Animals confirmed with diabetes were grouped into 2 groups. The control group only received oral dose of PBS while the test group was treated with ethanolic extract of MO orally twice daily for 5-6 days. Data showed that the extract significantly lowered glucose level to normal values and did not cause any significant cytotoxicity compared to the control group (P = 0.0698); there was no gain in weight between the MO treated and the control groups (P > 0.8115). However, data showed that treatment with an ethanolic extract of MO caused a decrease in bicarbonate (P < 0.0001), and more than twofold increase in anion gap (P < 0.0001); metformin treatment also decreased bicarbonate (P < 0.0001) and resulted in a threefold increase in anion gap (P < 0.0001). Conclusively, these data show that while MO appears to have antidiabetic and noncytotoxic properties, it is associated with statistically significant anion gap acidosis in alloxan induced type 2 diabetic rats.

  16. Mammalian Metabolism of β-Carotene: Gaps in Knowledge

    PubMed Central

    Shete, Varsha; Quadro, Loredana

    2013-01-01

    β-carotene is the most abundant provitamin A carotenoid in human diet and tissues. It exerts a number of beneficial functions in mammals, including humans, owing to its ability to generate vitamin A as well as to emerging crucial signaling functions of its metabolites. Even though β-carotene is generally considered a safer form of vitamin A due to its highly regulated intestinal absorption, detrimental effects have also been ascribed to its intake, at least under specific circumstances. A better understanding of the metabolism of β-carotene is still needed to unequivocally discriminate the conditions under which it may exert beneficial or detrimental effects on human health and thus to enable the formulation of dietary recommendations adequate for different groups of individuals and populations worldwide. Here we provide a general overview of the metabolism of this vitamin A precursor in mammals with the aim of identifying the gaps in knowledge that call for immediate attention. We highlight the main questions that remain to be answered in regards to the cleavage, uptake, extracellular and intracellular transport of β-carotene as well as the interactions between the metabolism of β-carotene and that of other macronutrients such as lipids. PMID:24288025

  17. Regulation of mitochondrial function by voltage dependent anion channels in ethanol metabolism and the Warburg effect.

    PubMed

    Lemasters, John J; Holmuhamedov, Ekhson L; Czerny, Christoph; Zhong, Zhi; Maldonado, Eduardo N

    2012-06-01

    Voltage dependent anion channels (VDAC) are highly conserved proteins that are responsible for permeability of the mitochondrial outer membrane to hydrophilic metabolites like ATP, ADP and respiratory substrates. Although previously assumed to remain open, VDAC closure is emerging as an important mechanism for regulation of global mitochondrial metabolism in apoptotic cells and also in cells that are not dying. During hepatic ethanol oxidation to acetaldehyde, VDAC closure suppresses exchange of mitochondrial metabolites, resulting in inhibition of ureagenesis. In vivo, VDAC closure after ethanol occurs coordinately with mitochondrial uncoupling. Since acetaldehyde passes through membranes independently of channels and transporters, VDAC closure and uncoupling together foster selective and more rapid oxidative metabolism of toxic acetaldehyde to nontoxic acetate by mitochondrial aldehyde dehydrogenase. In single reconstituted VDAC, tubulin decreases VDAC conductance, and in HepG2 hepatoma cells, free tubulin negatively modulates mitochondrial membrane potential, an effect enhanced by protein kinase A. Tubulin-dependent closure of VDAC in cancer cells contributes to suppression of mitochondrial metabolism and may underlie the Warburg phenomenon of aerobic glycolysis. This article is part of a Special Issue entitled: VDAC structure, function, and regulation of mitochondrial metabolism.

  18. Band gap reduction in GaNSb alloys due to the anion mismatch

    SciTech Connect

    Veal, T.D.; Piper, L.F.J.; Jollands, S.; Bennett, B.R.; Jefferson, P.H.; Thomas, P.A.; McConville, C.F.; Murdin, B.N.; Buckle, L.; Smith, G.W.; Ashley, T.

    2005-09-26

    The structural and optoelectronic properties in GaN{sub x}Sb{sub 1-x} alloys (0{<=}x<0.02) grown by molecular-beam epitaxy on both GaSb substrates and AlSb buffer layers on GaAs substrates are investigated. High-resolution x-ray diffraction (XRD) and reciprocal space mapping indicate that the GaN{sub x}Sb{sub 1-x} epilayers are of high crystalline quality and the alloy composition is found to be independent of substrate, for identical growth conditions. The band gap of the GaNSb alloys is found to decrease with increasing nitrogen content from absorption spectroscopy. Strain-induced band-gap shifts, Moss-Burstein effects, and band renormalization were ruled out by XRD and Hall measurements. The band-gap reduction is solely due to the substitution of dilute amounts of highly electronegative nitrogen for antimony, and is greater than observed in GaNAs with the same N content.

  19. Effect of band gap engineering in anionic-doped TiO2 photocatalyst

    NASA Astrophysics Data System (ADS)

    Samsudin, Emy Marlina; Abd Hamid, Sharifah Bee

    2017-01-01

    A simple yet promising strategy to modify TiO2 band gap was achieved via dopants incorporation which influences the photo-responsiveness of the photocatalyst. The mesoporous TiO2 was successfully mono-doped and co-doped with nitrogen and fluorine dopants. The results indicate that band gap engineering does not necessarily requires oxygen substitution with nitrogen or/and fluorine, but from the formation of additional mid band and Ti3+ impurities states. The formation of oxygen vacancies as a result of modified color centres and Ti3+ ions facilitates solar light absorption and influences the transfer, migration and trapping of the photo-excited charge carriers. The synergy of dopants in co-doped TiO2 shows better optical properties relative to single N and F doped TiO2 with c.a 0.95 eV band gap reduction. Evidenced from XPS, the synergy between N and F in the co-doped TiO2 uplifts the valence band towards the conduction band. However, the photoluminescence data reveals poorer electrons and holes separation as compared to F-doped TiO2. This observation suggests that efficient solar light harvesting was achievable via N and F co-doping, but excessive defects could act as charge carriers trapping sites.

  20. Regulation of Mitochondrial Function by Voltage Dependent Anion Channels in Ethanol Metabolism and the Warburg Effect

    PubMed Central

    Lemasters, John J.; Holmuhamedov, Ekhson L.; Czerny, Christoph; Zhong, Zhi; Maldonado, Eduardo N.

    2012-01-01

    Voltage dependent anion channels (VDAC) are highly conserved proteins that are responsible for permeability of the mitochondrial outer membrane to hydrophilic metabolites like ATP, ADP and respiratory substrates. Although previously assumed to remain open, VDAC closure is emerging as an important mechanism for regulation of global mitochondrial metabolism in apoptotic cells and also in cells that are not dying. During hepatic ethanol oxidation to acetaldehyde, VDAC closure suppresses exchange of mitochondrial metabolites, resulting in inhibition of ureagenesis. In vivo, VDAC closure after ethanol occurs coordinately with mitochondrial uncoupling. Since acetaldehyde passes through membranes independently of channels and transporters, VDAC closure and uncoupling together foster selective and more rapid oxidative metabolism of toxic acetaldehyde to nontoxic acetate by mitochondrial aldehyde dehydrogenase. In single reconstituted VDAC, tubulin decreases VDAC conductance, and in HepG2 hepatoma cells, free tubulin negatively modulates mitochondrial membrane potential, an effect enhanced by protein kinase A. Tubulin-dependent closure of VDAC in cancer cells contributes to suppression of mitochondrial metabolism and may underlie the Warburg phenomenon of aerobic glycolysis. PMID:22172804

  1. [Nutrition, acid-base metabolism, cation-anion difference and total base balance in humans].

    PubMed

    Mioni, R; Sala, P; Mioni, G

    2008-01-01

    The relationship between dietary intake and acid-base metabolism has been investigated in the past by means of the inorganic cation-anion difference (C(+)(nm)-A(-)(nm)) method based on dietary ash-acidity titration after the oxidative combustion of food samples. Besides the inorganic components of TA (A(-)(nm)-C(+)(nm)), which are under renal control, there are also metabolizable components (A(-)(nm)-C(+)(nm)) of TA, which are under the control of the intermediate metabolism. The whole body base balance, NBb(W), is obtained only by the application of C(+)(nm)-A(-)(nm) to food, feces and urine, while the metabolizable component (A(-)(nm)-C(+)(nm)) is disregarded. A novel method has been subsequently suggested to calculate the net balance of fixed acid, made up by the difference between the input of net endogenous acid production: NEAP = SO(4)(2-)+A(-)(m)-(C(+)(nm)-A(-)(nm)), and the output of net acid excretion: NAE = TA + NH(4)(+) - HCO(3)(-). This approach has been criticized because 1) it includes metabolizable acids, whose production cannot be measured independently; 2) the specific control of metabolizable acid and base has been incorrectly attributed to the kidney; 3) the inclusion of A-m in the balance input generates an acid overload; 4) the object of measurement in making up a balance has to be the same, a condition not fulfilled as NEAP is different from NAE. Lastly, by rearranging the net balance of the acid equation, the balance of nonmetabolizable acid equation is obtained. Therefore, any discrepancy between these two equations is due to the inaccuracy in the urine measurement of metabolizable cations and/or anions.

  2. Modifications in nitric oxide and superoxide anion metabolism induced by fructose overload in rat heart are prevented by (-)-epicatechin.

    PubMed

    Calabró, Valeria; Piotrkowski, Barbara; Fischerman, Laura; Vazquez Prieto, Marcela A; Galleano, Monica; Fraga, Cesar G

    2016-04-01

    Fructose overload promotes functional and metabolic derangements in humans and in animal experimental models. Evidence suggests that dietary flavonoids have the ability to prevent/attenuate the development of metabolic diseases. In this work we investigated the effects of (-)-epicatechin on the modifications induced by fructose overload in the rat heart in terms of nitric oxide and superoxide metabolism. Male Sprague Dawley rats received 10% (w/v) fructose in the drinking water for 8 weeks, with or without (-)-epicatechin (20 mg per kg body weight per day) in the rat chow diet. These conditions of fructose overload did not lead to overt manifestations of heart hypertrophy or tissue remodeling. However, biochemical and molecular changes were observed and could represent the onset of functional alterations. (-)-Epicatechin prevented a compromised NO bioavailability and the development of oxidative stress produced by fructose overload essentially acting on superoxide anion metabolism. In this line, the increase in superoxide anion production, the overexpression of NOX2 subunit p47phox and of NOX4, the decrease in superoxide dismutase activity, and the higher oxidized/reduced glutathione ratio installed by fructose overload were absent in the rats receiving (-)-epicatechin. These results support the hypothesis that diets rich in (-)-epicatechin could prevent the onset and progression of heart dysfunctions associated with metabolic alterations.

  3. Effect of anionic salts on selenium metabolism in nonlactating, pregnant dairy cows.

    PubMed

    Gant, R G; Sanchez, W; Kincaid, R L

    1998-06-01

    The objective of this trial was to determine whether anionic salts in the diets of nonlactating, pregnant cows for 14 to 21 d prepartum affected measures of Se status. One of three dietary treatments (control, anionic salts, and anionic salts plus Se) was administered to 34 nonlactating, pregnant cows using a completely randomized design with repeated measures. The anionic salts were delivered via gelatin capsules that were administered orally in two equal amounts per day, and the Se (3 mg/d) was administered via an intraruminal bolus. The incidence of milk fever among cows was not significantly different across dietary treatments. The severity of hypocalcemia as indicated by concentrations of ionized Ca in serum collected < 2 h postpartum was significantly lessened by dietary anionic salts. Supplementation of anionic salts to the diet did not significantly affect serum Ca concentrations at either 7 d prepartum or 7 d postpartum. Anionic salts did not affect concentrations of Se in blood; however, Se supplementation of the diets of cows significantly increased postpartum concentrations of Se in serum. No treatment effects were detected for concentrations of Se in either serum or whole blood of newborn calves. In conclusion, these data indicate that diets supplemented with anionic salts for 14 to 21 d prepartum and the supplementation of diets with Se had independent effects on concentrations of minerals in blood. Thus, anionic salts administered to prevent milk fever without danger of significantly reducing the transfer of Se from the dam to the calf and without compromising the Se status of the cow when the anionic salts are limited to administration for 14 to 21 d before calving.

  4. A 44-year-old woman with metabolic acidosis, high anion gap, and delayed neurologic deterioration.

    PubMed

    Vakil, Abhay; Upadhyay, Hinesh; Sherani, Khalid; Cervellione, Kelly; Trepeta, Scott; Patel, Mahendra C

    2015-01-01

    A 44-year-old woman was brought to the ED from John F. Kennedy International Airport. The patient was returning with her son from a 3-month visit to Bangladesh. Her journey started with a 4-h flight from Dhaka, Bangladesh to Dubai, United Arab Emirates. She consumed 240 mL of whiskey during the flight. This was followed by a 14-h flight from Dubai to New York. According to the patient's son, she did not consume any alcohol during the second flight. The patient was in her usual state of health with normal mentation throughout her journey. Upon landing, she started complaining of shortness of breath. After disembarking, she was witnessed to have seizure-like activity with involuntary passage of urine, following which she collapsed. The patient was intubated by emergency medical services in the field.

  5. Tuning the near-gap electronic structure of Cu2O by anion-cation co-doping for enhanced solar energy conversion

    NASA Astrophysics Data System (ADS)

    Si, Yuan; Yang, Hao-Ming; Wu, Hong-Yu; Huang, Wei-Qing; Yang, Ke; Peng, Ping; Huang, Gui-Fang

    2017-01-01

    Doping is an effective strategy to tune the electronic properties of semiconductors, but some side effects caused by mono-doping degrade the specific performance of matrixes. As a model system to minimize photoproduced electron-hole pairs recombination by anion-cation co-doping, we investigate the electronic structures and optical properties of (Fe+N) co-doped Cu2O using the first-principles calculations. Compared to the case of mono-doping, the FeCuNO (a Fe (N) atom substituting a Cu (O) atom) co-doping reduces the energy cost of doping as a consequence of the charge compensation between the iron and nitrogen impurities, which eliminates the isolated levels (induced by mono-dopant) in the band gap. Interestingly, it is found that the contributions of different host atoms (Cu and O) away from anion (N) and cation (Fe) dopants to the variation of near band gap electronic structure of the co-doped Cu2O are different. Moreover, co-doping reduces the band gap and increases the visible-light absorption of Cu2O. Both band gap reduction and low recombination rate are critical elements for efficient light-to-current conversion in co-doped semiconductor photocatalysts. These findings raise the prospect of using co-doped Cu2O with specifically engineered electronic properties in a variety of solar applications.

  6. Gap-filling analysis of the iJO1366 Escherichia coli metabolic network reconstruction for discovery of metabolic functions

    PubMed Central

    2012-01-01

    Background The iJO1366 reconstruction of the metabolic network of Escherichia coli is one of the most complete and accurate metabolic reconstructions available for any organism. Still, because our knowledge of even well-studied model organisms such as this one is incomplete, this network reconstruction contains gaps and possible errors. There are a total of 208 blocked metabolites in iJO1366, representing gaps in the network. Results A new model improvement workflow was developed to compare model based phenotypic predictions to experimental data to fill gaps and correct errors. A Keio Collection based dataset of E. coli gene essentiality was obtained from literature data and compared to model predictions. The SMILEY algorithm was then used to predict the most likely missing reactions in the reconstructed network, adding reactions from a KEGG based universal set of metabolic reactions. The feasibility of these putative reactions was determined by comparing updated versions of the model to the experimental dataset, and genes were predicted for the most feasible reactions. Conclusions Numerous improvements to the iJO1366 metabolic reconstruction were suggested by these analyses. Experiments were performed to verify several computational predictions, including a new mechanism for growth on myo-inositol. The other predictions made in this study should be experimentally verifiable by similar means. Validating all of the predictions made here represents a substantial but important undertaking. PMID:22548736

  7. Metabolic acidosis.

    PubMed

    Lim, Salim

    2007-01-01

    Acute metabolic acidosis is frequently encountered in critically ill patients. Metabolic acidosis can occur as a result of either the accumulation of endogenous acids that consumes bicarbonate (high anion gap metabolic acidosis) or loss of bicarbonate from the gastrointestinal tract or the kidney (hyperchloremic or normal anion gap metabolic acidosis). The cause of high anion gap metabolic acidosis includes lactic acidosis, ketoacidosis, renal failure and intoxication with ethylene glycol, methanol, salicylate and less commonly with pyroglutamic acid (5-oxoproline), propylene glycole or djenkol bean (gjenkolism). The most common causes of hyperchloremic metabolic acidosis are gastrointestinal bicarbonate loss, renal tubular acidosis, drugs-induced hyperkalemia, early renal failure and administration of acids. The appropriate treatment of acute metabolic acidosis, in particular organic form of acidosis such as lactic acidosis, has been very controversial. The only effective treatment for organic acidosis is cessation of acid production via improvement of tissue oxygenation. Treatment of acute organic acidosis with sodium bicarbonate failed to reduce the morbidity and mortality despite improvement in acid-base parameters. Further studies are required to determine the optimal treatment strategies for acute metabolic acidosis.

  8. Linkage of organic anion transporter-1 to metabolic pathways through integrated "omics"-driven network and functional analysis.

    PubMed

    Ahn, Sun-Young; Jamshidi, Neema; Mo, Monica L; Wu, Wei; Eraly, Satish A; Dnyanmote, Ankur; Bush, Kevin T; Gallegos, Tom F; Sweet, Douglas H; Palsson, Bernhard Ø; Nigam, Sanjay K

    2011-09-09

    The main kidney transporter of many commonly prescribed drugs (e.g. penicillins, diuretics, antivirals, methotrexate, and non-steroidal anti-inflammatory drugs) is organic anion transporter-1 (OAT1), originally identified as NKT (Lopez-Nieto, C. E., You, G., Bush, K. T., Barros, E. J., Beier, D. R., and Nigam, S. K. (1997) J. Biol. Chem. 272, 6471-6478). Targeted metabolomics in knockouts have shown that OAT1 mediates the secretion or reabsorption of many important metabolites, including intermediates in carbohydrate, fatty acid, and amino acid metabolism. This observation raises the possibility that OAT1 helps regulate broader metabolic activities. We therefore examined the potential roles of OAT1 in metabolic pathways using Recon 1, a functionally tested genome-scale reconstruction of human metabolism. A computational approach was used to analyze in vivo metabolomic as well as transcriptomic data from wild-type and OAT1 knock-out animals, resulting in the implication of several metabolic pathways, including the citric acid cycle, polyamine, and fatty acid metabolism. Validation by in vitro and ex vivo analysis using Xenopus oocyte, cell culture, and kidney tissue assays demonstrated interactions between OAT1 and key intermediates in these metabolic pathways, including previously unknown substrates, such as polyamines (e.g. spermine and spermidine). A genome-scale metabolic network reconstruction generated some experimentally supported predictions for metabolic pathways linked to OAT1-related transport. The data support the possibility that the SLC22 and other families of transporters, known to be expressed in many tissues and primarily known for drug and toxin clearance, are integral to a number of endogenous pathways and may be involved in a larger remote sensing and signaling system (Ahn, S. Y., and Nigam, S. K. (2009) Mol. Pharmacol. 76, 481-490, and Wu, W., Dnyanmote, A. V., and Nigam, S. K. (2011) Mol. Pharmacol. 79, 795-805). Drugs may alter metabolism by

  9. Influence of different calcium contents in diets supplemented with anionic salts on bone metabolism in periparturient dairy cows.

    PubMed

    Liesegang, A; Chiappi, C; Risteli, J; Kessler, J; Hess, H D

    2007-04-01

    At the initiation of lactation, Ca homeostatic mechanisms have to react to a tremendous increase in demand for Ca. Mobilization of Ca from bone and increased absorption from the gastrointestinal tract are required to re-establish homeostasis. It has been shown that dietary anions play an important role in the prevention of milk fever by mobilizing Ca from bone and by increasing Ca absorption in the GI tract. The purpose of the present study was to investigate the influence of different Ca contents in diets supplemented with anionic salts on bone metabolism of dairy cows. Twenty-four holstein cows (housed inside, second to fourth lactation) without a milk fever history were divided into four groups (A, B, C, D). Each group was fed a different diet which was given from day 263 of gestation till the day of parturition. Group A and B received a low calcium diet (4 g/kg DM) whereas group C and D received a high Ca diet (8 g/kg DM). In addition group B and D received anionic salts. The DCAD was calculated with the formula: DCAD (mEq/kg DM)=(0.2 Ca2++0.16 Mg2++Na++K+)-(Cl-+0.6 S2-+0.65 P3-). Blood and urine samples were collected on days 256, 270 and 277 of gestation, on the day of parturition as well as the following 5 days and on days 9, 14 and 19 after parturition. Serum Ca, P, Mg, ICTP, OC, VITD, PTH and urinary pH were analysed. The bone resorption marker ICTP showed a significant increase after parturition in all the groups. On the contrary, the bone formation marker OC decreased after parturition in all the groups. The VITD concentrations in group D and the urinary pH in group B were significantly lower compared to the other groups (p<0.05). The Ca concentrations tended to be higher in group B around parturition than in all the other groups. No significant influence of the four different diets on all the other parameters could be shown. In conclusion, this data showed that the addition of anions and the different Ca contents had no significant influence on bone

  10. Effects of anionic salts in a pre-partum dairy ration on calcium metabolism.

    PubMed

    van Dijk, C J; Lourens, D C

    2001-06-01

    The effects of anionic salts in the transition diet on serum and urine calcium at calving and on peripartal health, subsequent milk production and fertility performance were studied in a well-managed, high-producing Friesland dairy herd. Over a period of a year, approximately 21 days before the expected date of calving, 28 pre-partum heifers and 44 multiparous dry cows were randomly allocated within parity to 1 of 2 transition diets, designated control and experimental anionic diets. The anionic diet contained the same quantities of the basic transition ration fed to the control group as well as a standard anionic salt mixture containing 118 g NH4Cl, 36 g (NH4)2SO4 and 68 g MgSO4 (total 222 g) per animal per day. This reduced the DCAD to -11.68 mEq/100 g dietary dry matter compared to +13.57 for the control diet. Blood and urine were randomly sampled from 7 to 8 animals within each category within 3 hours post-partum. Serum calcium (total and ionised) and creatinine, urine calcium and creatinine and the fractional clearance of calcium were assessed. Relevant clinical, milk production, and fertility data were collected. The total serum calcium (2.07 versus 1.60 mmol/l), serum ionised calcium (1.12 vs 1.02 mmol/l), urine calcium (0.92 vs 0.10 mmol/l) and the fractional clearance of calcium (1.88 vs 0.09%) were significantly higher(P <0.01) at calving for multiparous cows fed the anionic diet compared to those fed the control diet. In the primiparous cows there were no significant differences in serum calcium levels. However, the urine calcium (1.07 vs 0.43 mmol/l) and the fractional clearance of calcium was higher (1.75 vs 0.45%) in cows fed the anionic diet (P <0.05 and 0.01 respectively). These results illustrated that there were benefits, although no differences were demonstrated with respect to health, milk production or fertility. The supplementation of diets with anionic salts in the last 2-3 weeks before calving has the potential to significantly improve

  11. Voltage-dependent anion channels modulate mitochondrial metabolism in cancer cells: regulation by free tubulin and erastin.

    PubMed

    Maldonado, Eduardo N; Sheldon, Kely L; DeHart, David N; Patnaik, Jyoti; Manevich, Yefim; Townsend, Danyelle M; Bezrukov, Sergey M; Rostovtseva, Tatiana K; Lemasters, John J

    2013-04-26

    Respiratory substrates and adenine nucleotides cross the mitochondrial outer membrane through the voltage-dependent anion channel (VDAC), comprising three isoforms--VDAC1, 2, and 3. We characterized the role of individual isoforms in mitochondrial metabolism by HepG2 human hepatoma cells using siRNA. With VDAC3 to the greatest extent, all VDAC isoforms contributed to the maintenance of mitochondrial membrane potential, but only VDAC3 knockdown decreased ATP, ADP, NAD(P)H, and mitochondrial redox state. Cells expressing predominantly VDAC3 were least sensitive to depolarization induced by increased free tubulin. In planar lipid bilayers, free tubulin inhibited VDAC1 and VDAC2 but not VDAC3. Erastin, a compound that interacts with VDAC, blocked and reversed mitochondrial depolarization after microtubule destabilizers in intact cells and antagonized tubulin-induced VDAC blockage in planar bilayers. In conclusion, free tubulin inhibits VDAC1/2 and limits mitochondrial metabolism in HepG2 cells, contributing to the Warburg phenomenon. Reversal of tubulin-VDAC interaction by erastin antagonizes Warburg metabolism and restores oxidative mitochondrial metabolism.

  12. Comparison of the regulation, metabolic functions, and roles in virulence of the glyceraldehyde-3-phosphate dehydrogenase homologues gapA and gapB in Staphylococcus aureus.

    PubMed

    Purves, Joanne; Cockayne, Alan; Moody, Peter C E; Morrissey, Julie A

    2010-12-01

    The Gram-positive bacterium Staphylococcus aureus contains two glyceraldehyde-3-phosphate dehydrogenase (GAPDH) homologues known as GapA and GapB. GapA has been characterized as a functional GAPDH protein, but currently there is no biological evidence for the role of GapB in metabolism in S. aureus. In this study we show through a number of complementary methods that S. aureus GapA is essential for glycolysis while GapB is essential in gluconeogenesis. These proteins are reciprocally regulated in response to glucose concentrations, and both are influenced by the glycolysis regulator protein GapR, which is the first demonstration of the role of this regulator in S. aureus and the first indication that GapR homologues control genes other than those within the glycolytic operon. Furthermore, we show that both GapA and GapB are important in the pathogenesis of S. aureus in a Galleria mellonella model of infection, showing for the first time in any bacteria that both glycolysis and gluconeogenesis have important roles in virulence.

  13. Effects of altering dietary cation-anion difference on calcium and energy metabolism in peripartum cows.

    PubMed

    Moore, S J; VandeHaar, M J; Sharma, B K; Pilbeam, T E; Beede, D K; Bucholtz, H F; Liesman, J S; Horst, R L; Goff, J P

    2000-09-01

    Our objective was to determine the effects of varying dietary cation-anion differences (DCAD: meq[(Na + K) - (Cl + S)]/100 g of dry matter) in prepartum diets on Ca, energy, and endocrine status prepartum and postpartum. Holstein cows (n = 21) and heifers (n = 34) were fed diets with varying amounts of CaCl2, CaSO4, and MgSO4 to achieve a DCAD of +15 (control), 0, or -15 meq/100 g of dry matter for the last 24 d before expected calving. Dietary Ca concentration was increased (by CaCO3 supplementation) with decreasing DCAD. Plasma ionized Ca concentrations prepartum and at calving in both cows and heifers increased with reduced DCAD in the diet. At calving, plasma ionized Ca concentration was 3.67, 3.85, and 4.35 for cows and 4.44, 4.57, and 4.62 mg/dl for heifers fed diets containing +15, 0, and -15 DCAD, respectively. All heifers had normal concentrations of plasma ionized Ca (>4 mg/dl) at calving. Also at calving, plasma concentrations ofparathyroid hormone and calcitriol were less in cows and heifers fed diets containing reduced DCAD, but the plasma concentration of hydroxyproline was not affected by diet. Prepartum dry matter intake, energy balance, and body weight gains were lower and concentration of liver triglyceride was higher for heifers but not cows fed the -15 DCAD diet. Also, nonesterified fatty acids the last week prepartum were positively correlated with liver triglyceride for heifers but not cows. Feeding of anionic salts plus CaCO3 to reduce DCAD to -15 and increase Ca in prepartum diets prevents hypocalcemia at calving in cows, but decreases prepartum dry matter intake and increases the concentration of liver triglyceride in heifers. That heifers maintained calcium homeostasis at calving regardless of diet but ate less when fed the -15 DCAD diet suggests that they should not be fed anionic salts before calving.

  14. Cell metabolic changes of porphyrins and superoxide anions by anthracene and benzo(a)pyrene.

    PubMed

    Uribe-Hernández, Raúl; Pérez-Zapata, Aura J; Vega-Barrita, María L; Ramón-Gallegos, Eva; Amezcua-Allieri, Myriam A

    2008-09-01

    The aim of this work was to evaluate the induction of protoporphyrins IX (PpIX) activity and superoxide anions (SO) in human leukocytes exposed to anthracene (ANT) and benzo(a)pyrene (B(a)P). The leukocyte LC(50)s for both hydrocarbons and the PpIX accumulation and SO overproduction were measured. The LC(50)s were 0.35 and 3.23μM for ANT and B(a)P, respectively. A linear relationship (r=0.97, p<0.01) between PpIX and ANT concentration was obtained. The induced accumulation of PpIX was proportional (r=0.63, p<0.01) to B(a)P concentration. SO overproduction showed a linear relationship (r=0.83, p<0.05) with ANT concentrations. The linear regression analysis of the effect of B(a)P on the superoxide anion overproduction showed a good coefficient (r=0.97, p<0.01), showed that ANT and B(a)P exposure induces PpIX accumulation, probably by disruption of the haem biosynthesis. ANT and B(a)P induce SO overproduction, perhaps through a process of redox cycling.

  15. Likelihood-based gene annotations for gap filling and quality assessment in genome-scale metabolic models

    SciTech Connect

    Benedict, Matthew N.; Mundy, Michael B.; Henry, Christopher S.; Chia, Nicholas; Price, Nathan D.; Maranas, Costas D.

    2014-10-16

    Genome-scale metabolic models provide a powerful means to harness information from genomes to deepen biological insights. With exponentially increasing sequencing capacity, there is an enormous need for automated reconstruction techniques that can provide more accurate models in a short time frame. Current methods for automated metabolic network reconstruction rely on gene and reaction annotations to build draft metabolic networks and algorithms to fill gaps in these networks. However, automated reconstruction is hampered by database inconsistencies, incorrect annotations, and gap filling largely without considering genomic information. Here we develop an approach for applying genomic information to predict alternative functions for genes and estimate their likelihoods from sequence homology. We show that computed likelihood values were significantly higher for annotations found in manually curated metabolic networks than those that were not. We then apply these alternative functional predictions to estimate reaction likelihoods, which are used in a new gap filling approach called likelihood-based gap filling to predict more genomically consistent solutions. To validate the likelihood-based gap filling approach, we applied it to models where essential pathways were removed, finding that likelihood-based gap filling identified more biologically relevant solutions than parsimony-based gap filling approaches. We also demonstrate that models gap filled using likelihood-based gap filling provide greater coverage and genomic consistency with metabolic gene functions compared to parsimony-based approaches. Interestingly, despite these findings, we found that likelihoods did not significantly affect consistency of gap filled models with Biolog and knockout lethality data. This indicates that the phenotype data alone cannot necessarily be used to discriminate between alternative solutions for gap filling and therefore, that the use of other information is necessary to

  16. Likelihood-based gene annotations for gap filling and quality assessment in genome-scale metabolic models

    DOE PAGES

    Benedict, Matthew N.; Mundy, Michael B.; Henry, Christopher S.; ...

    2014-10-16

    Genome-scale metabolic models provide a powerful means to harness information from genomes to deepen biological insights. With exponentially increasing sequencing capacity, there is an enormous need for automated reconstruction techniques that can provide more accurate models in a short time frame. Current methods for automated metabolic network reconstruction rely on gene and reaction annotations to build draft metabolic networks and algorithms to fill gaps in these networks. However, automated reconstruction is hampered by database inconsistencies, incorrect annotations, and gap filling largely without considering genomic information. Here we develop an approach for applying genomic information to predict alternative functions for genesmore » and estimate their likelihoods from sequence homology. We show that computed likelihood values were significantly higher for annotations found in manually curated metabolic networks than those that were not. We then apply these alternative functional predictions to estimate reaction likelihoods, which are used in a new gap filling approach called likelihood-based gap filling to predict more genomically consistent solutions. To validate the likelihood-based gap filling approach, we applied it to models where essential pathways were removed, finding that likelihood-based gap filling identified more biologically relevant solutions than parsimony-based gap filling approaches. We also demonstrate that models gap filled using likelihood-based gap filling provide greater coverage and genomic consistency with metabolic gene functions compared to parsimony-based approaches. Interestingly, despite these findings, we found that likelihoods did not significantly affect consistency of gap filled models with Biolog and knockout lethality data. This indicates that the phenotype data alone cannot necessarily be used to discriminate between alternative solutions for gap filling and therefore, that the use of other information is necessary

  17. Likelihood-based gene annotations for gap filling and quality assessment in genome-scale metabolic models.

    PubMed

    Benedict, Matthew N; Mundy, Michael B; Henry, Christopher S; Chia, Nicholas; Price, Nathan D

    2014-10-01

    Genome-scale metabolic models provide a powerful means to harness information from genomes to deepen biological insights. With exponentially increasing sequencing capacity, there is an enormous need for automated reconstruction techniques that can provide more accurate models in a short time frame. Current methods for automated metabolic network reconstruction rely on gene and reaction annotations to build draft metabolic networks and algorithms to fill gaps in these networks. However, automated reconstruction is hampered by database inconsistencies, incorrect annotations, and gap filling largely without considering genomic information. Here we develop an approach for applying genomic information to predict alternative functions for genes and estimate their likelihoods from sequence homology. We show that computed likelihood values were significantly higher for annotations found in manually curated metabolic networks than those that were not. We then apply these alternative functional predictions to estimate reaction likelihoods, which are used in a new gap filling approach called likelihood-based gap filling to predict more genomically consistent solutions. To validate the likelihood-based gap filling approach, we applied it to models where essential pathways were removed, finding that likelihood-based gap filling identified more biologically relevant solutions than parsimony-based gap filling approaches. We also demonstrate that models gap filled using likelihood-based gap filling provide greater coverage and genomic consistency with metabolic gene functions compared to parsimony-based approaches. Interestingly, despite these findings, we found that likelihoods did not significantly affect consistency of gap filled models with Biolog and knockout lethality data. This indicates that the phenotype data alone cannot necessarily be used to discriminate between alternative solutions for gap filling and therefore, that the use of other information is necessary to

  18. Hydrophilic interaction chromatography-mass spectrometry for anionic metabolic profiling of urine from antibiotic-treated rats.

    PubMed

    Kok, Miranda G M; Swann, Jonathan R; Wilson, Ian D; Somsen, Govert W; de Jong, Gerhardus J

    2014-04-01

    Hydrophilic interaction chromatography-mass spectrometry (HILIC-MS) was used for anionic metabolic profiling of urine from antibiotic-treated rats to study microbial-host co-metabolism. Rats were treated with the antibiotics penicillin G and streptomycin sulfate for four or eight days and compared to a control group. Urine samples were collected at day zero, four and eight, and analyzed by HILIC-MS. Multivariate data analysis was applied to the urinary metabolic profiles to identify biochemical variation between the treatment groups. Principal component analysis found a clear distinction between those animals receiving antibiotics and the control animals, with twenty-nine discriminatory compounds of which twenty were down-regulated and nine up-regulated upon treatment. In the treatment group receiving antibiotics for four days, a recovery effect was observed for seven compounds after cessation of antibiotic administration. Thirteen discriminatory compounds could be putatively identified based on their accurate mass, including aconitic acid, benzenediol sulfate, ferulic acid sulfate, hippuric acid, indoxyl sulfate, penicillin G, phenol and vanillin 4-sulfate. The rat urine samples had previously been analyzed by capillary electrophoresis (CE) with MS detection and proton nuclear magnetic resonance ((1)H NMR) spectroscopy. Using CE-MS and (1)H NMR spectroscopy seventeen and twenty-five discriminatory compounds were found, respectively. Both hippuric acid and indoxyl sulfate were detected across all three platforms. Additionally, eight compounds were observed with both HILIC-MS and CE-MS. Overall, HILIC-MS appears to be highly complementary to CE-MS and (1)H NMR spectroscopy, identifying additional compounds that discriminate the urine samples from antibiotic-treated and control rats.

  19. Experimental studies on the impact of an increased dose of anionic salts on the metabolism of dairy cows.

    PubMed

    Gelfert, C C; Passfeld, M; Löptien, A; Montag, N; Baumgartner, W; Staufenbiel, R

    2006-12-01

    This study was initiated to investigate the influence of a daily dose of anionic salts (AS) above the valid upper limit at present on metabolism of dairy cows. Eleven non-pregnant and non-lactating Holstein-Friesian crossbred cows with a permanent rumen cannula were used in a study with a controlled feeding design. The initial daily dose was 2500 meq/day, which resulted in a Dietary Cation Anion Difference (DCAD) of -211 meq/kg dry matter. Every seven days,the daily dose was raised by 500 meq. If a cow stopped eating, the application of AS was stopped and these cows were monitored over the next seven days. On day 30 another batch of hay, having the same DCAD but higher concentrations of minerals and energy, was fed. Blood and urine samples were taken to monitor acid-base balance and calcium concentrations. Acid-base balance was strongly influenced by AS. Blood pH dropped steadily and reached values around 7.23. Urine pH dropped quickly below 6 and remained at that level regardless of the increased dosage of AS. Net acid base excretion (NABE) fell continuously with the increase of the dosage of AS and reached values below -200 mmol/l. Calcium concentrations in the serum were nearly stable, but those in urine increased sharply and remained on an elevated level with increasing doses of AS. A few days before the individual cow's refusal of feed intake, calcium excretion in urine decreased. The majority of cows stopped eating while consuming a diet containing 3500 to 4000 meq AS except two animals who consumed up to 6000 meq/day AS but they received the better hay in the second half of the treatment period. In this time pH in blood increased slowly. NABE remained stable on a low level at -100 mmol/l. The results showed that with an increasing amount of AS fed the risk of clinical acidosis increased. The decreasing urine concentrations of calcium indicate a breakdown of the compensation capability of the single cow. Besides the dose of AS fed, the quality of the feed

  20. The impact of dietary cation anion difference (DCAD) on the acid-base balance and calcium metabolism of non-lactating, non-pregnant dairy cows fed equal amounts of different anionic salts.

    PubMed

    Gelfert, Carl-Christian; Leonie Loeffler, S; Frömer, Sven; Engel, Maike; Hartmann, Helmut; Männer, Klaus; Baumgartner, Walter; Staufenbiel, Rudolf

    2007-08-01

    We evaluated the impact of the dietary cation-anion difference (DCAD) on the influence of anionic salts (AS) on the metabolism of dairy cows using a study-design that included control of feed intake. Ten mature, non-lactating, non-pregnant, Holstein-Friesian-crossbreed cows received 2000 mEq of either one of the seven anionic salts tested, two combinations of the anionic salts or water as control via a rumen cannula. Salts and controls were assigned in a 10x10 Latin square design. Whole blood, serum and urine samples were taken during treatment (TP) and washout period. Samples of whole blood were tested for pH, base-excess and bicarbonate concentrations. In urine, pH and net acid-base excretion (NABE) were analysed. Calcium was measured in serum and urine. According to the different batches of hay, five groups of DCAD were created regarding cluster analysis. Changes in urine and blood parameters were statistically analysed for each DCAD group separately. The different DCAD had an impact on the amount of change in acid-base balance (ABB) and calcium metabolism and for how long these changes lasted. In the DCAD group receiving the highest amount of AS (239 mEq/kg dry matter with AS), changes of ABB were only noticeable in urine and these changes only differed from day zero in the first week of TP (P<0.05). In the other four groups changes of ABB were also visible in blood parameters, but only on a few days of TP did the deviations differ significantly (P<0.05) from day zero. Changes of ABB parameters in urine samples were more pronounced than those in blood and differed clearly from day zero (P<0.05). Parallel to the changes of ABB, calcium concentrations in these samples were significantly increased (P<0.001) in all DCAD groups. Except for the highest DCAD group, ionized calcium concentrations changed over time (P<0.020). However, the differences were very small and only differed from day zero on a few TP days. We conclude that the DCAD of a dairy cow's diet has an

  1. Meneco, a Topology-Based Gap-Filling Tool Applicable to Degraded Genome-Wide Metabolic Networks

    PubMed Central

    Prigent, Sylvain; Frioux, Clémence; Dittami, Simon M.; Larhlimi, Abdelhalim; Collet, Guillaume; Gutknecht, Fabien; Got, Jeanne; Eveillard, Damien; Bourdon, Jérémie; Plewniak, Frédéric; Tonon, Thierry; Siegel, Anne

    2017-01-01

    Increasing amounts of sequence data are becoming available for a wide range of non-model organisms. Investigating and modelling the metabolic behaviour of those organisms is highly relevant to understand their biology and ecology. As sequences are often incomplete and poorly annotated, draft networks of their metabolism largely suffer from incompleteness. Appropriate gap-filling methods to identify and add missing reactions are therefore required to address this issue. However, current tools rely on phenotypic or taxonomic information, or are very sensitive to the stoichiometric balance of metabolic reactions, especially concerning the co-factors. This type of information is often not available or at least prone to errors for newly-explored organisms. Here we introduce Meneco, a tool dedicated to the topological gap-filling of genome-scale draft metabolic networks. Meneco reformulates gap-filling as a qualitative combinatorial optimization problem, omitting constraints raised by the stoichiometry of a metabolic network considered in other methods, and solves this problem using Answer Set Programming. Run on several artificial test sets gathering 10,800 degraded Escherichia coli networks Meneco was able to efficiently identify essential reactions missing in networks at high degradation rates, outperforming the stoichiometry-based tools in scalability. To demonstrate the utility of Meneco we applied it to two case studies. Its application to recent metabolic networks reconstructed for the brown algal model Ectocarpus siliculosus and an associated bacterium Candidatus Phaeomarinobacter ectocarpi revealed several candidate metabolic pathways for algal-bacterial interactions. Then Meneco was used to reconstruct, from transcriptomic and metabolomic data, the first metabolic network for the microalga Euglena mutabilis. These two case studies show that Meneco is a versatile tool to complete draft genome-scale metabolic networks produced from heterogeneous data, and to

  2. Target Organ Metabolism, Toxicity, and Mechanisms of Trichloroethylene and Perchloroethylene: Key Similarities, Differences, and Data Gaps.

    PubMed

    Cichocki, Joseph A; Guyton, Kathryn Z; Guha, Neela; Chiu, Weihsueh A; Rusyn, Ivan; Lash, Lawrence H

    2016-10-01

    Trichloroethylene (TCE) and perchloroethylene or tetrachloroethylene (PCE) are high-production volume chemicals with numerous industrial applications. As a consequence of their widespread use, these chemicals are ubiquitous environmental contaminants to which the general population is commonly exposed. It is widely assumed that TCE and PCE are toxicologically similar; both are simple olefins with three (TCE) or four (PCE) chlorines. Nonetheless, despite decades of research on the adverse health effects of TCE or PCE, few studies have directly compared these two toxicants. Although the metabolic pathways are qualitatively similar, quantitative differences in the flux and yield of metabolites exist. Recent human health assessments have uncovered some overlap in target organs that are affected by exposure to TCE or PCE, and divergent species- and sex-specificity with regard to cancer and noncancer hazards. The objective of this minireview is to highlight key similarities, differences, and data gaps in target organ metabolism and mechanism of toxicity. The main anticipated outcome of this review is to encourage research to 1) directly compare the responses to TCE and PCE using more sensitive biochemical techniques and robust statistical comparisons; 2) more closely examine interindividual variability in the relationship between toxicokinetics and toxicodynamics for TCE and PCE; 3) elucidate the effect of coexposure to these two toxicants; and 4) explore new mechanisms for target organ toxicity associated with TCE and/or PCE exposure.

  3. Anion channel sensitivity to cytosolic organic acids implicates a central role for oxaloacetate in integrating ion flux with metabolism in stomatal guard cells

    PubMed Central

    Wang, Yizhou; Blatt, Michael R.

    2011-01-01

    Stomatal guard cells play a key role in gas exchange for photosynthesis and in minimizing transpirational water loss from plants by opening and closing the stomatal pore. The bulk of the osmotic content driving stomatal movements depends on ionic fluxes across both the plasma membrane and tonoplast, the metabolism of organic acids, primarily Mal (malate), and its accumulation and loss. Anion channels at the plasma membrane are thought to comprise a major pathway for Mal efflux during stomatal closure, implicating their key role in linking solute flux with metabolism. Nonetheless, little is known of the regulation of anion channel current (ICl) by cytosolic Mal or its immediate metabolite OAA (oxaloacetate). In the present study, we have examined the impact of Mal, OAA and of the monocarboxylic acid anion acetate in guard cells of Vicia faba L. and report that all three organic acids affect ICl, but with markedly different characteristics and sidedness to their activities. Most prominent was a suppression of ICl by OAA within the physiological range of concentrations found in vivo. These findings indicate a capacity for OAA to co-ordinate organic acid metabolism with ICl through the direct effect of organic acid pool size. The findings of the present study also add perspective to in vivo recordings using acetate-based electrolytes. PMID:21745184

  4. Organic anion-transporting polypeptide 1a4 (Oatp1a4) is important for secondary bile acid metabolism

    PubMed Central

    Zhang, Youcai; Csanaky, Iván L.; Selwyn, Felcy Pavithra; Lehman-McKeeman, Lois D.; Klaassen, Curtis D.

    2013-01-01

    Organic anion transporting polypeptides (human: OATPs; rodent: Oatps) were thought to have important functions in bile acid (BA) transport. Oatp1a1, 1a4, and 1b2 are the three major Oatp1 family members in rodent liver. Our previous studies have characterized the BA homeostasis in Oatp1a1-null and Oatp1b2-null mice. The present study investigated the physiological role of Oatp1a4 in BA homeostasis by using Oatp1a4-null mice. Oatp1a4 expression is female-predominant in livers of mice, and thereby it was expected that female Oatp1a4-null mice will have more prominent changes than males. Interestingly, the present study demonstrated that female Oatp1a4-null mice had no significant alterations in BA concentrations in serum or liver, though they had increased mRNA of hepatic BA efflux transporters (Mrp4 and Ostα/β) and ileal BA transporters (Asbt and Ostα/β). In contrast, male Oatp1a4-null mice showed significantly altered BA homeostasis, including increased concentrations of deoxycholic acid (DCA) in serum, liver and intestinal contents. After feeding a DCA-supplemented diet, male but not female Oatp1a4-null mice had higher concentrations of DCA in serum and livers than their WT controls. This suggested that Oatp1a4 is important for intestinal absorption of secondary BAs in male mice. Furthermore, loss of Oatp1a4 function did not decrease BA accumulation in serum or livers of bile-ductligated mice, suggesting that Oatp1a4 is not likely a BA uptake transporter. In summary, the present study for the first time demonstrates that Oatp1a4 does not appear to mediate the hepatic uptake of BAs, but plays an important male-predominant role in secondary BA metabolism in mice. PMID:23747753

  5. Alterations in metabolism and gap junction expression may determine the role of astrocytes as "good samaritans" or executioners.

    PubMed

    Farahani, Reza; Pina-Benabou, Mara H; Kyrozis, Andreas; Siddiq, Ayesha; Barradas, Penha C; Chiu, Fung-Chow; Cavalcante, Leny A; Lai, James C K; Stanton, Patric K; Rozental, Renato

    2005-06-01

    Our knowledge of astroglia and their physiological and pathophysiological role(s) in the central nervous system (CNS) has grown during the past decade, revealing a complex picture. It is becoming increasingly clear that glia play a significant role in the homeostasis and function of the CNS and that neurons should no longer be considered the only cell type that responds, both rapidly and slowly, to electrochemical activity. We discuss recent advances in the field with an emphasis on the impact of hypoxia and ischemia on astrocytic metabolism and the functional relationship between glucose metabolism and gap junctions in astrocytes. We also address the controversy over whether astrocytic gap junctions mediate protection or killing of neurons during or after hypoxic or ischemic insults.

  6. Bridging the gap: metabolic and endocrine care of patients during transition

    PubMed Central

    Hokken-Koelega, Anita; Hauffa, Berthold; Häusler, Gabriele; Johannsson, Gudmundur; Maghnie, Mohamad; Argente, Jesús; DeSchepper, Jean; Gleeson, Helena; Gregory, John W; Höybye, Charlotte; Keleştimur, Fahrettin; Luger, Anton; Müller, Hermann L; Neggers, Sebastian; Popovic-Brkic, Vera; Porcu, Eleonora; Sävendahl, Lars; Shalet, Stephen; Spiliotis, Bessie; Tauber, Maithé

    2016-01-01

    Objective Seamless transition of endocrine patients from the paediatric to adult setting is still suboptimal, especially in patients with complex disorders, i.e., small for gestational age, Turner or Prader–Willi syndromes; Childhood Cancer Survivors, and those with childhood-onset growth hormone deficiency. Methods An expert panel meeting comprised of European paediatric and adult endocrinologists was convened to explore the current gaps in managing the healthcare of patients with endocrine diseases during transition from paediatric to adult care settings. Results While a consensus was reached that a team approach is best, discussions revealed that a ‘one size fits all’ model for transition is largely unsuccessful in these patients. They need more tailored care during adolescence to prevent complications like failure to achieve target adult height, reduced bone mineral density, morbid obesity, metabolic perturbations (obesity and body composition), inappropriate/inadequate puberty, compromised fertility, diminished quality of life and failure to adapt to the demands of adult life. Sometimes it is difficult for young people to detach emotionally from their paediatric endocrinologist and/or the abrupt change from an environment of parental responsibility to one of autonomy. Discussions about impending transition and healthcare autonomy should begin in early adolescence and continue throughout young adulthood to ensure seamless continuum of care and optimal treatment outcomes. Conclusions Even amongst a group of healthcare professionals with a great interest in improving transition services for patients with endocrine diseases, there is still much work to be done to improve the quality of healthcare for transition patients. PMID:27803155

  7. Superconducting gap function in the organic superconductor (TMTSF)2ClO4 with anion ordering; First-principles calculations and quasiclassical analysis for angle-resolved heat capacity

    NASA Astrophysics Data System (ADS)

    Nagai, Yuki; Nakamura, Hiroki; Machida, Masahiko

    2011-03-01

    We calculate angle-dependent heat capacity in a low magnetic field range on the basis of the Kramer-Pesch approximation together with an electronic structure obtained by first-principles calculations to determine a superconducting gap function of (TMTSF)2ClO4 through its comparisons with experiments. The present comparative studies reveal that a nodal d-wave gap function consistently explains the experimental results for (TMTSF)2ClO4. It is especially emphasized that the observed unusual axis asymmetry of the angle dependence eliminates the possibility of s-wave and nodeless d-wave functions. It is also found that the directional ordering of ClO4 anions does not have any significant effects on the Fermi surface structure contrary to the previous modelings since the two Fermi surfaces obtained by the band calculations almost cross within the present full accuracy in first-principles calculations.

  8. Bridging the Gap between Gene Expression and Metabolic Phenotype via Kinetic Models

    DTIC Science & Technology

    2013-07-22

    were computed from the smoothed data. The uptake rate of glucose and production rates of ethanol , glycerol, lactic acid, acetic acid, and CO2 were...alterations in yeast metabolism that mimicked measured metabolic fluxes and concentration changes. Further analyses generated mechanistic insights of...metabolome data to determine and interpret important features of the physiological response of yeast to stresses. Importantly, given its flexibility and

  9. The barley anion channel, HvALMT1, has multiple roles in guard cell physiology and grain metabolism.

    PubMed

    Xu, Muyun; Gruber, Benjamin D; Delhaize, Emmanuel; White, Rosemary G; James, Richard A; You, Jiangfeng; Yang, Zhenming; Ryan, Peter R

    2015-01-01

    The barley (Hordeum vulgare) gene HvALMT1 encodes an anion channel in guard cells and in certain root tissues indicating that it may perform multiple roles. The protein localizes to the plasma membrane and facilitates malate efflux from cells when constitutively expressed in barley plants and Xenopus oocytes. This study investigated the function of HvALMT1 further by identifying its tissue-specific expression and by generating and characterizing RNAi lines with reduced HvALMT1 expression. We show that transgenic plants with 18-30% of wild-type HvALMT1 expression had impaired guard cell function. They maintained higher stomatal conductance in low light intensity and lost water more rapidly from excised leaves than the null segregant control plants. Tissue-specific expression of HvALMT1 was investigated in developing grain and during germination using transgenic barley lines expressing the green fluorescent protein (GFP) with the HvALMT1 promoter. We found that HvALMT1 is expressed in the nucellar projection, the aleurone layer and the scutellum of developing barley grain. Malate release measured from isolated aleurone layers prepared from imbibed grain was significantly lower in the RNAi barley plants compared with control plants. These data provide molecular and physiological evidence that HvALMT1 functions in guard cells, in grain development and during germination. We propose that HvALMT1 releases malate and perhaps other anions from guard cells to promote stomatal closure. The likely roles of HvALMT1 during seed development and grain germination are also discussed.

  10. Dysfunction of Organic Anion Transporting Polypeptide 1a1 Alters Intestinal Bacteria and Bile Acid Metabolism in Mice

    PubMed Central

    Zhang, Youcai; Limaye, Pallavi B.; Lehman-McKeeman, Lois D.; Klaassen, Curtis D.

    2012-01-01

    Organic anion transporting polypeptide 1a1 (Oatp1a1) is predominantly expressed in liver and is able to transport bile acids (BAs) in vitro. Male Oatp1a1-null mice have increased concentrations of taurodeoxycholic acid (TDCA), a secondary BA generated by intestinal bacteria, in both serum and livers. Therefore, in the present study, BA concentrations and intestinal bacteria in wild-type (WT) and Oatp1a1-null mice were quantified to investigate whether the increase of secondary BAs in Oatp1a1-null mice is due to alterations in intestinal bacteria. The data demonstrate that Oatp1a1-null mice : (1) have similar bile flow and BA concentrations in bile as WT mice; (2) have a markedly different BA composition in the intestinal contents, with a decrease in conjugated BAs and an increase in unconjugated BAs; (3) have BAs in the feces that are more deconjugated, desulfated, 7-dehydroxylated, 3-epimerized, and oxidized, but less 7-epimerized; (4) have 10-fold more bacteria in the small intestine, and 2-fold more bacteria in the large intestine which is majorly due to a 200% increase in Bacteroides and a 30% reduction in Firmicutes; and (5) have a different urinary excretion of bacteria-related metabolites than WT mice. In conclusion, the present study for the first time established that lack of a liver transporter (Oatp1a1) markedly alters the intestinal environment in mice, namely the bacteria composition. PMID:22496825

  11. Effect of dietary cation-anion difference on ruminal metabolism, total apparent digestibility, blood and renal acid-base regulation in lactating dairy cows.

    PubMed

    Martins, C M M R; Arcari, M A; Welter, K C; Gonçalves, J L; Santos, M V

    2016-01-01

    The present study aimed to evaluate the effect of dietary cation-anion difference (DCAD) on ruminal fermentation, total apparent digestibility, blood and renal metabolism of lactating dairy cows. Sixteen Holstein cows were distributed in four contemporary 4×4 Latin Square designs, which consisted of four periods of 21 days and four treatments according to DCAD: +290; +192; +98 and -71 milliequivalent (mEq)/kg dry matter (DM). Ruminal pH and concentrations of acetic and butyric acid increased linearly according to the increase of DCAD. Similarly, NDF total apparent digestibility linearly increased by 6.38% when DCAD increased from -71 to 290 mEq/kg DM [Y=65.90 (SE=2.37)+0.0167 (SE=0.0068)×DCAD (mEq/kg DM)]. Blood pH was also increased according to DCAD, which resulted in reduction of serum concentrations of Na, K and ionic calcium (iCa). To maintain the blood acid-base homeostasis, renal metabolism played an important role in controlling serum concentrations of Na and K, since the Na and K urinary excretion increased linearly by 89.69% and 46.06%, respectively, from -71 to 290 mEq/kg DM. Changes in acid-base balance of biological fluids may directly affect the mineral composition of milk, as milk concentrations of Na, K, iCa and chlorides were reduced according to blood pH increased. Thus, it can be concluded that the increase of DCAD raises the pH of ruminal fluid, NDF total apparent digestibility, and blood pH, and decreases the milk concentration of cationic minerals, as well as the efficiency of Na utilization to milk production.

  12. Citric acid ingestion: a life-threatening cause of metabolic acidosis.

    PubMed

    DeMars, C S; Hollister, K; Tomassoni, A; Himmelfarb, J; Halperin, M L

    2001-11-01

    We present a case that illustrates the acute (<6 hours) metabolic and hemodynamic effects of the ingestion of a massive oral citric acid load. The principal findings included metabolic acidosis accompanied by an increase in the plasma anion gap that was not caused by L -lactic acidosis, hyperkalemia, and the abrupt onset of hypotension. A unique feature was a dramatic clinical improvement when ionized calcium was infused. The case illustrates the importance of considering the properties of the conjugate base (anion) of the added acid because, in this instance, the citrate anion had a unique and life-threatening consequence (lower ionized calcium level) that was rapidly reversible.

  13. Modulation of metabolic communication through gap junction channels by transjunctional voltage; synergistic and antagonistic effects of gating and ionophoresis

    PubMed Central

    Palacios-Prado, Nicolás; Bukauskas, Feliksas F.

    2011-01-01

    Gap junction (GJ) channels assembled from connexin (Cx) proteins provide a structural basis for direct electrical and metabolic cell-cell communication. Here, we focus on gating and permeability properties of Cx43/Cx45 heterotypic GJs exhibiting asymmetries of both voltage-gating and transjunctional flux (Jj) of fluorescent dyes depending on transjunctional voltage (Vj). Relatively small differences in the resting potential of communicating cells can substantially reduce or enhance this flux at relative negativity or positivity on Cx45 side, respectively. Similarly, series of Vj pulses resembling bursts of action potentials (APs) reduce Jj when APs initiate in the cell expressing Cx43 and increase Jj when APs initiate in the cell expressing Cx45. Jj of charged fluorescent dyes is affected by ionophoresis and Vj-gating and the asymmetry of Jj-Vj dependence in heterotypic GJs is enhanced or reduced when ionophoresis and Vj-gating work in a synergistic or antagonistic manner, respectively. Modulation of cell-to-cell transfer of metabolites and signaling molecules by Vj may occur in excitable as well as non-excitable tissues and may be more expressed in the border between normal and pathological regions where intercellular gradients of membrane potential and concentration of ions are substantially altered. PMID:21930112

  14. Diet-induced metabolic acidosis.

    PubMed

    Adeva, María M; Souto, Gema

    2011-08-01

    The modern Western-type diet is deficient in fruits and vegetables and contains excessive animal products, generating the accumulation of non-metabolizable anions and a lifespan state of overlooked metabolic acidosis, whose magnitude increases progressively with aging due to the physiological decline in kidney function. In response to this state of diet-derived metabolic acidosis, the kidney implements compensating mechanisms aimed to restore the acid-base balance, such as the removal of the non-metabolizable anions, the conservation of citrate, and the enhancement of kidney ammoniagenesis and urinary excretion of ammonium ions. These adaptive processes lower the urine pH and induce an extensive change in urine composition, including hypocitraturia, hypercalciuria, and nitrogen and phosphate wasting. Low urine pH predisposes to uric acid stone formation. Hypocitraturia and hypercalciuria are risk factors for calcium stone disease. Even a very mild degree of metabolic acidosis induces skeletal muscle resistance to the insulin action and dietary acid load may be an important variable in predicting the metabolic abnormalities and the cardiovascular risk of the general population, the overweight and obese persons, and other patient populations including diabetes and chronic kidney failure. High dietary acid load is more likely to result in diabetes and systemic hypertension and may increase the cardiovascular risk. Results of recent observational studies confirm an association between insulin resistance and metabolic acidosis markers, including low serum bicarbonate, high serum anion gap, hypocitraturia, and low urine pH.

  15. Topiramate and metabolic acidosis.

    PubMed

    Wilner, A; Raymond, K; Pollard, R

    1999-06-01

    Topiramate (TPM) is a novel antiepileptic medication (AED) with at least three mechanisms of action. A possible fourth mechanism, that of a carbonic anhydrase inhibitor, also may contribute to its antiepileptic properties. We report a patient with intractable epilepsy and normal renal function who developed a normal anion gap metabolic acidosis, which worsened during elective surgery for temporal lobectomy. We believe this side effect of TPM can become clinically significant during surgery, concomitant use of another carbonic anhydrase inhibitor, and potentially with the ketogenic diet.

  16. Metabolism

    MedlinePlus

    Metabolism refers to all the physical and chemical processes in the body that convert or use energy, ... Tortora GJ, Derrickson BH. Metabolism. In: Tortora GJ, Derrickson ... Physiology . 14th ed. Hoboken, NJ: John Wiley & Sons; 2014:chap ...

  17. Metabolism

    MedlinePlus

    ... El metabolismo Metabolism Basics Our bodies get the energy they need from food through metabolism, the chemical ... that convert the fuel from food into the energy needed to do everything from moving to thinking ...

  18. (-)-Epicatechin prevents alterations in the metabolism of superoxide anion and nitric oxide in the hearts of L-NAME-treated rats.

    PubMed

    Piotrkowski, Barbara; Calabró, Valeria; Galleano, Mónica; Fraga, César G

    2015-01-01

    The aim of this work was to evaluate the effects of (-)-epicatechin administration in the heart of a rat model with reduced NO production that follows a short-term treatment with L-NAME. Sprague-Dawley rats were treated for 4 d with L-NAME in the absence or presence of (-)-epicatechin in the diet. The redox status in cardiac tissue was improved by (-)-epicatechin administration. L-NAME treatment induced a decrease in NO synthase activity (-62%, p<0.05) and an increase in NADPH-dependent superoxide anion production (+300%, p<0.05) that were totally prevented by (-)-epicatechin administration. These effects of (-)-epicatechin were associated with a higher endothelial NO synthase phosphorylation at an activation site and a reduced expression of the regulatory subunit, p47(phox), suggesting the involvement of posttranslational mechanisms in (-)-epicatechin action. Thus, the (-)-epicatechin treatment would restore NO steady state levels in vivo through effects on both, its synthesis and degradation via the reaction with superoxide anion. The fact that (-)-epicatechin is commonly present in human diet makes this compound a reasonable explanation for the positive cardiovascular effects of a high consumption of fruits and vegetables.

  19. Evolution of Microbial Quorum Sensing to Human Global Quorum Sensing: An Insight into How Gap Junctional Intercellular Communication Might Be Linked to the Global Metabolic Disease Crisis

    PubMed Central

    Trosko, James E.

    2016-01-01

    The first anaerobic organism extracted energy for survival and reproduction from its source of nutrients, with the genetic means to ensure protection of its individual genome but also its species survival. While it had a means to communicate with its community via simple secreted molecules (“quorum sensing”), the eventual shift to an aerobic environment led to multi-cellular metazoan organisms, with evolutionary-selected genes to form extracellular matrices, stem cells, stem cell niches, and a family of gap junction or “connexin” genes. These germinal and somatic stem cells responded to extracellular signals that triggered intra-cellular signaling to regulate specific genes out of the total genome. These extra-cellular induced intra-cellular signals also modulated gap junctional intercellular communication (GJIC) in order to regulate the new cellular functions of symmetrical and asymmetrical cell division, cell differentiation, modes of cell death, and senescence. Within the hierarchical and cybernetic concepts, differentiated by neurons organized in the brain of the Homo sapiens, the conscious mind led to language, abstract ideas, technology, myth-making, scientific reasoning, and moral decision–making, i.e., the creation of culture. Over thousands of years, this has created the current collision between biological and cultural evolution, leading to the global “metabolic disease” crisis. PMID:27314399

  20. Evolution of Microbial Quorum Sensing to Human Global Quorum Sensing: An Insight into How Gap Junctional Intercellular Communication Might Be Linked to the Global Metabolic Disease Crisis.

    PubMed

    Trosko, James E

    2016-06-15

    The first anaerobic organism extracted energy for survival and reproduction from its source of nutrients, with the genetic means to ensure protection of its individual genome but also its species survival. While it had a means to communicate with its community via simple secreted molecules ("quorum sensing"), the eventual shift to an aerobic environment led to multi-cellular metazoan organisms, with evolutionary-selected genes to form extracellular matrices, stem cells, stem cell niches, and a family of gap junction or "connexin" genes. These germinal and somatic stem cells responded to extracellular signals that triggered intra-cellular signaling to regulate specific genes out of the total genome. These extra-cellular induced intra-cellular signals also modulated gap junctional intercellular communication (GJIC) in order to regulate the new cellular functions of symmetrical and asymmetrical cell division, cell differentiation, modes of cell death, and senescence. Within the hierarchical and cybernetic concepts, differentiated by neurons organized in the brain of the Homo sapiens, the conscious mind led to language, abstract ideas, technology, myth-making, scientific reasoning, and moral decision-making, i.e., the creation of culture. Over thousands of years, this has created the current collision between biological and cultural evolution, leading to the global "metabolic disease" crisis.

  1. Anion exchange membrane

    DOEpatents

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  2. Anions in Cometary Comae

    NASA Technical Reports Server (NTRS)

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  3. Metabolism

    MedlinePlus

    ... and intestines. Several of the hormones of the endocrine system are involved in controlling the rate and direction ... For Kids For Parents MORE ON THIS TOPIC Endocrine System What Can I Do About My High Metabolism? ...

  4. Metabolism

    MedlinePlus

    ... symptoms. Metabolic diseases and conditions include: Hyperthyroidism (pronounced: hi-per-THIGH-roy-dih-zum). Hyperthyroidism is caused ... or through surgery or radiation treatments. Hypothyroidism (pronounced: hi-po-THIGH-roy-dih-zum). Hypothyroidism is caused ...

  5. Filling Knowledge Gaps in Biological Networks: integrating global approaches to understand H2 metabolism in Chlamydomonas reinhardtii - Final Report

    SciTech Connect

    Posewitz, Matthew C

    2011-06-30

    The green alga Chlamydomonas reinhardtii (Chlamydomonas) has numerous genes encoding enzymes that function in fermentative pathways. Among these genes, are the [FeFe]-hydrogenases, pyruvate formate lyase, pyruvate ferredoxin oxidoreductase, acetate kinase, and phosphotransacetylase. We have systematically undertaken a series of targeted mutagenesis approaches to disrupt each of these key genes and omics techniques to characterize alterations in metabolic flux. Funds from DE-FG02-07ER64423 were specifically leveraged to generate mutants with disruptions in the genes encoding the [FeFe]-hydrogenases HYDA1 and HYDA2, pyruvate formate lyase (PFL1), and in bifunctional alcohol/aldehyde alcohol dehydrogenase (ADH1). Additionally funds were used to conduct global transcript profiling experiments of wildtype Chlamydomonas cells, as well as of the hydEF-1 mutant, which is unable to make H2 due to a lesion in the [FeFe]-hydrogenase biosynthetic pathway. In the wildtype cells, formate, acetate and ethanol are the dominant fermentation products with traces of CO2 and H2 also being produced. In the hydEF-1 mutant, succinate production is increased to offset the loss of protons as a terminal electron acceptor. In the pfl-1 mutant, lactate offsets the loss of formate production, and in the adh1-1 mutant glycerol is made instead of ethanol. To further probe the system, we generated a double mutant (pfl1-1 adh1) that is unable to synthesize both formate and ethanol. This strain, like the pfl1 mutants, secreted lactate, but also exhibited a significant increase in the levels of extracellular glycerol, acetate, and intracellular reduced sugars, and a decline in dark, fermentative H2 production. Whereas wild-type Chlamydomonas fermentation primarily produces formate and ethanol, the double mutant performs a complete rerouting of the glycolytic carbon to lactate and glycerol. Lastly, transcriptome data have been analysed for both the wildtype and hydEF-1, that correlate with our

  6. Ethylene glycol induces hyperoxaluria without metabolic acidosis in rats.

    PubMed

    Green, Mike L; Hatch, Marguerite; Freel, Robert W

    2005-09-01

    Ethylene glycol (EG) consumption is commonly employed as an experimental regimen to induce hyperoxaluria in animal models of calcium oxalate nephrolithiasis. This approach has, however, been criticized because EG overdose induces metabolic acidosis in humans. We tested the hypothesis that EG consumption (0.75% in drinking water for 4 wk) induces metabolic acidosis by comparing arterial blood gases, serum electrolytes, and urinary chemistries in five groups of Sprague-Dawley rats: normal controls (CON), those made hyperoxaluric (HYP) with EG administration, unilaterally nephrectomized controls (UNI), unilaterally nephrectomized rats fed EG (HRF), and a metabolic acidosis (MA) reference group imbibing sweetened drinking water (5% sucrose) containing 0.28 M NH4Cl. Arterial pH, plasma bicarbonate concentrations, anion gap, urinary pH, and the excretion of titratable acid, ammonium, phosphate, citrate, and calcium in HYP rats were not significantly different from CON rats, indicating that metabolic acidosis did not develop in HYP rats with two kidneys. Unilateral nephrectomy alone (UNI group) did not significantly affect arterial pH, plasma bicarbonate, anion gap, or urinary pH compared with CON rats; however, HRF rats exhibited some signs of a nascent acidosis in having an elevated anion gap, higher phosphate excretion, lower urinary pH, and an increase in titratable acid. Frank metabolic acidosis was observed in the MA rats: decreased arterial pH and plasma HCO3(-) concentration with lower urinary pH and citrate excretion with elevated excretion of ammonium, phosphate and, hence, titratable acid. We conclude that metabolic acidosis does not develop in conventional EG treatments but may ensue with renal insufficiency resulting from an oxalate load.

  7. Anions coordinating anions: analysis of the interaction between anionic Keplerate nanocapsules and their anionic ligands.

    PubMed

    Melgar, Dolores; Bandeira, Nuno A G; Bonet Avalos, Josep; Bo, Carles

    2017-02-15

    Keplerates are a family of anionic metal oxide spherical capsules containing up to 132 metal atoms and some hundreds of oxygen atoms. These capsules holding a high negative charge of -12 coordinate both mono-anionic and di-anionic ligands thus increasing their charge up to -42, even up to -72, which is compensated by the corresponding counter-cations in the X-ray structures. We present an analysis of the relative importance of several energy terms of the coordinate bond between the capsule and ligands like carbonate, sulphate, sulphite, phosphinate, selenate, and a variety of carboxylates, of which the overriding component is contributed by solvation/de-solvation effects.

  8. R type anion channel

    PubMed Central

    Diatloff, Eugene; Peyronnet, Rémi; Colcombet, Jean; Thomine, Sébastien; Barbier-Brygoo, Hélène

    2010-01-01

    Plant genomes code for channels involved in the transport of cations, anions and uncharged molecules through membranes. Although the molecular identity of channels for cations and uncharged molecules has progressed rapidly in the recent years, the molecular identity of anion channels has lagged behind. Electrophysiological studies have identified S-type (slow) and R-type (rapid) anion channels. In this brief review, we summarize the proposed functions of the R-type anion channels which, like the S-type, were first characterized by electrophysiology over 20 years ago, but unlike the S-type, have still yet to be cloned. We show that the R-type channel can play multiple roles. PMID:21051946

  9. Anion-π catalysis.

    PubMed

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2014-02-05

    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  10. Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions

    PubMed Central

    Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

    2014-01-01

    Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism. PMID:25387603

  11. Quantum chemical approach to estimating the thermodynamics of metabolic reactions.

    PubMed

    Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

    2014-11-12

    Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism.

  12. Final Report: Filling Knowledge Gaps in Biological Networks: Integrated Global Approaches to Understand H{sub 2} Metabolism in Chlamydomonas Reinhardtii

    SciTech Connect

    Grossman, Arthur

    2012-05-01

    The major goal of our part of this project has been to generate mutants in fermentation metabolism and begin to decipher how lesions in the pathways associated with fermentation metabolism impact both H{sub 2} production and the production of other metabolites that accumulate as cells become anoxic. We are also trying to understand how metabolic pathways are regulated as O{sub 2} in the environment becomes depleted.

  13. A new coding system for metabolic disorders demonstrates gaps in the international disease classifications ICD-10 and SNOMED-CT, which can be barriers to genotype-phenotype data sharing.

    PubMed

    Sollie, Annet; Sijmons, Rolf H; Lindhout, Dick; van der Ploeg, Ans T; Rubio Gozalbo, M Estela; Smit, G Peter A; Verheijen, Frans; Waterham, Hans R; van Weely, Sonja; Wijburg, Frits A; Wijburg, Rudolph; Visser, Gepke

    2013-07-01

    Data sharing is essential for a better understanding of genetic disorders. Good phenotype coding plays a key role in this process. Unfortunately, the two most widely used coding systems in medicine, ICD-10 and SNOMED-CT, lack information necessary for the detailed classification and annotation of rare and genetic disorders. This prevents the optimal registration of such patients in databases and thus data-sharing efforts. To improve care and to facilitate research for patients with metabolic disorders, we developed a new coding system for metabolic diseases with a dedicated group of clinical specialists. Next, we compared the resulting codes with those in ICD and SNOMED-CT. No matches were found in 76% of cases in ICD-10 and in 54% in SNOMED-CT. We conclude that there are sizable gaps in the SNOMED-CT and ICD coding systems for metabolic disorders. There may be similar gaps for other classes of rare and genetic disorders. We have demonstrated that expert groups can help in addressing such coding issues. Our coding system has been made available to the ICD and SNOMED-CT organizations as well as to the Orphanet and HPO organizations for further public application and updates will be published online (www.ddrmd.nl and www.cineas.org).

  14. Complex anion inclusion compounds: flexible anion-exchange materials.

    PubMed

    Williams, Edward R; Leithall, Rebecca M; Raja, Robert; Weller, Mark T

    2013-01-11

    Copper chloropyrophosphate frameworks have been synthesised with a wide variety of complex inorganic anions trapped in a large, flexible, one-dimensional pore, with anions including chloride, bromide, phosphate and the complex metal halo-anions PtCl(4)(2-), PdBr(4)(2-), CuCl(4)(2-) and AuCl(4)(-).

  15. Gap junctions.

    PubMed

    Goodenough, Daniel A; Paul, David L

    2009-07-01

    Gap junctions are aggregates of intercellular channels that permit direct cell-cell transfer of ions and small molecules. Initially described as low-resistance ion pathways joining excitable cells (nerve and muscle), gap junctions are found joining virtually all cells in solid tissues. Their long evolutionary history has permitted adaptation of gap-junctional intercellular communication to a variety of functions, with multiple regulatory mechanisms. Gap-junctional channels are composed of hexamers of medium-sized families of integral proteins: connexins in chordates and innexins in precordates. The functions of gap junctions have been explored by studying mutations in flies, worms, and humans, and targeted gene disruption in mice. These studies have revealed a wide diversity of function in tissue and organ biology.

  16. Gap Junctions

    PubMed Central

    Goodenough, Daniel A.; Paul, David L.

    2009-01-01

    Gap junctions are aggregates of intercellular channels that permit direct cell–cell transfer of ions and small molecules. Initially described as low-resistance ion pathways joining excitable cells (nerve and muscle), gap junctions are found joining virtually all cells in solid tissues. Their long evolutionary history has permitted adaptation of gap-junctional intercellular communication to a variety of functions, with multiple regulatory mechanisms. Gap-junctional channels are composed of hexamers of medium-sized families of integral proteins: connexins in chordates and innexins in precordates. The functions of gap junctions have been explored by studying mutations in flies, worms, and humans, and targeted gene disruption in mice. These studies have revealed a wide diversity of function in tissue and organ biology. PMID:20066080

  17. Photodetachment of Lanthanide Oxide Anions

    NASA Astrophysics Data System (ADS)

    Covington, A. M.; Emmons, E. D.; Kraus, R. G.; Thompson, J. S.; Calabrese, D.; Davis, V. T.

    2007-06-01

    Laser photodetached electron spectroscopy (LPES) has been used to study the structure and collision properties of lanthanide oxide anions including LaOn^- and CeOn^-. Preliminary photoelectron spectra from these anions will be presented along with ion beam production data from these and other lanthanide oxide anions.

  18. Gap Junctions

    PubMed Central

    Nielsen, Morten Schak; Axelsen, Lene Nygaard; Sorgen, Paul L.; Verma, Vandana; Delmar, Mario; Holstein-Rathlou, Niels-Henrik

    2013-01-01

    Gap junctions are essential to the function of multicellular animals, which require a high degree of coordination between cells. In vertebrates, gap junctions comprise connexins and currently 21 connexins are known in humans. The functions of gap junctions are highly diverse and include exchange of metabolites and electrical signals between cells, as well as functions, which are apparently unrelated to intercellular communication. Given the diversity of gap junction physiology, regulation of gap junction activity is complex. The structure of the various connexins is known to some extent; and structural rearrangements and intramolecular interactions are important for regulation of channel function. Intercellular coupling is further regulated by the number and activity of channels present in gap junctional plaques. The number of connexins in cell-cell channels is regulated by controlling transcription, translation, trafficking, and degradation; and all of these processes are under strict control. Once in the membrane, channel activity is determined by the conductive properties of the connexin involved, which can be regulated by voltage and chemical gating, as well as a large number of posttranslational modifications. The aim of the present article is to review our current knowledge on the structure, regulation, function, and pharmacology of gap junctions. This will be supported by examples of how different connexins and their regulation act in concert to achieve appropriate physiological control, and how disturbances of connexin function can lead to disease. © 2012 American Physiological Society. Compr Physiol 2:1981-2035, 2012. PMID:23723031

  19. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  20. Anion permselective membrane

    NASA Astrophysics Data System (ADS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-07-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  1. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-01-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  2. Effect of anionic salts in prepartum diets based on alfalfa.

    PubMed

    Joyce, P W; Sanchez, W K; Goff, J P

    1997-11-01

    This study compared prepartum diets based on grass, alfalfa, or alfalfa and anionic salts to investigate their effect on Ca metabolism, acid-base status, endocrine response, disease incidence, and lactational performance of periparturient dairy cows. Forty-five nonlactating Holstein cows in their last 3 wk of gestation were fed a control diet based on grass hay with a dietary cation-anion difference [expressed as milli-equivalents of ((Na + K) - (Cl + S))/100 g of dietary dry matter] of +30 or diets based on alfalfa with a dietary cation-anion difference of either +35 or -7. Cows fed the diet with the dietary cation-anion difference of -7 had the lowest urine pH prepartum and had the highest concentrations of ionized Ca in blood and total Ca in serum at parturition. Increases in 1,25-(OH)2 vitamin D per unit decrease in total Ca in serum were greatest for cows fed the diet with a dietary cation-anion difference of -7. Also, cows fed this same diet consumed the most dry matter postpartum. Incidences of health disorders were 13% (10 of 75), 12% (9 of 75), and 5% (4 of 75) for cows fed the diets with dietary cation-anion differences of +30, +35, and -7, respectively. Results indicate that alfalfa, when supplemented with anionic salts, is a viable forage for prepartum dairy cows.

  3. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1980-01-01

    The efforts on the synthesis of polymer anion redox membranes were mainly concentrated in two areas, membrane development and membrane fabrication. Membrane development covered the preparation and evaluation of experimental membranes systems with improved resistance stability and/or lower permeability. Membrane fabrication covered the laboratory scale production of prime candidate membranes in quantities of up to two hundred and sizes up to 18 inches x 18 inches (46 cm x 46 cm). These small (10 in x 11 in) and medium sized membranes were mainly for assembly into multicell units. Improvements in processing procedures and techniques for preparing such membrane sets lifted yields to over 90 percent.

  4. Mixed Anion Heterostructure Materials

    DTIC Science & Technology

    2004-10-01

    data presented Sb(g) Sb(ads) Sb(s) Kads D (1) (2)Very low + GaAs no reaction ( 3 ) kexch 33 for As2 which indicates that the...Kads D (1) (2) ( 3 ) Anion Exchange kexch (4) Isoelectronic AsSb formation Favoured by As4 +As GaAsySb1-y + Sby(s) GaSb1-y + AsSby(s) +As kiso (5...experiment implemented for this investigation provided a basis for modeling the P(g) P(ads) P(s) + GaAs Kads D (1) (2) ( 3 ) kexch (4) +P GaPyAs1-y

  5. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1982-01-01

    The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

  6. Pseudorotation in fullerene anions

    NASA Astrophysics Data System (ADS)

    Dunn, Janette L.; Hands, Ian D.; Bates, Colin A.

    2007-07-01

    Jahn-Teller (JT) problems are often characterised by an adiabatic potential energy surface (APES) containing either a set of isoenergetic wells or a trough of equivalent-energy points, which may be warped by higher-order coupling terms or anisotropic effects. In all three cases, the JT effect will be dynamic. Either tunnelling between the wells or rotation (of a distortion) around the trough will restore the original symmetry of the system. This motion is referred to as pseudorotation. It should be possible to observe a JT system in a distorted geometry if measurements are made on a sufficiently short timescale. In various cubic systems, this timescale has been calculated to be the order of picoseconds. Such timescales are accessible using modern methods of ultrafast spectroscopy. Measurements of pseudorotation rates can lead to important information on the strength and nature of the JT coupling present. We will present analytical calculations that allow the rate of pseudorotation to be determined in terms of the vibronic coupling parameters. We will show how these results can be applied to E ⊗ e systems and then to the more complicated system applicable to C60- anions. This is of particular interest because of the high icosahedral symmetry of fullerene ions and also because of the many potential uses of materials containing these ions. We conclude by outlining experiments that should be capable of measuring pseudorotation in C 60 anions.

  7. Dynamic chemistry of anion recognition

    SciTech Connect

    Custelcean, Radu

    2012-01-01

    In the past 40 years, anion recognition by synthetic receptors has grown into a rich and vibrant research topic, developing into a distinct branch of Supramolecular Chemistry. Traditional anion receptors comprise organic scaffolds functionalized with complementary binding groups that are assembled by multistep organic synthesis. Recently, a new approach to anion receptors has emerged, in which the host is dynamically self-assembled in the presence of the anionic guest, via reversible bond formation between functional building units. While coordination bonds were initially employed for the self-assembly of the anion hosts, more recent studies demonstrated that reversible covalent bonds can serve the same purpose. In both cases, due to their labile connections, the molecular constituents have the ability to assemble, dissociate, and recombine continuously, thereby creating a dynamic combinatorial library (DCL) of receptors. The anionic guests, through specific molecular recognition, may then amplify (express) the formation of a particular structure among all possible combinations (real or virtual) by shifting the equilibria involved towards the most optimal receptor. This approach is not limited to solution self-assembly, but is equally applicable to crystallization, where the fittest anion-binding crystal may be selected. Finally, the pros and cons of employing dynamic combinatorial chemistry (DCC) vs molecular design for developing anion receptors, and the implications of both approaches to selective anion separations, will be discussed.

  8. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Alexander, S.; Hodgdon, R. B.

    1977-01-01

    The objective of NAS 3-20108 was the development and evaluation of improved anion selective membranes useful as efficient separators in a redox power storage cell system being constructed. The program was divided into three parts, (a) optimization of the selected candidate membrane systems, (b) investigation of alternative membrane/polymer systems, and (c) characterization of candidate membranes. The major synthesis effort was aimed at improving and optimizing as far as possible each candidate system with respect to three critical membrane properties essential for good redox cell performance. Substantial improvements were made in 5 candidate membrane systems. The critical synthesis variables of cross-link density, monomer ratio, and solvent composition were examined over a wide range. In addition, eight alternative polymer systems were investigated, two of which attained candidate status. Three other alternatives showed potential but required further research and development. Each candidate system was optimized for selectivity.

  9. Organic Anion Transporting Polypeptides

    PubMed Central

    Stieger, Bruno; Hagenbuch, Bruno

    2013-01-01

    Organic anion transporting polypeptides or OATPs are central transporters in the disposition of drugs and other xenobiotics. In addition, they mediate transport of a wide variety of endogenous substrates. The critical role of OATPs in drug disposition has spurred research both in academia and in the pharmaceutical industry. Translational aspects with clinical questions are the focus in academia, while the pharmaceutical industry tries to define and understand the role these transporters play in pharmacotherapy. The present overview summarizes our knowledge on the interaction of food constituents with OATPs, and on the OATP transport mechanisms. Further, it gives an update on the available information on the structure-function relationship of the OATPs, and finally, covers the transcriptional and posttranscriptional regulation of OATPs. PMID:24745984

  10. Anion transport and supramolecular medicinal chemistry.

    PubMed

    Gale, Philip A; Davis, Jeffery T; Quesada, Roberto

    2017-04-05

    New approaches to the transmembrane transport of anions are discussed in this review. Advances in the design of small molecule anion carriers are reviewed in addition to advances in the design of synthetic anion channels. The application of anion transporters to the potential future treatment of disease is discussed in the context of recent findings on the selectivity of anion transporters.

  11. Ethylene glycol poisoning: a rare but life-threatening cause of metabolic acidosis—a single-centre experience

    PubMed Central

    Kimmel, Martin; Alscher, Mark Dominik; Braun, Niko

    2012-01-01

    Background. Intoxication with ethylene glycol happen all around the world and without rapid recognition and early treatment, mortality from this is high. Methods. In our study, we retrospectively analysed six cases of ethylene glycol intoxication in our department. We measured ethylene glycol or glycolate levels, lactate levels and calculated the osmolal and anion gap. Results. Data from six patients admitted to the nephrology department between 1999 and 2011 with ethylene glycol poisoning are reported. All patients were men. The mean pH on admission was 7.15 ± 0.20 and the anion and osmolal gap were elevated in five of six patients. Four patients had an acute kidney injury and one patient had an acute-on-chronic kidney injury. All patients survived and after being discharged, two patients required chronic intermittent haemodialysis. Interestingly, at the time of admission, all patients had elevated lactate levels but there was no linear regression between toxic levels and lactate levels and no linear correlation was found between initial lactate levels and anion gap and osmolal gap. Conclusions. The initial diagnosis of ethylene glycol poisoning is difficult and poisoning with ethylene glycol is rare but life threatening and needs rapid recognition and early treatment. Therefore, intoxication with ethylene glycol should not be misdiagnosed as lactic acidosis in patients with metabolic acidosis and elevated lactate levels. PMID:25503773

  12. Conditioned medium of human adipose-derived mesenchymal stem cells mediates protection in neurons following glutamate excitotoxicity by regulating energy metabolism and GAP-43 expression.

    PubMed

    Hao, Peng; Liang, Zhanhua; Piao, Hua; Ji, Xiaofei; Wang, Yachen; Liu, Yong; Liu, Rutao; Liu, Jing

    2014-03-01

    Glutamate excitotoxicity has been implicated as one of the pathological mechanisms contributing to neuronal cell death and is involved in many neurological disorders. Stem cell transplantation is a promising approach for the treatment of nervous system damage or diseases. Previous studies have shown that mesenchymal stem cells (MSCs) have important therapeutic effects in experimental animal and preclinical disease model of central nervous system pathology. However, it is not well understood whether neurogenesis of MSCs or MSC conditioned-medium (CM) containing microparticles mediates therapeutic effects. Here, we investigated the neuroprotective effects of human adipose-derived MSCs (AMSCs) on cortical neurons using models of glutamate excitotoxicity. Following exposure to glutamate (100 μM, 15 min), cortical neurons were co-cultured with either AMSCs separated by a semiporous membrane (prohibiting direct cell-cell contact) or with AMSC-CM for 18 h. Compared to untreated control groups, AMSCs and AMSC-CM partially and similarly reduced neuronal cell damages, as indicated by reduced LDH release, a decreased number of trypan-positive cells and a decline in the number of apoptotic nuclei. Protection by CM was associated with increased GAP-43 expression and an elevated number of GAP-43-positive neurites. Furthermore, CM increased levels of ATP, NAD(+) and NADH and the ratio of NAD(+)/NADH, while preventing a glutamate-induced decline in mitochondrial membrane potential. These results demonstrate that AMSC-CM mediates direct neuroprotection by inhibiting neuronal cell damage/apoptosis, promoting nerve regeneration and repair, and restoring bioenergy following energy depletion caused by glutamate excitotoxicity.

  13. Resonant spectra of quadrupolar anions

    NASA Astrophysics Data System (ADS)

    Fossez, K.; Mao, Xingze; Nazarewicz, W.; Michel, N.; Garrett, W. R.; Płoszajczak, M.

    2016-09-01

    In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-rotor problem using a nonadiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. The rotor is treated as a linear triad of point charges with zero monopole and dipole moments and nonzero quadrupole moment. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational bands could be identified above the detachment threshold. We study the evolution of a bound state of an anion as it dives into the continuum at a critical quadrupole moment and we show that the associated critical exponent is α =2 . Everything considered, quadrupolar anions represent a perfect laboratory for the studies of marginally bound open quantum systems.

  14. Bound Anionic States of Aadenine

    SciTech Connect

    Haranczyk, Maciej; Gutowski, Maciej S.; Li, Xiang; Bowen, Kit H.

    2007-03-20

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases are thought to be adiabatically unbound. Contrary to this expectation,wehave demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the newfound anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The new valence states observed here, unlike the dipole-bound state, could exist in condensed phases and might be relevant to radiobiological damage. The discovery of these valence anionic states of adenine was facilitated by the development of (i) an experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a combinatorial/quantum chemical approach for identification of the most stable tautomers of organic molecules.

  15. Bound Anionic States of Adenine

    SciTech Connect

    Haranczyk, Maciej; Gutowski, Maciej S.; Li, Xiang; Bowen, Kit H.

    2007-03-20

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the newfound anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The new valence states observed here, unlike the dipole-bound state, could exist in condensed phases and might be relevant to radiobiological damage. The discovery of these valence anionic states of adenine was facilitated by the development of (i) an experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (it) a combinatorial/quantum chemical approach for identification of the most stable tautomers of organic molecules.

  16. Characterisation of metabolic acidosis in Kenyan children admitted to hospital for acute non-surgical conditions.

    PubMed

    Sasi, P; English, M; Berkley, J; Lowe, B; Shebe, M; Mwakesi, R; Kokwaro, G

    2006-05-01

    Metabolic acidosis is associated with most severe malaria deaths in African children, and most deaths occur before maximum antimalarial action is achieved. Thus, specific acidosis treatment may reduce mortality. However, the underlying mechanisms remain poorly understood and no specific interventions have been developed. A detailed characterisation of this acidosis is critical in treatment development. We used the traditional and Stewart's approach to characterise acidosis in consecutive paediatric admissions for malaria and other acute non-surgical conditions to Kilifi District Hospital in Kenya. The overall acidosis prevalence was 21%. Gastroenteritis had the highest prevalence (61%). Both the mean albumin-corrected anion gap and the strong ion gap were high (>13 mmol/l and >0 mmol/l, respectively) in malaria, gastroenteritis, lower respiratory tract infection and malnutrition. Presence of salicylate in plasma was not associated with acidosis but was associated with signs of severe illness (odds ratio 2.11, 95% CI 1.1-4.2). In malaria, mean (95% CI) strong ion gap was 15 (14-7) mmol/l, and lactate, creatinine and inorganic phosphorous explained only approximately 40% of the variability in base excess (adjusted R2 = 0.397). Acidosis may be more common than previously recognised amongst paediatric admissions in Africa and is characterised by the presence of currently unidentified strong anions. In malaria, lactate and ketones, but not salicylate, are associated with acidosis. However, unidentified anions may be more important.

  17. Anion-exchange nanospheres as titration reagents for anionic analytes.

    PubMed

    Zhai, Jingying; Xie, Xiaojiang; Bakker, Eric

    2015-08-18

    We present here anion-exchange nanospheres as novel titration reagents for anions. The nanospheres contain a lipophilic cation for which the counterion is initially Cl(-). Ion exchange takes place between Cl(-) in the nanospheres and a more lipophilic anion in the sample, such as ClO4(-) and NO3(-). Consecutive titration in the same sample solution for ClO4(-) and NO3(-) were demonstrated. As an application, the concentration of NO3(-) in spinach was successfully determined using this method.

  18. Anion selectivity in biological systems.

    PubMed

    Wright, E M; Diamond, J M

    1977-01-01

    As background for appreciating the still-unsolved problems of monovalent anion selectivity, we summarize the facts and intepretations that seem reasonably well established. In section II we saw that specific effects of monovalent anions on biological and physical systems define qualitative patterns, in that only certain sequences of anion effects are observed. For example, the 4 halides can be permitted on paper as 4! = 24 sequences, yet only 5 of these sequences have been observed in nature as potency sequences. In addition, there are quantitative regularities in anion potency that permit the construction of so-called empirical selectivity isotherms (Figs. 4 and 13). That is, a given potency sequence is found to be associated with only a certain modest range of selectivity ratios. The sequences and isotherms apply to effects with a nonequilibrium component (e.g., permeability and conductance sequences) as well as to purely equilibrium effects. Since students of cation selectivity have had difficulty accepting this conclusion, we discuss the reasons why it is not as paradoxical as it at first seems. In sections III and IV we develop four theoretical models to account for the observed anion potency sequences as sequences of equilibrium binding energies. Two of these models involve calculation of electrostatic binding energies between anions and monopolar or dipolar cationic sites, assuming anions as well as sites to be rigid and nonpolarizable. The other two models use thermochemically measured binding energies between anions and thealkali cations or occasionally alkaline-earth cations, which in fact approximate rigid, nonpolarizable spheres. All four models consider the anion selectivity pattern of a given cationic site to be determined by anion differences in the balance between hydration energies and ion-site binding energies. Site differences in anion selectivity pattern are attributed to site differences in radius, charge, coordination number, or dipole length

  19. Anion transporters and biological systems.

    PubMed

    Gale, Philip A; Pérez-Tomás, Ricardo; Quesada, Roberto

    2013-12-17

    In this Account, we discuss the development of new lipid bilayer anion transporters based on the structure of anionophoric natural products (the prodigiosins) and purely synthetic supramolecular systems. We have studied the interaction of these compounds with human cancer cell lines, and, in general, the most active anion transporter compounds possess the greatest anti-cancer properties. Initially, we describe the anion transport properties of synthetic molecules that are based on the structure of the family of natural products known as the prodiginines. Obatoclax, for example, is a prodiginine derivative with an indole ring that is currently in clinical trials for use as an anti-cancer drug. The anion transport properties of the compounds were correlated with their toxicity toward small cell human lung cancer GLC4 cells. We studied related compounds with enamine moieties, tambjamines, that serve as active transporters. These molecules and others in this series could depolarize acidic compartments within GLC4 cells and trigger apoptosis. In a study of the variation of lipophilicity of a series of these compounds, we observed that, as log P increases, the anion transport efficiency reaches a peak and then decreases. In addition, we discuss the anion transport properties of series of synthetic supramolecular anion receptor species. We synthesized trisureas and thioureas based on the tren backbone, and found that the thiourea compounds effectively transport anions. Fluorination of the pendant phenyl groups in this series of compounds greatly enhances the transport properties. Similar to our earlier results, the most active anion transporters reduced the viability of human cancer cell lines by depolarizing acidic compartments in GLC4 cells and triggering apoptosis. In an attempt to produce simpler transporters that obey Lipinski's Rule of Five, we synthesized simpler systems containing a single urea or thiourea group. Once again the thiourea systems, and in particular

  20. Metabolic acidosis mimicking diabetic ketoacidosis after use of calorie-free mineral water.

    PubMed

    Dahl, Gry T; Woldseth, Berit; Lindemann, Rolf

    2012-09-01

    A previously healthy boy was admitted with fever, tachycardia, dyspnea, and was vomiting. A blood test showed a severe metabolic acidosis with pH 7.08 and an anion gap of 36 mmol/L. His urine had an odor of acetone. The serum glucose was 5.6 mmol/L, and no glucosuria was found. Diabetic ketoacidosis could therefore be eliminated. Lactate level was normal. Tests for the most common metabolic diseases were negative. Because of herpes stomatitis, the boy had lost appetite and only been drinking Diet Coke and water the last days. Diet Coke or Coca-Cola Light is sweetened with a blend containing cyclamates, aspartame, and acesulfame potassium, all free of calories. The etiology of the metabolic acidosis appeared to be a catabolic situation exaggerated by fasting with no intake of calories. The elevated anion gap was due to a severe starvation ketoacidosis, mimicking a diabetic ketoacidosis. Pediatricians should recommend carbohydrate/calorie-containing fluids for rehydration of children with acute fever, diarrhea, or illness.

  1. Anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

    2013-07-23

    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  2. Bound anionic states of adenine

    SciTech Connect

    Haranczyk, Maciej; Gutowski, Maciej S; Li, Xiang; Bowen, Kit H

    2007-03-20

    Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases, are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the new-found anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The discovery of these valence anionic states of adenine was facilitated by the development of: (i) a new experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a new combinatorial/ quantum chemical approach for identification of the most stable tautomers of organic molecules. The computational portion of this work was supported by the: (i) Polish State Committee for Scientific Research (KBN) Grants: DS/8000-4-0140-7 (M.G.) and N204 127 31/2963 (M.H.), (ii) European Social Funds (EFS) ZPORR/2.22/II/2.6/ARP/U/2/05 (M.H.), and (iii) US DOE Office of Biological and Environmental Research, Low Dose Radiation Research Program (M.G.). M.H. holds the Foundation for Polish Science (FNP) award for young scientists. The calculations were performed at the Academic

  3. Acute renal failure and metabolic acidosis due to oxalic acid intoxication: a case report.

    PubMed

    Yamamoto, Rie; Morita, Seiji; Aoki, Hiromichi; Nakagawa, Yoshihide; Yamamoto, Isotoshi; Inokuchi, Sadaki

    2011-12-20

    Most of the reports of oxalic acid intoxication are in cases of ethylene glycol intoxication. These symptoms are known to be central nerve system manifestations, cardiopulmonary manifestations and acute renal failure. There have been only a few reports of direct oxalic acid intoxication. However, there have been a few recent reports of oxalic acid intoxication due to the ingestion of star fruit and ascorbic acid. We herein report the case of a patient with acute renal failure and metabolic acidosis caused directly by consumption of oxalic acid. During the initial examination by the physician at our hospital, the patient presented with tachypnea, a precordinal burning sensation, nausea and metabolic acidosis. After admission, the patient developed renal failure and anion gap high metabolic acidosis, but did not develop any CNS or cardio-pulmonary manifestations in the clinical course. The patient benefitted symptomatically from hemodialysis.

  4. Citrate metabolism in blood transfusions and its relationship due to metabolic alkalosis and respiratory acidosis

    PubMed Central

    Li, Kai; Xu, Yuan

    2015-01-01

    Metabolic alkalosis commonly results from excessive hydrochloric acid (HCl), potassium (K+) and water (H2O) loss from the stomach or through the urine. The plasma anion gap increases in non-hypoproteinemic metabolic alkalosis due to an increased negative charge equivalent on albumin and the free ionized calcium (Ca++) content of plasma decreases. The mean citrate load in all patients was 8740±7027 mg from 6937±6603 mL of transfused blood products. The citrate load was significantly higher in patients with alkalosis (9164±4870 vs. 7809±3967, P < 0.05). The estimated mean total citrate administered via blood and blood products was calculated as 43.2±34.19 mg/kilogram/day. In non-massive and frequent blood transfusions, the elevated carbon dioxide output has been shown to occur. Due to citrate metabolism causes intracellular acidosis. As a result of intracellular acidosis compensation, decompensated metabolic alkalosis + respiratory acidosis and electrolyte imbalance may develop, blood transfusions may result in certain complications. PMID:26131288

  5. Hydrogen in anion vacancies of semiconductors

    SciTech Connect

    Du, Mao-Hua; Singh, David J

    2009-01-01

    Density functional calculations show that, depending on the anion size, hydrogen in anion vacancies of various II-VI semiconductors can be either two-fold or four-fold coordinated, and has either amphoteric or shallow donor character. In general, the multi-coordination of hydrogen in an anion vacancy is the indication of an anionic H, H { ion, in the relatively ionic environment. In more covalent semiconductors, H would form a single cation-H bond in the anion vacancy.

  6. Organic anion uptake by hepatocytes.

    PubMed

    Wolkoff, Allan W

    2014-10-01

    Many of the compounds taken up by the liver are organic anions that circulate tightly bound to protein carriers such as albumin. The fenestrated sinusoidal endothelium of the liver permits these compounds to have access to hepatocytes. Studies to characterize hepatic uptake of organic anions through kinetic analyses, suggested that it was carrier-mediated. Attempts to identify specific transporters by biochemical approaches were largely unsuccessful and were replaced by studies that utilized expression cloning. These studies led to identification of the organic anion transport proteins (oatps), a family of 12 transmembrane domain glycoproteins that have broad and often overlapping substrate specificities. The oatps mediate Na(+)-independent organic anion uptake. Other studies identified a seven transmembrane domain glycoprotein, Na(+)/taurocholate transporting protein (ntcp) as mediating Na(+)-dependent uptake of bile acids as well as other organic anions. Although mutations or deficiencies of specific members of the oatp family have been associated with transport abnormalities, there have been no such reports for ntcp, and its physiologic role remains to be determined, although expression of ntcp in vitro recapitulates the characteristics of Na(+)-dependent bile acid transport that is seen in vivo. Both ntcp and oatps traffic between the cell surface and intracellular vesicular pools. These vesicles move through the cell on microtubules, using the microtubule based motors dynein and kinesins. Factors that regulate this motility are under study and may provide a unique mechanism that can alter the plasma membrane content of these transporters and consequently their accessibility to circulating ligands.

  7. Anions in Nucleic Acid Crystallography.

    PubMed

    D'Ascenzo, Luigi; Auffinger, Pascal

    2016-01-01

    Nucleic acid crystallization buffers contain a large variety of chemicals fitting specific needs. Among them, anions are often solely considered for pH-regulating purposes and as cationic co-salts while their ability to directly bind to nucleic acid structures is rarely taken into account. Here we review current knowledge related to the use of anions in crystallization buffers along with data on their biological prevalence. Chloride ions are frequently identified in crystal structures but display low cytosolic concentrations. Hence, they are thought to be distant from nucleic acid structures in the cell. Sulfate ions are also frequently identified in crystal structures but their localization in the cell remains elusive. Nevertheless, the characterization of the binding properties of these ions is essential for better interpreting the solvent structure in crystals and consequently, avoiding mislabeling of electron densities. Furthermore, understanding the binding properties of these anions should help to get clues related to their potential effects in crowded cellular environments.

  8. Pu Anion Exchange Process Intensification

    SciTech Connect

    Taylor-Pashow, K.

    2015-10-08

    This project seeks to improve the efficiency of the plutonium anion-exchange process for purifying Pu through the development of alternate ion-exchange media. The objective of the project in FY15 was to develop and test a porous foam monolith material that could serve as a replacement for the current anion-exchange resin, Reillex® HPQ, used at the Savannah River Site (SRS) for purifying Pu. The new material provides advantages in efficiency over the current resin by the elimination of diffusive mass transport through large granular resin beads. By replacing the large resin beads with a porous foam there is much more efficient contact between the Pu solution and the anion-exchange sites present on the material. Several samples of a polystyrene based foam grafted with poly(4-vinylpyridine) were prepared and the Pu sorption was tested in batch contact tests.

  9. Selective astrocytic gap junctional trafficking of molecules involved in the glycolytic pathway: Impact on cellular brain imaging

    PubMed Central

    Gandhi, Gautam K.; Cruz, Nancy F.; Ball, Kelly K.; Theus, Sue A.; Dienel, Gerald A.

    2009-01-01

    To assess the specificity of metabolite trafficking among gap junction-coupled astrocytes, we developed novel, real-time, single-cell enzymatic fluorescence assays to assay cell-to-cell transfer of unlabeled glycolytic intermediates and report (i) highly restricted transfer of glucose-6-phosphate(P) and two analogs, deoxyglucose-6-P (DG-6-P), and 2-NBDG-6-P, compared to DG and 2- and 6-NBDG, (ii) extensive junctional diffusion of glyceraldehyde-3-P, NADH, and NADPH plus three anionic fluorescent dyes used as internal standards for transfer assays, and (iii) stimulation of gap junctional communication by increased intracellular Na+ that also evokes metabolic responses in nearby coupled astrocytes. Thus, dye transfer does not predict gap junctional permeability of endogenous metabolites. Intracellular retention of flux-regulating compounds (e.g., glucose-6-P) may be necessary for local metabolic control, whereas ‘syncytial sharing’ may dissipate the work load on peri-synaptic astrocytes. Imaging of brain functional activity depends on local accumulation of exogenous or endogenous signals, and DG-6-P is trapped in the cell where it is phosphorylated, whereas rapid dispersal of cytoplasmic NAD(P)H and labeled glucose metabolites throughout the astrocytic syncytium can interfere with cellular assessment of neuron-astrocyte relationships in autoradiographic, fluorescence microscopic, and magnetic resonance spectroscopic studies. PMID:19457076

  10. Anion binding in biological systems

    NASA Astrophysics Data System (ADS)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  11. Association of two single-isomer anionic CD in NACE for the chiral and achiral separation of fenbendazole, its sulphoxide and sulphone metabolites: application to their determination after in vitro metabolism.

    PubMed

    Rousseau, Anne; Gillotin, Florian; Chiap, Patrice; Crommen, Jacques; Fillet, Marianne; Servais, Anne-Catherine

    2010-05-01

    A NACE method was developed for the separation of fenbendazole (FBZ), a prochiral drug giving rise to chiral (oxfendazole or OFZ) and nonchiral (FBZ sulphone or FBZSO(2)) metabolites. First, the effect of the nature and the concentration of CD as well as that of the acidic BGE on the enantiomeric separation of OFZ were studied. OFZ enantiomers were completely resolved using a BGE made up of 10 mM ammonium formate and 0.5 M TFA in methanol containing 10 mM heptakis(2,3-di-O-acetyl-6-O-sulfo)-beta-CD and 10 mM heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-CD. Moreover, the NACE method was found to be particularly well suited to the simultaneous determination of FBZ, OFZ enantiomers, and FBZSO(2). Thiabendazole was selected as an internal standard. The CD-NACE potential was then evaluated for in vitro metabolism studies using FBZ as a model case. The OFZ enantiomers and FBZSO(2) could be detected after incubation of FBZ in the phenobarbital-induced male rat liver microsomes systems.

  12. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.

    1997-01-01

    Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  13. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.

    1997-09-23

    Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  14. Binding Hydrated Anions with Hydrophobic Pockets.

    PubMed

    Sokkalingam, Punidha; Shraberg, Joshua; Rick, Steven W; Gibb, Bruce C

    2016-01-13

    Using a combination of isothermal titration calorimetry and quantum and molecular dynamics calculations, we demonstrate that relatively soft anions have an affinity for hydrophobic concavity. The results are consistent with the anions remaining partially hydrated upon binding, and suggest a novel strategy for anion recognition.

  15. Anion Solvation in Carbonate Electrolytes

    SciTech Connect

    Zhang, Zhengcheng

    2015-11-16

    With the correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  16. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

  17. Aza compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

  18. Aza compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.Q.; McBreen, J.

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

  19. Hosting anions. The energetic perspective.

    PubMed

    Schmidtchen, Franz P

    2010-10-01

    Hosting anions addresses the widely spread molecular recognition event of negatively charged species by dedicated organic compounds in condensed phases at equilibrium. The experimentally accessible energetic features comprise the entire system including the solvent, any buffers, background electrolytes or other components introduced for e.g. analysis. The deconvolution of all these interaction types and their dependence on subtle structural variation is required to arrive at a structure-energy correlation that may serve as a guide in receptor construction. The focus on direct host-guest interactions (lock-and-key complementarity) that have dominated the binding concepts of artificial receptors in the past must be widened in order to account for entropic contributions which constitute very significant fractions of the total free energy of interaction. Including entropy necessarily addresses the ambiguity and fuzziness of the host-guest structural ensemble and requires the appreciation of the fact that most liquid phases possess distinct structures of their own. Apparently, it is the perturbation of the intrinsic solvent structure occurring upon association that rules ion binding in polar media where ions are soluble and abundant. Rather than specifying peculiar structural elements useful in anion binding this critical review attempts an illumination of the concepts and individual energetic contributions resulting in the final observation of specific anion recognition (95 references).

  20. Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

    NASA Astrophysics Data System (ADS)

    Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

    This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through noncovalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymeric materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous media. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions.

  1. From anion receptors to transporters.

    PubMed

    Gale, Philip A

    2011-03-15

    Cystic fibrosis is the most well-known of a variety of diseases termed channelopathies, in which the regulation of ion transport across cell membranes is so disrupted that the threshold of a pathology is passed. The human toll exacted by these diseases has led a number of research groups, including our own, to create compounds that mediate ion transport across lipid bilayers. In this Account, we discuss three classes of synthetic compounds that were refined to bind and transport anions across lipid bilayer membranes. All of the compounds were originally designed as anion receptors, that is, species that would simply create stable complexes with anions, but were then further developed as transporters. By studying structurally simple systems and varying their properties to change the degree of preorganization, the affinity for anions, or the lipophilicity, we have begun to rationalize why particular anion transport mechanisms (cotransport or antiport processes) occur in particular cases. For example, we have studied the chloride transport properties of receptors based on the closely related structures of isophthalamide and pyridine-2,6-dicarboxamide: the central ring in each case was augmented with pendant methylimidazole groups designed to cotransport H(+) and Cl(-). We observed that the more preorganized pyridine-based receptor was the more efficient transporter, a finding replicated with a series of isophthalamides in which one contained hydroxyl groups designed to preorganize the receptor. This latter class of compound, together with the natural product prodigiosin, can transport bicarbonate (as part of a chloride/bicarbonate antiport process) across lipid bilayer membranes. We have also studied the membrane transport properties of calix[4]pyrroles. Although the parent meso-octamethylcalix[4]pyrrole functions solely as a Cs(+)/Cl(-) cotransporter, other compounds with increased anion affinities can function through an antiport process. One example is octafluoro

  2. The use of chloride-sodium ratio in the evaluation of metabolic acidosis in critically ill neonates.

    PubMed

    Kurt, Abdullah; Ecevit, Ayşe; Ozkiraz, Servet; Ince, Deniz Anuk; Akcan, Abdullah Baris; Tarcan, Aylin

    2012-06-01

    Acid-base disturbances have been usually evaluated with the traditional Henderson-Hasselbach method and Stewart's physiochemical approach by quantifying anions of tissue acids (TA). It is hypothesized that an increase in tissue acids during metabolic acidosis would cause a compensatory decrease in the plasma chloride (Cl) relative to sodium (Cl-Na ratio) in order to preserve electroneutral balance. Therefore, we aimed to investigate the use of Cl-Na ratio as a bedside tool to evaluate the identifying raised TA in neonates as an alternative to complex calculations of Stewart's physiochemical approach. This retrospective study was conducted between January 2008 and December 2009. Infants were included in the study when blood gas analysis reveals a metabolic acidosis; pH <7.25 and sHCO(3) concentration was <22 mEq/L. The Cl-Na ratio, sodium-chloride difference (Diff(NaCl)), anion gap (AG), albumin-corrected AG (AG(corr)), strong ion difference (SID), unmeasured anions (UMA), and TA were calculated at each episode of metabolic acidosis. A total of 105 metabolic acidosis episodes occurred in 59 infants during follow-up. Hypochloremic metabolic acidosis occurred in 17 (16%) of samples, and all had increased TA. The dominant component of TA was UMA rather than lactate. There was a negative correlation between the Cl-Na ratio and SID, AG(corr), UMA, and TA. Also, there was a positive correlation between Diff(NaCl) and SID, AG(corr), UMA, and TA. Base deficit and actual bicarbonate performed poorly in identifying the TA. In conclusion, our study suggested that Diff(NaCl) and Cl-Na ratio are simple and fast, and may be an alternative method to complex Stewart's physiochemical approach in identifying raised UMA and TA in critically ill neonates.

  3. Pyrazole complexes as anion receptors.

    PubMed

    Nieto, Sonia; Pérez, Julio; Riera, Lucía; Riera, Víctor; Miguel, Daniel

    2006-03-01

    The behavior of the receptors [Re(CO)3(Hdmpz)3]BAr'4 (Hdmpz = 3,5-dimethylpyrazole) (1) and [Re(CO)3(HtBupz)3]BAr'4 (HtBupz = 3(5)-tert-butylpyrazole) (2; Ar' = 3,5-bis(trifluoromethyl)phenyl) toward the anions fluoride, chloride, bromide, iodide, hydrogensulfate, dihydrogenphosphate, nitrate, and perrhenate was studied in CD3CN solution. In most cases, the receptors were stable. Anion exchange was fast, and binding constants were calculated from the NMR titration profiles. The structure of the adduct [Re(CO)3(HtBupz)3] x NO3 (3) was determined by X-ray diffraction. Two pyrazole moieties are hydrogen-bonded to one nitrate oxygen atom, and the third pyrazole moiety is hydrogen-bonded to an oxygen atom of an adjacent nitrate, leading to infinite chains. The structure of the adduct [Re(CO)3(Hdmpz)3]BAr'4acetone (4), also determined by X-ray diffraction, showed a similar interaction of two pyrazole N-H groups with the acetone oxygen atom. F- and H2PO4(-) deprotonate the receptors, and HSO4(-) decomposed 1. The structure of one of the decomposition products (5), determined by X-ray diffraction, is consistent with pyrazole protonation and substitution by sulfate.

  4. The brain metabolic activity after resuscitation with liposome-encapsulated hemoglobin in a rat model of hypovolemic shock.

    PubMed

    Rao, Geeta; Hedrick, Andria F; Yadav, Vivek R; Xie, Jun; Hussain, Alamdar; Awasthi, Vibhudutta

    2015-09-01

    We examined the effect of resuscitation with liposome-encapsulated hemoglobin (LEH) on cerebral bioenergetics in a rat model of 45% hypovolemia. The rats were resuscitated with isovolemic LEH or saline after 15 minutes of shock and followed up to 6 hours. Untreated hypovolemic rats received no fluid. The cerebral uptake of F-18-fluorodeoxyglucose (FDG) was measured by PET, and at 6 hours, the brain was collected for various assays. Hypovolemia decreased cellular adenosine triphosphate (ATP), phosphocreatine, nicotinamide adenine dinucleotide (NAD)/NADH ratio, citrate synthase activity, glucose-6-phosphate, and nerve growth factor (NGF), even when FDG uptake remained unchanged. The FDG uptake was reduced by saline, but not by LEH infusion. The reduced FDG uptake in saline group was associated with a decrease in hexokinase I expression. The LEH infusion effectively restored ATP content, NAD/NADH ratio, and NGF expression, and reduced the hypovolemia-induced accumulation of pyruvate and ubiquitinated proteins; in comparison, saline was significantly less effective. The LEH infusion was associated with low pH and high anion gap, indicating anionic gap acidosis. The results suggest that hypovolemic shock perturbs glucose metabolism at the level of pyruvate utilization, resulting in deranged cerebral energy stores. The correction of volume and oxygen deficits by LEH recovers the cerebral metabolism and creates a prosurvival phenotype.

  5. Behind the Pay Gap

    ERIC Educational Resources Information Center

    Dey, Judy Goldberg; Hill, Catherine

    2007-01-01

    Women have made remarkable gains in education during the past three decades, yet these achievements have resulted in only modest improvements in pay equity. The gender pay gap has become a fixture of the U.S. workplace and is so ubiquitous that many simply view it as normal. "Behind the Pay Gap" examines the gender pay gap for college graduates.…

  6. Tunable electronic interactions between anions and perylenediimide.

    PubMed

    Goodson, Flynt S; Panda, Dillip K; Ray, Shuvasree; Mitra, Atanu; Guha, Samit; Saha, Sourav

    2013-08-07

    Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

  7. Analysis of anions in beer using ion chromatography

    PubMed Central

    Bruce, Jonathan

    2002-01-01

    The majority of anions found in beer are a consequence of impurities derived from the water used during the brewing process. The process of beer manufacture consists of malting, brewing and fermentation followed by maturation before filtration and finally storage. Strict quality control is required because the presence of certain anions outside strictly defined tolerance limits can affect the flavour characteristics of the finished product. The anions present were quantified using the technique of ion chromatography with the Metrohm modular system following sample preparation. The analysis produced a result of the order 200 mg l-1 for chloride, phosphate and sulphate and around 20 mg l-1 for nitrate. If the chloride level exceeds 250 mg l-1, then the sweetness of the beer is enhanced, but yeast flocculation can be hindered. An excess of sulphate can give a sharp, dry edge to hopped beers and excessive amounts of nitrate have been found to harm the yeast metabolism after conversion to the nitrite form. As water is a primary ingredient within beer, its quality and type is a fundamental factor in establishing many of the distinctive regional beers that can be found in the United Kingdom and is thus monitored carefully. PMID:18924733

  8. Analysis of anions in beer using ion chromatography.

    PubMed

    Bruce, Jonathan

    2002-01-01

    The majority of anions found in beer are a consequence of impurities derived from the water used during the brewing process. The process of beer manufacture consists of malting, brewing and fermentation followed by maturation before filtration and finally storage. Strict quality control is required because the presence of certain anions outside strictly defined tolerance limits can affect the flavour characteristics of the finished product. The anions present were quantified using the technique of ion chromatography with the Metrohm modular system following sample preparation. The analysis produced a result of the order 200 mg l(-1) for chloride, phosphate and sulphate and around 20 mg l(-1) for nitrate. If the chloride level exceeds 250 mg l(-1), then the sweetness of the beer is enhanced, but yeast flocculation can be hindered. An excess of sulphate can give a sharp, dry edge to hopped beers and excessive amounts of nitrate have been found to harm the yeast metabolism after conversion to the nitrite form. As water is a primary ingredient within beer, its quality and type is a fundamental factor in establishing many of the distinctive regional beers that can be found in the United Kingdom and is thus monitored carefully.

  9. Effects of dietary cation-anion difference on the acid-base status of dry cows.

    PubMed

    Vagnoni, D B; Oetzel, G R

    1998-06-01

    Responses in dry matter intake (DMI) and acidbase balance to three sources of anionic salts (dietary cation-anion difference = -63 to -40 meq/kg of dry matter), an acidified fermentation by-product, MgSO4.7H2O + NH4Cl, and MgSO4.7H2O + CaCl2.2H2O + CaSO4, were evaluated relative to the responses of cows fed a control diet (dietary cationanion difference = 203 meq/kg of dry matter) that did not contain anionic salts. Diets were fed for 1-wk periods to eight nonlactating Holsteins assigned to two replicated 4 x 4 Latin squares. Daily DMI increased as time of access to the diet increased up to d 5; mean DMI over d 5 to 7 was reduced by dietary anionic salts. Diets containing anionic salts induced a mild metabolic acidosis that was completely compensated by nonrespiratory mechanisms (decreased blood bicarbonate and base excess; pCO2 and pH values were unaffected). Urinary pH values and bicarbonate excretion were reduced, and urinary NH4+ and titratable acidity excretion were increased, for cows fed diets containing anionic salts. Strong ion difference in urine was decreased by dietary anionic salts because of the relatively greater excretions of Cl- and S2- versus Na+ and K+ by cows fed these diets. Dietary anionic salts decreased mean ruminal pH by 0.12 units, possibly because of the reduced strong ion difference of ruminal fluid. Dietary anionic salts increased mean ruminal NH3 concentration by 2.2 mM, probably because of the higher nonprotein N content of these diets. The strong negative relationship (r2 = 0.95) between urinary pH and net acid excretion by cows fed the diets containing anionic salts suggested that urinary pH measurement might be a useful tool to assess the degree of metabolic acidosis that was imposed by dietary anionic salts.

  10. Anion adsorption induced surface reconstructions

    NASA Astrophysics Data System (ADS)

    Tang, Lei

    2005-11-01

    Surface stress plays an important role in the behavior of solid surfaces. Potential-controlled anion adsorption in electrolytes alters the surface stress of the electrode and results in morphology changes to the surfaces. With a combination of potential-induced surface stress measurement and in situ electrochemical scanning tunneling microscopy (STM), it is demonstrated that anion adsorption induces changes in structure of thin films and modifies the growth morphology and stress evolution in epitaxially grown films. Surface structural transitions in the heteroepitaxial system consisting of one to two gold monolayers on platinum substrates were observed. By increasing the potential, structural transitions, from (1 x 1), to a striped phase, to a hexagonal structure, occurred in the gold bilayer. This hexagonal structure was related to the formation of an ordered sulfate adlayer with a ( 3x7 ) structure. Such transitions were repeatable by cycling the potential. Furthermore, the transitions between various dislocation structures were affected by anion adsorption. The surface composition of the gold bilayer on Pt was measured by underpotential deposition of copper. By subtracting the contribution of a pure Pt surface from the gold bi-layer on Pt, a stress change of -2.4 N/m was observed, which agrees with the stress change of -2.46 N/m predicted to accompany formation of 1.5 MLs of coherent Au on Pt(111) from epitaxy theory. The Cu monolayer deposited on Au(111) from an acid sulfate electrolyte was found to be pseudomorphic while the Cu monolayer formed on Au(111) in vacuum was incoherent. The stress-thickness change associated with the coherent monolayer of copper on Au(111) in electrolyte was -0.6 N/m, while conventional epitaxy theories predict a value of +7.76 N/m. STM results elucidated the sulfate adsorption on the copper monolayer caused an expansion of the layer as evidenced by a Moire Structure. For the Cu monolayer on Au(111), the sulfate-induced expansion

  11. Nexal membrane permeability to anions

    PubMed Central

    1978-01-01

    The permeability of the septa of the earthworm in the median axon has been calculated for the anions fluorescein and its halogen derivatives. The values ranged from 5.4 X 10(-5) to 4 X 10(-6) cm/s. Previously, the septa had been shown to contain nexuses. By using freeze-fracture material, the surface area of nexus on the septal membranes was determined to be 4.5%, very similar to the percentage of nexus in the intercalated disk of mammalian myocardium. Plasma membrane permeability to these dyes was also calculated and shown to be much less than that of the septal membranes. In addition, an estimate of cytoplasmic binding for each dye was made, and most dyes showed little or no binding with the exception of aminofluorescein. PMID:702107

  12. Relative acidifying activity of anionic salts commonly used to prevent milk fever.

    PubMed

    Goff, J P; Ruiz, R; Horst, R L

    2004-05-01

    High cation diets can cause milk fever in dairy cows as they induce a metabolic alkalosis reducing the ability of the cow to maintain calcium homeostasis at the onset of lactation. Adding anions to the diet can offset the effect of the high cation forages by inducing a mild metabolic acidosis, restoring the ability to maintain calcium homeostasis. The difference in mEq of dietary cations and anions (DCAD) is most often expressed as (Na(+) + K+) - (Cl- + S(--)). This equation implies that a mEq of chloride and a mEq of sulfate are equipotent in their ability to alter acid-base balance of the cow. Using blood and urine pH to monitor effects on acid-base balance, experiments were conducted to test the relative acidifying activity of various sulfate and chloride anion sources in nonpregnant, nonlactating Jersey cows. Across all experiments, chloride proved to have about 1.6 times the acidifying activity of sulfate. Calcium and magnesium, ignored by the common DCAD equation, had a small but significant alkalinizing effect when accompanying chloride or sulfate. The ranking of the anion sources tested at a dose of 2 Eq/d, from most to least potent urine acidifier, was hydrochloric acid, ammonium chloride, calcium chloride, calcium sulfate, magnesium sulfate, and sulfur. These data should allow more accurate prediction of the response of late gestation cows to dietary cation-anion manipulation.

  13. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

    Kuswandi, Bambang; Nuriman; Verboom, Willem; Reinhoudt, David N.

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  14. Creating molecular macrocycles for anion recognition

    PubMed Central

    2016-01-01

    Summary The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures. PMID:27340452

  15. Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

    PubMed Central

    Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

    2010-01-01

    This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through non-covalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymer materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous environments. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions. PMID:20871791

  16. Polymers for anion recognition and sensing.

    PubMed

    Rostami, Ali; Taylor, Mark S

    2012-01-16

    In biological systems, the selective and high-affinity recognition of anionic species is accomplished by macromolecular hosts (anion-binding proteins) that have been "optimized" through evolution. Surprisingly, it is only recently that chemists have systematically attempted to develop anion-responsive synthetic macromolecules for potential applications in medicine, national security, or environmental monitoring. Recent results indicating that unique features of polymeric systems such as signal amplification, multivalency, and cooperative behavior may be exploited productively in the context of anion recognition and sensing are documented. The wide variety of interactions-including Lewis acid/base, ion-pairing, and hydrogen bonding-that have been employed for this purpose is reflected in the structural diversity of anion-responsive macromolecules identified to date.

  17. Asymmetric Anion-π Catalysis on Perylenediimides.

    PubMed

    Wang, Chao; Miros, François N; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-11-07

    Anion-π catalysis, that is the stabilization of anionic transition states on π-acidic aromatic surfaces, has so far been developed with naphthalenediimides (NDIs). This report introduces perylenediimides (PDIs) to anion-π catalysis. The quadrupole moment of PDIs (+23.2 B) is found to exceed that of NDIs and reach new records with acceptors in the core (+70.9 B), and their larger surface provides space to better accommodate chemical transformations. Unlike NDIs, the activity of PDI catalysts for enolate and enamine addition is determined by the twist of their π surface rather than their reducibility. These results, further strengthened by nitrate inhibition and circular dichroism spectroscopy, support an understanding of anion-π interactions centered around quadrupole moments, i.e., electrostatic contributions, rather than redox potentials and charge transfer. The large PDI surfaces provide access to the highest enantioselectivities observed so far in anion-π catalysis (96 % ee).

  18. Organic anion transporter (Slc22a) family members as mediators of toxicity

    SciTech Connect

    Sweet, Douglas H. . E-mail: sweetd@musc.edu

    2005-05-01

    Exposure of the body to toxic organic anions is unavoidable and occurs from both intentional and unintentional sources. Many hormones, neurotransmitters, and waste products of cellular metabolism, or their metabolites, are organic anions. The same is true for a wide variety of medications, herbicides, pesticides, plant and animal toxins, and industrial chemicals and solvents. Rapid and efficient elimination of these substances is often the body's best defense for limiting both systemic exposure and the duration of their pharmacological or toxicological effects. For organic anions, active transepithelial transport across the renal proximal tubule followed by elimination via the urine is a major pathway in this detoxification process. Accordingly, a large number of organic anion transport proteins belonging to several different gene families have been identified and found to be expressed in the proximal nephron. The function of these transporters, in combination with the high volume of renal blood flow, predisposes the kidney to increased toxic susceptibility. Understanding how the kidney mediates the transport of organic anions is integral to achieving desired therapeutic outcomes in response to drug interactions and chemical exposures, to understanding the progression of some disease states, and to predicting the influence of genetic variation upon these processes. This review will focus on the organic anion transporter (OAT) family and discuss the known members, their mechanisms of action, subcellular localization, and current evidence implicating their function as a determinant of the toxicity of certain endogenous and xenobiotic agents.

  19. Coma, metabolic acidosis, and methemoglobinemia in a patient with acetaminophen toxicity.

    PubMed

    Kanji, Hussein D; Mithani, Shazma; Boucher, Paul; Dias, Valerian C; Yarema, Mark C

    2013-01-01

    We present a case of early coma, metabolic acidosis and methemoglobinemia after substantial acetaminophen toxicity in the absence of hepatic failure. A 77-year-old female presented to the emergency department with a decreased level of consciousness. She was found unresponsive by a family member in her bed, and was reported to be acting normally when she was last seen eight hours earlier. Laboratory results on arrival were: pH 7.19, sodium 139 mmol/L, chloride 106 mmol/L, potassium 3.3 mmol/L, CO2 8 mmol/L, and an anion gap of 25. Both venous lactate (10.2 mmol/L) and methemoglobin (9.4 %) were elevated. The patient's acetaminophen concentration was markedly elevated at 7138 µmol/L (1078 µg/ml). Hepatic enzymes and coagulation tests were normal [alanine transaminase (ALT) 8 U/L, international normalized ratio (INR) 1.0]. Intravenous N-acetylcysteine (NAC) was initiated at a dose of 150 mg/kg over 15 minutes, followed by 50 mg/kg over the next four hours, followed by 100 mg/kg over the next 16 hours. Twenty-four hours after admission, the anion gap metabolic acidosis had resolved, and the methemoglobin was 2.1%. Aminotransferases peaked at 44 U/L and INR peaked at 1.9. A urine 5-oxoproline assay performed five days after admission was negative, suggesting no evidence of a 5-oxoprolinase deficiency. We describe the pathophysiology and discuss the literature on acetaminophen-induced coma and metabolic acidosis in the absence of hepatic injury; and propose mechanisms for associated methemoglobinemia. 

  20. Anion stripping as a general method to create cationic porous framework with mobile anions.

    PubMed

    Mao, Chengyu; Kudla, Ryan A; Zuo, Fan; Zhao, Xiang; Mueller, Leonard J; Bu, Xianhui; Feng, Pingyun

    2014-05-28

    Metal-organic frameworks (MOFs) with cationic frameworks and mobile anions have many applications from sensing, anion exchange and separation, to fast ion conductivity. Despite recent progress, the vast majority of MOFs have neutral frameworks. A common mechanism for the formation of neutral frameworks is the attachment of anionic species such as F(-) or OH(-) to the framework metal sites, neutralizing an otherwise cationic scaffolding. Here, we report a general method capable of converting such neutral frameworks directly into cationic ones with concurrent generation of mobile anions. Our method is based on the differential affinity between distinct metal ions with framework anionic species. Specifically, Al(3+) is used to strip F(-) anions away from framework Cr(3+) sites, leading to cationic frameworks with mobile Cl(-) anions. The subsequent anion exchange with OH(-) further leads to a porous network with mobile OH(-) anions. New materials prepared by anion stripping can undergo ion exchange with anionic organic dyes and also exhibit much improved ionic conductivity compared to the original unmodified MOFs.

  1. Closing the Pay Gap

    DTIC Science & Technology

    2000-10-01

    the pay gap has been narrowed, hut only to just under 10 percent. And current military compensation legislation does not close the gap until 2026. There...will continue to be a pay gap until 2026 unless the next administration and the next Congress provide more for pay above the 1999 legislated ramp- up...of .5 percent (one half of one percent) per year to attain pay equality . That means that soldiers, sailors, airmen, marines and Coast Guardsmen

  2. Anionic Derivatives of Perfluorinated Trimethylgold.

    PubMed

    Menjón, Babil; Pérez-Bitrián, Alberto; Martínez-Salvador, Sonia; Baya, Miguel; Casas, José María; Martín, Antonio; Orduna, Jesús

    2017-03-20

    The homoleptic compound [PPh₄][CF₃AuCF₃] cleanly undergoes photoinduced oxidative addition of CF₃I to afford the organogold(III) derivative [PPh₄][(CF₃)₃AuI] in good yield and under mild conditions. This compound provides a convenient entry to the chemistry of the perfluorinated (CF₃)₃Au fragment whose properties are analyzed with the aid of DFT methods and compared with those of the homologous non-fluorinated (CH₃)₃Au moiety. It is found that reductive elimination of CX₃-CX₃ in the former (X = F) requires a much higher energy barrier than in the latter (X = H) and is therefore considerably less favored. This can be considered as one of the main features underlying the significantly higher stability associated to the (CF₃)₃Au fragment and its derivatives. This unsaturated, 14-electron species can be stabilized by coordination of any of the halide ligands, including fluoride. In fact, the whole series of anionic [PPh₄][(CF₃)₃AuX] complexes (X = F, Cl, Br, I, CN) has now been isolated and conveniently characterized. Evidence for intermolecular decomposition pathways upon thermolysis in the condensed phase is presented.

  3. Anion conductance selectivity mechanism of the CFTR chloride channel.

    PubMed

    Linsdell, Paul

    2016-04-01

    All ion channels are able to discriminate between substrate ions to some extent, a process that involves specific interactions between permeant anions and the so-called selectivity filter within the channel pore. In the cystic fibrosis transmembrane conductance regulator (CFTR) anion-selective channel, both anion relative permeability and anion relative conductance are dependent on anion free energy of hydration--anions that are relatively easily dehydrated tend to show both high permeability and low conductance. In the present work, patch clamp recording was used to investigate the relative conductance of different anions in CFTR, and the effect of mutations within the channel pore. In constitutively-active E1371Q-CFTR channels, the anion conductance sequence was Cl(-) > NO3(-) > Br(-) > formate > SCN(-) > I(-). A mutation that disrupts anion binding in the inner vestibule of the pore (K95Q) disrupted anion conductance selectivity, such that anions with different permeabilities showed almost indistinguishable conductances. Conversely, a mutation at the putative narrowest pore region that is known to disrupt anion permeability selectivity (F337A) had minimal effects on anion relative conductance. Ion competition experiments confirmed that relatively tight binding of permeant anions resulted in relatively low conductance. These results suggest that the relative affinity of ion binding in the inner vestibule of the pore controls the relative conductance of different permeant anions in CFTR, and that the pore has two physically distinct anion selectivity filters that act in series to control anion conductance selectivity and anion permeability selectivity respectively.

  4. Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

    PubMed

    Ghosh, Semanti; Bagchi, Angshuman

    2015-12-01

    Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio-hydrogen.

  5. Photoelectron spectroscopy of nitromethane anion clusters

    NASA Astrophysics Data System (ADS)

    Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

    2016-08-01

    Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

  6. Anion photoelectron imaging spectroscopy of glyoxal

    NASA Astrophysics Data System (ADS)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei

    2016-09-01

    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  7. Senseless Extravagance, Shocking Gaps

    ERIC Educational Resources Information Center

    Weissbourd, Richard; Dodge, Trevor

    2012-01-01

    Although most people in the United States believe, at least theoretically, in educational equality, fewer and fewer appear to care about the resource gaps between affluent and poor schools, says Weissbourd. He illustrates these gaps with vivid descriptions of what he calls an "opulence arms race" among affluent independent schools, but…

  8. Information Gap Activities.

    ERIC Educational Resources Information Center

    Cicekdag, Mehmet Ali

    1995-01-01

    Focuses on a real world technique used to teach language proficiency in the classroom. This method involves creating deliberate information and opinion gaps by administering pop quizzes and other communicative games and filling those gaps through cooperative action. Use of this technique generated heated discussion among students. (nine…

  9. Bridging a Cultural Gap

    ERIC Educational Resources Information Center

    Leviatan, Talma

    2008-01-01

    There has been a broad wave of change in tertiary calculus courses in the past decade. However, the much-needed change in tertiary pre-calculus programmes--aimed at bridging the gap between high-school mathematics and tertiary mathematics--is happening at a far slower pace. Following a discussion on the nature of the gap and the objectives of a…

  10. Narrowing Participation Gaps

    ERIC Educational Resources Information Center

    Hand, Victoria; Kirtley, Karmen; Matassa, Michael

    2015-01-01

    Shrinking the achievement gap in mathematics is a tall order. One way to approach this challenge is to think about how the achievement gap manifests itself in the classroom and take concrete action. For example, opportunities to participate in activities that involve mathematical reasoning and argumentation in a safe and supportive manner are…

  11. Confronting the Achievement Gap

    ERIC Educational Resources Information Center

    Gardner, David

    2007-01-01

    This article talks about the large achievement gap between children of color and their white peers. The reasons for the achievement gap are varied. First, many urban minorities come from a background of poverty. One of the detrimental effects of growing up in poverty is receiving inadequate nourishment at a time when bodies and brains are rapidly…

  12. The National "Expertise Gap"

    ERIC Educational Resources Information Center

    Hamilton, Kendra

    2005-01-01

    This article discusses the Woodrow Wilson National Fellowship Foundation's report, "Diversity and the Ph.D.," released in May, which documents in troubling detail the exact dimensions of what the foundation's president, Dr. Robert Weisbuch, is calling the national "expertise gap." Weisbuch states that the expertise gap extends beyond the…

  13. The Parenting Gap

    ERIC Educational Resources Information Center

    Reeves, Richard V.; Howard, Kimberly

    2013-01-01

    The parenting gap is a big factor in the opportunity gap. The chances of upward social mobility are lower for children with parents struggling to do a good job--in terms of creating a supportive and stimulating home environment. Children lucky enough to have strong parents are more likely to succeed at all the critical life stages, which means…

  14. Which Achievement Gap?

    ERIC Educational Resources Information Center

    Anderson, Sharon; Medrich, Elliott; Fowler, Donna

    2007-01-01

    From the halls of Congress to the local elementary school, conversations on education reform have tossed around the term "achievement gap" as though people all know precisely what that means. As it's commonly used, "achievement gap" refers to the differences in scores on state or national achievement tests between various…

  15. States Address Achievement Gaps.

    ERIC Educational Resources Information Center

    Christie, Kathy

    2002-01-01

    Summarizes 2 state initiatives to address the achievement gap: North Carolina's report by the Advisory Commission on Raising Achievement and Closing Gaps, containing an 11-point strategy, and Kentucky's legislation putting in place 10 specific processes. The North Carolina report is available at www.dpi.state.nc.us.closingthegap; Kentucky's…

  16. Kinetics and mechanism of exogenous anion exchange in FeFbpA-NTA: significance of periplasmic anion lability and anion binding activity of ferric binding protein A.

    PubMed

    Heymann, Jared J; Gabricević, Mario; Mietzner, Timothy A; Crumbliss, Alvin L

    2010-02-01

    The bacterial transferrin ferric binding protein A (FbpA) requires an exogenous anion to facilitate iron sequestration, and subsequently to shuttle the metal across the periplasm to the cytoplasmic membrane. In the diverse conditions of the periplasm, numerous anions are known to be present. Prior in vitro experiments have demonstrated the ability of multiple anions to fulfill the synergistic iron-binding requirement, and the identity of the bound anion has been shown to modulate important physicochemical properties of iron-bound FbpA (FeFbpA). Here we address the kinetics and mechanism of anion exchange for the FeFbpA-nitrilotriacetate (NTA) assembly with several biologically relevant anions (citrate, oxalate, phosphate, and pyrophosphate), with nonphysiologic NTA serving as a representative synergistic anion/chelator. The kinetic data are consistent with an anion-exchange process that occurs in multiple steps, dependent on the identity of both the entering anion and the leaving anion. The exchange mechanism may proceed either as a direct substitution or through an intermediate FeFbpA-X* assembly based on anion (X) identity. Our kinetic results further develop an understanding of exogenous anion lability in the periplasm, as well as address the final step of the iron-free FbpA (apo-FbpA)/Fe(3+) sequestration mechanism. Our results highlight the kinetic significance of the FbpA anion binding site, demonstrating a correlation between apo-FbpA/anion affinity and the FeFbpA rate of anion exchange, further supporting the requirement of an exogenous anion to complete tight sequestration of iron by FbpA, and developing a mechanism for anion exchange within FeFbpA that is dependent on the identity of both the entering anion and the leaving anion.

  17. Lactate versus non-lactate metabolic acidosis: a retrospective outcome evaluation of critically ill patients

    PubMed Central

    Gunnerson, Kyle J; Saul, Melissa; He, Shui; Kellum, John A

    2006-01-01

    Introduction Acid–base abnormalities are common in the intensive care unit (ICU). Differences in outcome exist between respiratory and metabolic acidosis in similar pH ranges. Some forms of metabolic acidosis (for example, lactate) seem to have worse outcomes than others (for example, chloride). The relative incidence of each type of disorder is unknown. We therefore designed this study to determine the nature and clinical significance of metabolic acidosis in critically ill patients. Methods An observational, cohort study of critically ill patients was performed in a tertiary care hospital. Critically ill patients were selected on the clinical suspicion of the presence of lactic acidosis. The inpatient mortality of the entire group was 14%, with a length of stay in hospital of 12 days and a length of stay in the ICU of 5.8 days. Results We reviewed records of 9,799 patients admitted to the ICUs at our institution between 1 January 2001 and 30 June 2002. We selected a cohort in which clinicians caring for patients ordered a measurement of arterial lactate level. We excluded patients in which any necessary variable required to characterize an acid–base disorder was absent. A total of 851 patients (9% of ICU admissions) met our criteria. Of these, 548 patients (64%) had a metabolic acidosis (standard base excess < -2 mEq/l) and these patients had a 45% mortality, compared with 25% for those with no metabolic acidosis (p < 0.001). We then subclassified metabolic acidosis cases on the basis of the predominant anion present (lactate, chloride, or all other anions). The mortality rate was highest for lactic acidosis (56%); for strong ion gap (SIG) acidosis it was 39% and for hyperchloremic acidosis 29% (p < 0.001). A stepwise logistic regression model identified serum lactate, SIG, phosphate, and age as independent predictors of mortality. Conclusion In critically ill patients in which a measurement of lactate level was ordered, lactate and SIG were strong

  18. A new class of organocatalysts: sulfenate anions.

    PubMed

    Zhang, Mengnan; Jia, Tiezheng; Yin, Haolin; Carroll, Patrick J; Schelter, Eric J; Walsh, Patrick J

    2014-09-26

    Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate-catalyzed (1-10 mol%) coupling of benzyl halides in the presence of base to generate trans-stilbenes in good to excellent yields (up to 99%). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst.

  19. Anionic Lewis Acids. A Chemical Oxymoron.

    DTIC Science & Technology

    1995-10-17

    NUMBER OF PAGES12 anionic lewis acid ab initio synthesis 1 2 methide FT NMR 16. PRICE CODE imide multi-nule r 17. SECURITY CLASSIFICATION 18...chemically robust, thermally stable, non-toxic, environmentally safe, and cost-effective. One of our current areas of interest involves the synthesis and...developing a predictive knowledge base that can be used to guide the synthesis of new locally electron-deficient anions. Additionally, we proposed to

  20. Fluorescence-lifetime-based sensors for anions

    NASA Astrophysics Data System (ADS)

    Teichmann, Maria; Draxler, Sonja; Kieslinger, Dietmar; Lippitsch, Max E.

    1997-05-01

    Sensing of anions has been investigated using the fluorescence decaytime as the information carrier. The sensing mechanism is based on the coextraction of an anion and a proton, and the presence of a fluorophore with a rather long fluorescence decaytime inside the membrane to act as a pH indicator. The relevant theory is discussed shortly. As an example a sensor for nitrate is shown, and the influence of ionic additives on the working function has been investigated.

  1. High Performance Anion Chromatography of Gadolinium Chelates.

    PubMed

    Hajós, Peter; Lukács, Diana; Farsang, Evelin; Horváth, Krisztian

    2016-11-01

    High performance anion chromatography (HPIC) method to separate ionic Gd chelates, [Formula: see text], [Formula: see text], [Formula: see text] and free matrix anions was developed. At alkaline pHs, polydentate complexing agents such as ethylene-diamine-tetraacetate, diethylene-triamine pentaacetate and trans-1,2-diamine-cyclohexane-tetraacetate tend to form stable Gd chelate anions and can be separated by anion exchange. Separations were studied in the simple isocratic chromatographic run over the wide range of pH and concentration of carbonate eluent using suppressed conductivity detection. The ion exchange and complex forming equilibria were quantitatively described and demonstrated in order to understand major factors in the control of selectivity of Gd chelates. Parameters of optimized resolution between concurrent ions were presented on a 3D resolution surface. The applicability of the developed method is represented by the simultaneous analysis of Gd chelates and organic/inorganic anions. Inductively coupled plasma atomic emission spectroscopy  (ICP-AES) analysis was used for confirmation of HPIC results for Gd. Collection protocols for the heart-cutting procedure of chromatograms were applied. SPE procedures were also developed not only to extract traces of free gadolinium ions from samples, but also to remove the high level of interfering anions of the complex matrices. The limit of detection, the recoverability and the linearity of the method were also presented.

  2. Use of hydrochloric acid as a source of anions for prevention of milk fever.

    PubMed

    Goff, J P; Horst, R L

    1998-11-01

    Diets that contain high amounts of K induce milk fever by alkalinizing the blood of the cow, reducing the ability of homeostatic mechanisms to maintain normal blood concentrations of Ca. The addition of anions to the diet induces metabolic acidosis, which counteracts the alkalinizing effect of the high cation diets commonly fed to cows. Currently, anions are usually added as anionic salts, such as CaCl2 or MgSO4, and the pH of urine is often monitored to assess the degree of metabolic acidification resulting from the addition of anions to the diet. An alternative source of anions is HCl. In Experiment 1, the addition of HCl to the diet of cows that were not pregnant and not lactating significantly reduced the pH of urine and blood within 24 h. After HCl was removed from the diet, the pH of urine returned to baseline levels within 48 h. In Experiment 2, the inclusion of HCl into the prepartum ration of Jersey cows entering the third or greater lactation significantly reduced the incidence of milk fever from 63% of control cows to 11% of the treated cows and also reduced the degree of hypocalcemia that was experienced by the cows during the periparturient period. Plasma Ca concentrations at 0.5 d after calving were 5.33 +/- 0.52 and 6.69 +/- 0.51 mg/dl in the control and the HCl-treated cows, respectively. In Experiment 2, the prepartum consumption of the ration with HCl was greater than the consumption of the control ration. In liquid form, HCl remains dangerous to handle and corrosive to machinery. Commercial preparations of HCl mixed into common feed ingredients as a premix could offer an inexpensive and palatable alternative to anionic salts as a means of controlling the incidence of milk fever in dairy cows.

  3. SPARK GAP SWITCH

    DOEpatents

    Neal, R.B.

    1957-12-17

    An improved triggered spark gap switch is described, capable of precisely controllable firing time while switching very large amounts of power. The invention in general comprises three electrodes adjustably spaced and adapted to have a large potential impressed between the outer electrodes. The central electrode includes two separate elements electrically connected togetaer and spaced apart to define a pair of spark gaps between the end electrodes. Means are provided to cause the gas flow in the switch to pass towards the central electrode, through a passage in each separate element, and out an exit disposed between the two separate central electrode elements in order to withdraw ions from the spark gap.

  4. Starvation Ketoacidosis as a Cause of Unexplained Metabolic Acidosis in the Perioperative Period

    PubMed Central

    Mostert, Monique; Bonavia, Anthony

    2016-01-01

    Patient: Female, 24 Final Diagnosis: Starvation ketoacidosis Symptoms: None Medication: — Clinical Procedure: Lumbar laminectomy Specialty: Orthopedics and Traumatology Objective: Unusual clinical course Background: Besides providing anesthesia for surgery, the anesthesiologist’s role is to optimize the patient for surgery and for post-surgical recovery. This involves timely identification and treatment of medical comorbidities and abnormal laboratory values that could complicate the patient’s perioperative course. There are several potential causes of anion and non-anion gap metabolic acidosis in surgical patients, most of which could profoundly affect a patient’s surgical outcome. Thus, the presence of an acute acid-base disturbance requires a thorough workup, the results of which will influence the patient’s anesthetic management. Case Report: An otherwise-healthy 24-year-old female presented for elective spine surgery and was found to have metabolic acidosis, hypotension, and polyuria intraoperatively. Common causes of acute metabolic acidosis were investigated and systematically ruled out, including lactic acidosis, diabetic ketoacidosis, drug-induced ketoacidosis, ingestion of toxic alcohols (e.g., methanol, ethylene glycol), uremia, and acute renal failure. Laboratory workup was remarkable only for elevated serum and urinary ketone levels, believed to be secondary to starvation ketoacidosis. Due to the patient’s unexplained acid-base disturbance, she was kept intubated postoperatively to allow for further workup and management. Conclusions: Starvation ketoacidosis is not widely recognized as a perioperative entity, and it is not well described in the medical literature. Lack of anesthesiologist awareness about this disorder may complicate the differential diagnosis for acute intraoperative metabolic acidosis and lead to a prolonged postoperative stay and an increase in hospital costs. The short- and long-term implications of perioperative

  5. Fiber optic gap gauge

    DOEpatents

    Wood, Billy E.; Groves, Scott E.; Larsen, Greg J.; Sanchez, Roberto J.

    2006-11-14

    A lightweight, small size, high sensitivity gauge for indirectly measuring displacement or absolute gap width by measuring axial strain in an orthogonal direction to the displacement/gap width. The gap gauge includes a preferably titanium base having a central tension bar with springs connecting opposite ends of the tension bar to a pair of end connector bars, and an elongated bow spring connected to the end connector bars with a middle section bowed away from the base to define a gap. The bow spring is capable of producing an axial strain in the base proportional to a displacement of the middle section in a direction orthogonal to the base. And a strain sensor, such as a Fabry-Perot interferometer strain sensor, is connected to measure the axial strain in the base, so that the displacement of the middle section may be indirectly determined from the measurement of the axial strain in the base.

  6. Sulfate Is Both a Substrate and an Activator of the Voltage-Dependent Anion Channel of Arabidopsis Hypocotyl Cells1

    PubMed Central

    Frachisse, Jean-Marie; Thomine, Sébastien; Colcombet, Jean; Guern, Jean; Barbier-Brygoo, Hélène

    1999-01-01

    On the basis of the anion content of in vitro-cultured Arabidopsis plantlets, we explored the selectivity of the voltage-dependent anion channel of the plasma membrane of hypocotyl cells. In the whole-cell configuration, substitution of cytosolic Cl− by different anions led to the following sequence of relative permeabilities: NO3− (2.6) ≥ SO42− (2.0) > Cl− (1.0) > HCO3− (0.8) ≫ malate2− (0.03). Large whole-cell currents were measured for NO3− and SO42−, about five to six times higher than the equivalent Cl− currents. Since SO42− is usually considered to be a weakly permeant or non-permeant ion, the components of the large whole-cell current were explored in more detail. Aside from its permeation through the channel with a unitary conductance, about two-thirds that of Cl−, SO42− had a regulatory effect on channel activity by preventing the run-down of the anion current both in the whole-cell and the outside-out configuration, increasing markedly the whole-cell current. The fact that the voltage-dependent plasma membrane anion channel of hypocotyl cells can mediate large NO3− and SO42− currents and is regulated by nucleotides favors the idea that this anion channel can contribute to the cellular homeostasis of important metabolized anions. PMID:10482681

  7. Characterization of Antisense Transformed Plants Deficient in the Tobacco Anionic Peroxidase.

    PubMed Central

    Lagrimini, L. M.; Gingas, V.; Finger, F.; Rothstein, S.; Liu, TTY.

    1997-01-01

    On the basis of the biological compounds that they metabolize, plant peroxidases have long been implicated in plant growth, cell wall biogenesis, lignification, and host defenses. Transgenic tobacco (Nicotiana tabacum L.) plants that underexpress anionic peroxidase were generated using antisense RNA. The antisense RNA was found to be specific for the anionic isoenzyme and highly effective, reducing endogenous transcript levels and total peroxidase activity by as much as 1600-fold. Antisense-transformed plants appeared normal at initial observation; however, growth studies showed that plants with reduced peroxidase activity grow taller and flower sooner than control plants. In contrast, previously transformed plants overproducing anionic peroxidase were shorter and flowered later than controls. Axillary buds were more developed in antisense-transformed plants and less developed in plants overproducing this enzyme. It was found that the lignin content in leaf, stem, and root was unchanged in antisense-transformed plants, which does not support a role for anionic peroxidase in the lignification of secondary xylem vessels. However, studies of wounded tissue show some reduction in wound-induced deposition of lignin-like polymers. The data support a possible role for tobacco anionic peroxidase in host defenses but not without a reduction in growth potential. PMID:12223765

  8. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

  9. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-12-11

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  10. Isatinphenylsemicarbazones as efficient colorimetric sensors for fluoride and acetate anions - anions induce tautomerism.

    PubMed

    Jakusová, Klaudia; Donovalová, Jana; Cigáň, Marek; Gáplovský, Martin; Garaj, Vladimír; Gáplovský, Anton

    2014-04-05

    The anion induced tautomerism of isatin-3-4-phenyl(semicarbazone) derivatives is studied herein. The interaction of F(-), AcO(-), H2PO4(-), Br(-) or HSO4(-) anions with E and Z isomers of isatin-3-4-phenyl(semicarbazone) and N-methylisatin-3-4-phenyl(semicarbazone) as sensors influences the tautomeric equilibrium of these sensors in the liquid phase. This tautomeric equilibrium is affected by (1) the inter- and intra-molecular interactions' modulation of isatinphenylsemicarbazone molecules due to the anion induced change in the solvation shell of receptor molecules and (2) the sensor-anion interaction with the urea hydrogens. The acid-base properties of anions and the difference in sensor structure influence the equilibrium ratio of the individual tautomeric forms. Here, the tautomeric equilibrium changes were indicated by "naked-eye" experiment, UV-VIS spectral and (1)H NMR titration, resulting in confirmation that appropriate selection of experimental conditions leads to a high degree of sensor selectivity for some investigated anions. Sensors' E and Z isomers differ in sensitivity, selectivity and sensing mechanism. Detection of F(-) or CH3COO(-) anions at high weakly basic anions' excess is possible.

  11. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, Kristen

    2004-12-01

    This project have focuses on the basic chemical aspects of anion receptor design of functional pH independent systems, with the ultimate goal of targeting the selective binding of sulfate, as well as design of separations strategies for selective and efficient removal of targeted anions. Key findings include: (1) the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. Areas probed during the last funding period include: the design, synthesis, and physical and structural characterization of receptors and investigation of anion and dual ion pair extraction using lipophilic amide receptors for anion binding. A new collaboration has been added to the project in addition to the one with Dr. Bruce Moyer at Oak Ridge National Laboratory, with Professor Jonathan Sessler at the University of Texas at Austin.

  12. Putting anion-π interactions into perspective.

    PubMed

    Frontera, Antonio; Gamez, Patrick; Mascal, Mark; Mooibroek, Tiddo J; Reedijk, Jan

    2011-10-04

    Supramolecular chemistry is a field of scientific exploration that probes the relationship between molecular structure and function. It is the chemistry of the noncovalent bond, which forms the basis of highly specific recognition, transport, and regulation events that actuate biological processes. The classic design principles of supramolecular chemistry include strong, directional interactions like hydrogen bonding, halogen bonding, and cation-π complexation, as well as less directional forces like ion pairing, π-π, solvophobic, and van der Waals potentials. In recent years, the anion-π interaction (an attractive force between an electron-deficient aromatic π system and an anion) has been recognized as a hitherto unexplored noncovalent bond, the nature of which has been interpreted through both experimental and theoretical investigations. The design of selective anion receptors and channels based on this interaction represent important advances in the field of supramolecular chemistry. The objectives of this Review are 1) to discuss current thinking on the nature of this interaction, 2) to survey key experimental work in which anion-π bonding is demonstrated, and 3) to provide insights into the directional nature of anion-π contact in X-ray crystal structures.

  13. Infrared spectroscopy of anionic hydrated fluorobenzenes

    NASA Astrophysics Data System (ADS)

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-09-01

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C6F6-•H2O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules.

  14. Cytotoxic mechanisms of hydrosulfide anion and cyanide anion in primary rat hepatocyte cultures.

    PubMed

    Thompson, Rodney W; Valentine, Holly L; Valentine, William M

    2003-06-30

    Hydrogen sulfide and hydrogen cyanide are known to compromise mitochondrial respiration through inhibition of cytochrome c oxidase and this is generally considered to be their primary mechanism of toxicity. Experimental studies and the efficiency of current treatment protocols suggest that H(2)S may exert adverse physiological effects through additional mechanisms. To evaluate the role of alternative mechanisms in H(2)S toxicity, the relative contributions of electron transport inhibition, uncoupling of mitochondrial respiration, and opening of the mitochondrial permeability transition pore (MPTP) to hydrosulfide and cyanide anion cytotoxicity in primary hepatocyte cultures were examined. Supplementation of hepatocytes with the glycolytic substrate, fructose, rescued hepatocytes from cyanide anion induced toxicity, whereas fructose supplementation increased hydrosulfide anion toxicity suggesting that hydrosulfide anion may compromise glycolysis in hepatocytes. Although inhibitors of the MPTP opening were protective for hydrosulfide anion, they had no effect on cyanide anion toxicity, consistent with an involvement of the permeability transition pore in hydrosulfide anion toxicity but not cyanide anion toxicity. Exposure of isolated rat liver mitochondria to hydrosulfide did not result in large amplitude swelling suggesting that if H(2)S induces the permeability transition it does so indirectly through a mechanism requiring other cellular components. Hydrosulfide anion did not appear to be an uncoupler of mitochondrial respiration in hepatocytes based upon the inability of oligomycin and fructose to protect hepatocytes from hydrosulfide anion toxicity. These findings support mechanisms additional to inhibition of cytochrome c oxidase in hydrogen sulfide toxicity. Further investigations are required to assess the role of the permeability transition in H(2)S toxicity, determine whether similar affects occur in other cell types or in vivo and evaluate whether this may

  15. Vibrational spectroscopy of microhydrated conjugate base anions.

    PubMed

    Asmis, Knut R; Neumark, Daniel M

    2012-01-17

    Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aerosols, which are a central component of atmospheric and oceanic chemical cycles. In this Account, as a means of studying conjugate-base anions in water, we describe infrared multiple-photon dissociation spectroscopy on clusters in which the sulfate, nitrate, bicarbonate, and suberate anions are hydrated by a known number of water molecules. This spectral technique, used over the range of 550-1800 cm(-1), serves as a structural probe of these clusters. The experiments follow how the solvent network around the conjugate-base anion evolves, one water molecule at a time. We make structural assignments by comparing the experimental infrared spectra to those obtained from electronic structure calculations. Our results show how changes in anion structure, symmetry, and charge state have a profound effect on the structure of the solvent network. Conversely, they indicate how hydration can markedly affect the structure of the anion core in a microhydrated cluster. Some key results include the following. The first few water molecules bind to the anion terminal oxo groups in a bridging fashion, forming two anion-water hydrogen bonds. Each oxo group can form up to three hydrogen bonds; one structural result, for example, is the highly symmetric, fully coordinated SO(4)(2-)(H(2)O)(6) cluster, which only contains bridging water molecules. Adding more water molecules results in the formation of a solvent network comprising water-water hydrogen bonding in addition to hydrogen bonding to the anion. For the nitrate, bicarbonate, and suberate anions, fewer bridging sites are available, namely, three, two, and one (per carboxylate group), respectively. As a result, an earlier onset of water

  16. Precision gap particle separator

    DOEpatents

    Benett, William J.; Miles, Robin; Jones, II., Leslie M.; Stockton, Cheryl

    2004-06-08

    A system for separating particles entrained in a fluid includes a base with a first channel and a second channel. A precision gap connects the first channel and the second channel. The precision gap is of a size that allows small particles to pass from the first channel into the second channel and prevents large particles from the first channel into the second channel. A cover is positioned over the base unit, the first channel, the precision gap, and the second channel. An port directs the fluid containing the entrained particles into the first channel. An output port directs the large particles out of the first channel. A port connected to the second channel directs the small particles out of the second channel.

  17. MULTIPLE SPARK GAP SWITCH

    DOEpatents

    Schofield, A.E.

    1958-07-22

    A multiple spark gap switch of unique construction is described which will permit controlled, simultaneous discharge of several capacitors into a load. The switch construction includes a disc electrode with a plurality of protuberances of generally convex shape on one surface. A firing electrode is insulatingly supponted In each of the electrode protuberances and extends substantially to the apex thereof. Individual electrodes are disposed on an insulating plate parallel with the disc electrode to form a number of spark gaps with the protuberances. These electrodes are each connected to a separate charged capacitor and when a voltage ls applied simultaneously between the trigger electrodes and the dlsc electrode, each spark gap fires to connect its capacitor to the disc electrode and a subsequent load.

  18. Templating irreversible covalent macrocyclization by using anions.

    PubMed

    Kataev, Evgeny A; Kolesnikov, Grigory V; Arnold, Rene; Lavrov, Herman V; Khrustalev, Victor N

    2013-03-11

    Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of the intermediate plays a decisive role in determining the product distribution. For the macrocyclization under kinetic control, it was shown that the amount of a template, the conformational rigidity of building blocks, and the anion affinities of reaction components and intermediates are important parameters that one should take into consideration to achieve high yields.

  19. Electron anions and the glass transition temperature

    PubMed Central

    Sushko, Peter V.; Tomota, Yudai; Hosono, Hideo

    2016-01-01

    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32]2+ ⋅ (e–)2, we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design. PMID:27559083

  20. Discovering lead-free perovskite solar materials with a split-anion approach.

    PubMed

    Sun, Yi-Yang; Shi, Jian; Lian, Jie; Gao, Weiwei; Agiorgousis, Michael L; Zhang, Peihong; Zhang, Shengbai

    2016-03-28

    Organic-inorganic hybrid perovskite solar materials, being low-cost and high-performance, are promising for large-scale deployment of the photovoltaic technology. A key challenge that remains to be addressed is the toxicity of these materials since the high-efficiency solar cells are made of lead-containing materials, in particular, CH3NH3PbI3. Here, based on first-principles calculation, we search for lead-free perovskite materials based on the split-anion approach, where we replace Pb with non-toxic elements while introducing dual anions (i.e., splitting the anion sites) that preserve the charge neutrality. We show that CH3NH3BiSeI2 and CH3NH3BiSI2 exhibit improved band gaps and optical absorption over CH3NH3PbI3. The split-anion approach could also be applied to pure inorganic perovskites, significantly enlarging the pool of candidate materials in the design of low-cost, high-performance and environmentally-friendly perovskite solar materials.

  1. Rho GAPs and GEFs

    PubMed Central

    van Buul, Jaap D; Geerts, Dirk; Huveneers, Stephan

    2014-01-01

    Within blood vessels, endothelial cell–cell and cell–matrix adhesions are crucial to preserve barrier function, and these adhesions are tightly controlled during vascular development, angiogenesis, and transendothelial migration of inflammatory cells. Endothelial cellular signaling that occurs via the family of Rho GTPases coordinates these cell adhesion structures through cytoskeletal remodelling. In turn, Rho GTPases are regulated by GTPase-activating proteins (GAPs) and guanine nucleotide exchange factors (GEFs). To understand how endothelial cells initiate changes in the activity of Rho GTPases, and thereby regulate cell adhesion, we will discuss the role of Rho GAPs and GEFs in vascular biology. Many potentially important Rho regulators have not been studied in detail in endothelial cells. We therefore will first overview which GAPs and GEFs are highly expressed in endothelium, based on comparative gene expression analysis of human endothelial cells compared with other tissue cell types. Subsequently, we discuss the relevance of Rho GAPs and GEFs for endothelial cell adhesion in vascular homeostasis and disease. PMID:24622613

  2. Closing the Performance Gap.

    ERIC Educational Resources Information Center

    Riggins, Cheryl G.

    2002-01-01

    Describes how the principal of a K-2, 400-student suburban elementary school near Flint, Michigan, worked with her staff and superintendent to develop and implement a strategic plan to close the student achievement gap. Reports significant improvement in reading and math scores after 1 year. (PKP)

  3. STEMMING the Gap

    ERIC Educational Resources Information Center

    Kahler, Jim; Valentine, Nancy

    2011-01-01

    America has a gap when it comes to youth pursuing science and technology careers. In an effort to improve the knowledge and application of science, technology, engineering, and math (STEM), after-school programs can work in conjunction with formal in-school curriculum to improve science education. One organization that actively addresses this…

  4. Confronting the Autonomy Gap

    ERIC Educational Resources Information Center

    Adamowski, Steven; Petrilli, Michael J.

    2007-01-01

    "The Autonomy Gap," a recent study by the American Institute for Research and the Thomas B. Fordham Institute, found that many public elementary school principals feel constrained by a bureaucracy that impedes their ability to raise student achievement. Unfortunately, those principals are still held accountable for their school's results--even…

  5. The Academic Generation Gap

    ERIC Educational Resources Information Center

    Dronzek, Anna

    2008-01-01

    The current generation gap in academia is different--fundamentally shaped by the structural problems of academic employment. The job market has especially exacerbated tensions between senior and junior faculty by ratcheting up expectations and requirements at every stage of the academic career. The disparities have been mentioned often enough to…

  6. Structuring the Information Gap.

    ERIC Educational Resources Information Center

    Edge, Julian

    1984-01-01

    Describes an information gap procedure to teach a new structure which requires students to look for and exchange information in order to complete a task in an English as a second language class. Illustrates the method with a set of materials and suggests ways for teachers to produce similar materials. (SED)

  7. Multiple gap photovoltaic device

    DOEpatents

    Dalal, Vikram L.

    1981-01-01

    A multiple gap photovoltaic device having a transparent electrical contact adjacent a first cell which in turn is adjacent a second cell on an opaque electrical contact, includes utilizing an amorphous semiconductor as the first cell and a crystalline semiconductor as the second cell.

  8. Estimating Gender Wage Gaps

    ERIC Educational Resources Information Center

    McDonald, Judith A.; Thornton, Robert J.

    2011-01-01

    Course research projects that use easy-to-access real-world data and that generate findings with which undergraduate students can readily identify are hard to find. The authors describe a project that requires students to estimate the current female-male earnings gap for new college graduates. The project also enables students to see to what…

  9. California: Emigrant Gap

    Atmospheric Science Data Center

    2014-05-15

    ... Imaging SpectroRadiometer (MISR) images of the Central Valley and the Sierra Nevada Mountains show several smoke plumes from wildfires ... from the Emigrant Gap Fire, located about 40 kilometers west of Lake Tahoe. The animated panorama uses different MISR cameras to enable ...

  10. Bridging a Communication Gap

    ERIC Educational Resources Information Center

    Kahn, Ethel

    1972-01-01

    Description of a community program in cooperation with a regional extension service. The goals were to explore the generation gap, and conflict in life values, understand family role, increase self awareness, improve adult-youth communication, and understand the individual and his relationship to basic social principles. (Author/JB)

  11. Bridging the Development Gap.

    DTIC Science & Technology

    1999-11-01

    Bridging the Development Gap is contractual cooperative agreement between Mercury Computer Systems, Inc. and DARPA. This program was developed...processing, interfacing with I/O devices, memory constraints, as well as real-time throughput and latency challenges. Mercury has bridged the indicated

  12. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2010-12-07

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  13. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  14. Photoelectron spectroscopic studies of 5-halouracil anions

    SciTech Connect

    Radisic, Dunja; Ko, Yeon Jae; Nilles, John M.; Stokes, Sarah T.; Bowen, Kit H.; Sevilla, Michael D.; Rak, Janusz

    2011-01-07

    The parent negative ions of 5-chlorouracil, UCl{sup -} and 5-fluorouracil, UF{sup -} have been studied using anion photoelectron spectroscopy in order to investigate the electrophilic properties of their corresponding neutral halouracils. The vertical detachment energies (VDE) of these anions and the adiabatic electron affinities (EA) of their neutral molecular counterparts are reported. These results are in good agreement with the results of previously published theoretical calculations. The VDE values for both UCl{sup -} and UF{sup -} and the EA values for their neutral molecular counterparts are much greater than the corresponding values for both anionic and neutral forms of canonical uracil and thymine. These results are consistent with the observation that DNA is more sensitive to radiation damage when thymine is replaced by halouracil. While we also attempted to prepare the parent anion of 5-bromouracil, UBr{sup -}, we did not observe it, the mass spectrum exhibiting only Br{sup -} fragments, i.e., 5-bromouracil apparently underwent dissociative electron attachment. This observation is consistent with a previous assessment, suggesting that 5-bromouracil is the best radio-sensitizer among these three halo-nucleobases.

  15. Photoelectron spectroscopic studies of 5-halouracil anions

    NASA Astrophysics Data System (ADS)

    Radisic, Dunja; Ko, Yeon Jae; Nilles, John M.; Stokes, Sarah T.; Sevilla, Michael D.; Rak, Janusz; Bowen, Kit H.

    2011-01-01

    The parent negative ions of 5-chlorouracil, UCl- and 5-fluorouracil, UF- have been studied using anion photoelectron spectroscopy in order to investigate the electrophilic properties of their corresponding neutral halouracils. The vertical detachment energies (VDE) of these anions and the adiabatic electron affinities (EA) of their neutral molecular counterparts are reported. These results are in good agreement with the results of previously published theoretical calculations. The VDE values for both UCl- and UF- and the EA values for their neutral molecular counterparts are much greater than the corresponding values for both anionic and neutral forms of canonical uracil and thymine. These results are consistent with the observation that DNA is more sensitive to radiation damage when thymine is replaced by halouracil. While we also attempted to prepare the parent anion of 5-bromouracil, UBr-, we did not observe it, the mass spectrum exhibiting only Br- fragments, i.e., 5-bromouracil apparently underwent dissociative electron attachment. This observation is consistent with a previous assessment, suggesting that 5-bromouracil is the best radio-sensitizer among these three halo-nucleobases.

  16. Superelectrophilic amidine dications: dealkylation by triflate anion.

    PubMed

    Kovacevic, Luka S; Idziak, Christopher; Markevicius, Augustinas; Scullion, Callum; Corr, Michael J; Kennedy, Alan R; Tuttle, Tell; Murphy, John A

    2012-08-20

    Superelectrophiles: Formamides were designed that when treated with triflic anhydride would be transformed into superelectrophilic amidine dications. These dications were so electrophilic that they underwent in situ dealkylation by the triflate anion (see scheme; Tf = trifluoromethanesulfonyl). DFT calculations were used to determine the mechanistic details of the dealkylation reaction.

  17. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S [Los Alamos, NM; Thorn, David L [Los Alamos, NM

    2011-11-22

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  18. Anion-Conducting Polymer, Composition, and Membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2008-10-21

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  19. Interactions of dietary cation-anion balance and phosphorus: effects on growth and serum inorganic phosphorus in dairy calves.

    PubMed

    Beighle, D E; Tucker, W B; Hemken, R W

    1988-12-01

    Thirty-six male and female Holstein and Jersey calves were assigned at weaning to a randomized complete block design in a 2 x 3 factorial arrangement to evaluate the influence of two dietary cation-anion balances (-14 and +39 meq(Na + K)-(Cl + S) per 100 g diet DM) and three amounts of dietary P (.22, .29, and .37%) on performance and P metabolism from 9 to 19 wk of age. Feed intake, average daily gain, and serum inorganic P were higher on the anionic diets and increased with increasing dietary P. Body weights were higher on the .37% P diets by wk 3 and on the anionic diets by wk 6. The interaction of dietary P and cation-anion balance was responsible for significant differences in calf performance; the anionic diet exhibited marked improvement over the cationic diet at the lowest P concentration. Results indicate that the availability of P for young dairy calves may be higher with anionic than cationic diets.

  20. Non-invasive microfluidic gap junction assay.

    PubMed

    Chen, Sisi; Lee, Luke P

    2010-03-01

    Gap junctions are protein channels between cells that allow direct electrical and metabolic coupling via the exchange of biomolecules and ions. Their expression, though ubiquitous in most mammalian cell types, is especially important for the proper functioning of cardiac and neuronal systems. Many existing methods for studying gap junction communication suffer from either unquantifiable data or difficulty of use. Here, we measure the extent of dye spread and effective diffusivities through gap junction connected cells using a quantitative microfluidic cell biology platform. After loading dye by hydrodynamic focusing of calcein/AM, dye transfer dynamics into neighboring, unexposed cells can be monitored via timelapse fluorescent microscopy. By using a selective microfluidic dye loading over a confluent layer of cells, we found that high expression of gap junctions in C6 cells transmits calcein across the monolayer with an effective diffusivity of 3.4 x 10(-13) m(2)/s, which are highly coupled by Cx43. We also found that the gap junction blocker 18alpha-GA works poorly in the presence of serum even at high concentrations (50 microM); however, it is highly effective down to 2.5 microM in the absence of serum. Furthermore, when the drug is washed out, dye spread resumes rapidly within 1 min for all doses, indicating the drug does not affect transcriptional regulation of connexins in these Cx43+ cells, in contrast to previous studies. This integrated microfluidic platform enables the in situ monitoring of gap junction communication, yielding dynamic information about intercellular molecular transfer and pharmacological inhibition and recovery.

  1. Cationic-anionic mediated charge compensation on La2Ti2O7 for visible light photocatalysis.

    PubMed

    Liu, Peng; Nisar, Jawad; Pathak, Biswarup; Ahuja, Rajeev

    2013-10-28

    The cationic-anionic mediated charge compensation effect was studied in the layered perovskite La2Ti2O7 for the visible light photocatalysis. Our screened hybrid density functional study shows that the electronic structure of La2Ti2O7 can be tuned by the cationic (V, Nb, Ta)/anionic (N) mono- and co-doping. Such mono-doping creates impurity states in the band gap which helps the electron-hole recombination. But if the charge compensation is made by the cationic-anionic mediated co-doping then such impurity states can be removed and can be a promising strategy for visible light photocatalysis. The absolute band edge position of the doped La2Ti2O7 has been aligned with respect to the water oxidation/reduction potential. The calculated defect formation energy shows the stability of the co-doping system is improved due to the coulomb interactions and charge compensations effect.

  2. Anionic phospholipids modulate peptide insertion into membranes.

    PubMed

    Liu, L P; Deber, C M

    1997-05-06

    While the insertion of a hydrophobic peptide or membrane protein segment into the bilayer can be spontaneous and driven mainly by the hydrophobic effect, anionic lipids, which comprise ca. 20% of biological membranes, provide a source of electrostatic attractions for binding of proteins/peptides into membranes. To unravel the interplay of hydrophobicity and electrostatics in the binding of peptides into membranes, we designed peptides de novo which possess the typical sequence Lys-Lys-Ala-Ala-Ala-X-Ala-Ala-Ala-Ala-Ala-X-Ala-Ala-Trp-Ala-Ala-X-Ala-Al a-Ala-Lys-Lys-Lys-Lys-amide, where X residues correspond to "guest" residues which encompass a range of hydrophobicity (Leu, Ile, Gly, and Ser). Circular dichroism spectra demonstrated that peptides were partially (40-90%) random in aqueous buffer but were promoted to form 100% alpha-helical structures by anionic lipid micelles. In neutral lipid micelles, only the relatively hydrophobic peptides (X = L and I) spontaneously adopted the alpha-helical conformation, but when 25% of negatively charged lipids were mixed in to mimic the content of anionic lipids in biomembranes, the less hydrophobic (X = S and G) peptides then formed alpha-helical conformations. Consistent with these findings, fluorescence quenching by the aqueous-phase quencher iodide indicated that in anionic (dimyristoylphosphatidylglycerol) vesicles, the peptide Trp residue was buried in the lipid vesicle hydrophobic core, while in neutral (dimyristoylphosphatidylcholine) vesicles, only hydrophobic (X = L and I) peptides were shielded from the aqueous solution. Trp emission spectra of peptides in the presence of phospholipids doxyl-labeled at the 5-, 7-, 10-, 12-, and 16-fatty acid positions implied not only a transbilayer orientation for inserted peptides but also that mixed peptide populations (transbilayer + surface-associated) may arise. Overall results suggest that for hydrophobic peptides with segmental threshold hydrophobicity below that which

  3. Effect of dietary potassium and anionic salts on acid-base and mineral status in periparturient cows.

    PubMed

    Rérat, M; Schlegel, P

    2014-06-01

    Dry cow diets based on grassland forage from intensive production contain high amounts of K and could be responsible for a reduced ability to maintain Ca homoeostasis. The aim of this study was to determine whether a moderate anionic salt supplementation to a forage-based pre-calving diet with varying native K content affects the mineral and acid-base status in transition cows. Twenty-four dry and pregnant Holstein cows, without antecedent episodes of clinical hypocalcemia, were assigned to two diets during the last 4 weeks before estimated calving date. Twelve cows were fed a hay-based diet low in K (18 g K/kg DM), and 12, a hay-based diet high in K (35 g K/kg DM). Within each diet, six cows received anionic salts during the last 2 weeks before the estimated calving day. After calving, all cows received the high K diet ad libitum. Blood samples were taken daily from day 11 pre-partum to day 5 post-partum. Urine samples were taken on days 7 and 2 pre-partum and on day 2 post-partum. The anionic salt did not alter feed intake during the pre-partum period. Serum Ca was not influenced by the dietary treatments. Feeding pre-partum diets with low K concentrations induced a reduced metabolic alkalotic charge, as indicated by reduced pre-partum urinary base-acid quotient. Transition cows fed the low K diet including anionic salts induced a mild metabolic acidosis before calving, as indicated by higher urinary Ca, lower urinary pH and net acid-base excretion. Although serum Ca during the post-partum period was not affected by dietary treatment, feeding a low K diet moderately supplemented with anionic salts to reach a dietary cation-anion difference close to zero permitted to obtain a metabolic response in periparturient cows without altering the dry matter intake.

  4. Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion

    SciTech Connect

    Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J; Lynch, Vincent M.; Hay, Benjamin; Moyer, Bruce A; Sessler, Jonathan L.

    2014-01-01

    Cage-type calix[4]pyrroles 2 and 3 bearing two additional pyrrole groups on the strap have been synthesized. Compared with the parent calix[4]pyrrole (1), they were found to exhibit remarkably enhanced affinities for anions, including the sulfate anion (TBA+ salts), in organic media (CD2Cl2). This increase is ascribed to participation of the bipyrrole units in anion binding. Receptors 2 and 3 extract the hydrophilic sulfate anion (as the methyltrialkyl(C8-10)ammonium (A336+) salt)) from aqueous media into a chloroform phase with significantly improved efficiency (>10-fold relative to calix[4]pyrrole 1). These two receptors also solubilize into chloroform the otherwise insoluble sulfate salt, (TMA)2SO4 (tetramethylammonium sulfate).

  5. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Jonathan L. Sessler

    2007-09-21

    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  6. Understanding and modeling removal of anionic organic contaminants (AOCs) by anion exchange resins.

    PubMed

    Zhang, Huichun; Shields, Anthony J; Jadbabaei, Nastaran; Nelson, Maurice; Pan, Bingjun; Suri, Rominder P S

    2014-07-01

    Ionic organic contaminants (OCs) are a growing concern for water treatment and the environment and are removed inefficiently by many existing technologies. This study examined removal of anionic OCs by anion exchange resins (AXRs) as a promising alternative. Results indicate that two polystyrene AXRs (IRA910 and IRA96) have higher sorption capacities and selectivity than a polyacrylate resin (A860). For the polystyrene resins, selectivity follows: phenolates ≥ aromatic dicarboxylates > aromatic monocarboxylates > benzenesulfonate > aliphatic carboxylates. This trend can be explained based on hydration energy, the number of exchange groups, and aromaticity and hydrophobicity of the nonpolar moiety (NPM) of the anions. For A860, selectivity only varies within a narrow range (0.13-1.64). Despite the importance of the NPM of the anions, neutral solutes were sorbed much less, indicating synergistic combinations of electrostatic and nonelectrostatic interactions in the overall sorption. By conducting multiple linear regression between Abraham's descriptors and nature log of selectivity, induced dipole-related interactions and electrostatic interactions were found to be the most important interaction forces for sorption of the anions, while solute H-bond basicity has a negative effect. A predictive model was then developed for carboxylates and phenolates based on the poly parameter linear free energy relationships established for a diverse range of 16 anions and 5 neutral solutes, and was validated by accurate prediction of sorption of five test solutes within a wide range of equilibrium concentrations and that of benzoate at different pH.

  7. Anion-π interactions involving [MX(n)](m-) anions: a comprehensive theoretical study.

    PubMed

    Estarellas, Carolina; Quiñonero, David; Deyà, Pere M; Frontera, Antonio

    2013-01-14

    In this manuscript we perform a systematic study on the geometric and energetic features of anion-π complexes, wherein the anion is a metal complex of variable shapes and charges. Such a study is lacking in the literature. For the calculations we used the ab initio RI-MP2/def2-TZVPP level of theory. A search in the Cambridge Structural Database (CSD) provides the experimental starting point that inspired the subsequent theoretical study. The influence of [MX(n)](m-) on the anion-π interaction was analyzed in terms of energetic, geometric, and charge transfer properties and Bader's theory of "atom-in-molecules" (AIM). The binding energy depends on the coordination index, geometric features and different orientations adopted by the metallic anion. The binding mode resembling a stacking interaction for linear, trigonal planar and square-planar anions is the most favorable. For tetrahedral and octahedral anions the most favorable orientation is the one with three halogen atoms pointing to the ring.

  8. Three hydroxy aurone compounds as chemosensors for cyanide anions.

    PubMed

    Chen, Huihui; Sun, Yunhui; Zhou, Chuanjian; Cao, Duxia; Liu, Zhiqiang; Ma, Lin

    2013-12-01

    Three new 4-hydroxy aurone compounds 1-3 with dimethylamino (1), bromine (2) and cyano (3) as terminal group have been synthesized. Their photophysical properties as well as recognition properties for cyanide anions in acetonitrile and aqueous solution have also been examined. These compounds exhibit remarkable response to cyanide anions with obvious color and fluorescence change owing to hydrogen bonding reaction between cyanide anions and the O-H moiety of the sensors, which allows naked eye detection of cyanide anions.

  9. Minding the Gap

    SciTech Connect

    Firestone, Millicent Anne

    2015-02-23

    Neutron & X-ray scattering provides nano- to meso-scale details of complex fluid structure; 1D electronic density maps dervied from SAXS yield molecular level insights; Neutron reflectivity provides substructure details of substrate supported complex fluids; Complex fluids composition can be optimized to support a wide variety of both soluble and membrane proteins; The water gap dimensions can be finely tuned through polymer component.

  10. Variable Gap Conjugated Polymers

    DTIC Science & Technology

    2005-12-01

    conducting gold interfacial layer interjected between the ITO glass electrode and the PEDOT/PSS hole transport layer . A family of low band gap, and near IR...which can be used as both electrochromics and as the hole transport layers in light emitting diodes. Hybrid electrochromic and electroluminescent (EC...MEH-PPV, P3HT, etc.) in order to blanket the solar spectrum. Initial device results on these multi-component blends are promising. In addition, we

  11. Pharmacological “cross-inhibition” of connexin hemichannels and swelling activated anion channels

    PubMed Central

    Ye, Zu-Cheng; Oberheim, NancyAnn; Kettenmann, Helmut; Ransom, Bruce R.

    2009-01-01

    The study of ion channels has relied heavily on the use of pharmacological blocking agents. However, many of these agents have multiple effects, which may compromise interpretation of results when the affected mechanisms/pathways mediate similar functions. Volume regulated anion channels (VRAC) and connexin hemichannels can both mediate the release of glutamate and taurine, although these channels have distinct activation stimuli and hemichannels, but not VRAC, are permeable to Lucifer yellow (LY). It has been reported that some anion channel blockers may inhibit connexin hemichannels. We further examined the effects of classic gap junction/hemichannel blockers and anion channel blockers on these channels. The typical VRAC blockers NPPB, IAA-94 and tamoxifen blocked low divalent cation-induced glutamate and taurine release and LY loading, presumed due to hemichannel opening. The blocking action of these compounds on hemichannels was concentration dependent and fell within the same range where the drugs classically block VRACs. Conversely, carbenoxolone (CBX), the most widely used gap junction/hemichannel blocker, was an effective blocker of VRAC mediated glutamate and taurine release, and blocked these channels at similar concentrations at which it blocked hemichannels. The CBX effect on VRACs was verified using astrocytes from connexin 43 knock out (Cx43 KO) animals. In these cells, the hypotonic induced amino acid flux was retained while the low divalent cation solution flux was lost. These results extend our knowledge about ‘cross-inhibition’ of VRACs and gap junctions/hemichannels by certain pharmacological agents. Given the overlap in function of these two types of channels, great care must be exerted in using pharmacological blockers to identify one channel from the other. PMID:18837047

  12. Acyl anion free N-heterocyclic carbene organocatalysis.

    PubMed

    Ryan, Sarah J; Candish, Lisa; Lupton, David W

    2013-06-21

    Reaction discovery using N-heterocyclic carbene organocatalysis has been dominated by the chemistry of acyl anion equivalents. Recent studies demonstrate that NHCs are far more diverse catalysts, with a variety of reactions discovered that proceed without acyl anion equivalent formation. In this tutorial review selected examples of acyl anion free NHC catalysis using carbonyl compounds are presented.

  13. Experimental and theoretical studies on the electronic properties of vanadium-benzene sandwich cluster anions, V(n)Bz(n+1)- (n = 1-5).

    PubMed

    Masubuchi, Tsugunosuke; Ohi, Katsuya; Iwasa, Takeshi; Nakajima, Atsushi

    2012-12-14

    Vanadium-benzene cluster anions, V(n)Bz(n+1)(-) (Bz = C(6)H(6)) were generated by laser ablation and supersonic jet methods, and studied using photoelectron spectroscopy. The density functional theory was employed to compute their geometric and electronic structures. It is concluded that the V(n)Bz(n+1)(-) anions exhibit multiple-decker sandwich structures similar to their corresponding neutrals, and the adiabatic electron affinity increases with the cluster size. Our computation shows that the excess electron of the anion occupies the d orbitals of the vanadium atoms and that it is delocalized one-dimensionally. Furthermore, a very large HOMO-LUMO gap difference between majority and minority spin orbitals is observed for both the neutrals and the anions, and the V(n)Bz(n+1)(0∕-) clusters are found to be completely spin-polarized. These facts confirm the possibility of using V(n)Bz(n+1) clusters as spin filters.

  14. Mass transfer of single- and double-charged anions through an MA-41L anion-exchange membrane

    SciTech Connect

    Kulikova, O.M.; Sharkova, O.V.; Kulikov, S.M.

    1995-02-20

    Selective anion transfer through an MA-41L anion-exchange membrane in the Cl{sup -}-F{sup -}, Cl{sup -}-SO{sub 4}{sup 2-}, F{sup -}-SO{sub 4}{sup 2-}, and F{sup -}-CO{sub 3}{sup 2-} systems has been studied. The feasibility of partial anion separation in the chloride-sulfate system has been demonstrated. The separation of fluoride ions from accompanying anions was found to be practically impossible.

  15. Anion Solvation in Carbonate-Based Electrolytes

    SciTech Connect

    von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg; Peng, Jing; Russell, Selena M.; Wikner, Emily; Fu, Adele; Hu, Libo; Lee, Hung-Sui; Zhang, Zhengcheng; Yang, Xiao-Qing; Greenbaum, Steven; Amine, Khalil; Xu, Kang

    2015-11-16

    The correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. Now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. Moreover, as a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  16. Electron anions and the glass transition temperature

    SciTech Connect

    Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; Hosono, Hideo

    2016-08-24

    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32]2+ ∙ (e)2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

  17. Specific anion effects in Artemia salina.

    PubMed

    Lo Nostro, Pierandrea; Ninham, Barry W; Carretti, Emiliano; Dei, Luigi; Baglioni, Piero

    2015-09-01

    The specific anion effect on the vitality of Artemia salina was investigated by measuring the Lethal Time LT50 of the crustaceans in the presence of different sodium salts solutions at room temperature and at the same ionic strength as natural seawater. Fluoride, thiocyanate and perchlorate are the most toxic agents, while chloride, bromide and sulfate are well tolerated. The rates of oxygen consumption of brine shrimps were recorded in mixed NaCl+NaF or NaCl+NaSCN solutions as a function of time. The results are discussed in terms of the Hofmeister series, and suggest that, besides the biochemical processes that involve F(-), SCN(-) and ClO4(-), the different physico-chemical properties of the strong kosmotropic and chaotropic anions may contribute in determining their strong toxicity for A. salina.

  18. Nanoheterostructure cation exchange: anionic framework conservation.

    PubMed

    Jain, Prashant K; Amirav, Lilac; Aloni, Shaul; Alivisatos, A Paul

    2010-07-28

    In ionic nanocrystals the cationic sublattice can be replaced with a different metal ion via a fast, simple, and reversible place exchange, allowing postsynthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate that, during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu(2)Se/Cu(2)S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  19. An intracellular anion channel critical for pigmentation.

    PubMed

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-12-16

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation.

  20. Anion Solvation in Carbonate-Based Electrolytes

    DOE PAGES

    von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg; ...

    2015-11-16

    The correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. Now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. Moreover, as a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate,more » PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.« less

  1. Lowest autodetachment state of the water anion

    NASA Astrophysics Data System (ADS)

    Houfek, Karel; Čížek, Martin

    2016-05-01

    The potential energy surface of the ground state of the water anion H2O- is carefully mapped using multireference CI calculations for a large range of molecular geometries. Particular attention is paid to a consistent description of both the O-+H2 and OH-+H asymptotes and to a relative position of the anion energy to the ground state energy of the neutral molecule. The autodetachment region, where the anion state crosses to the electronic continuum is identified. The local minimum in the direction of the O- + H2 channel previously reported by Werner et al. [J. Chem. Phys. 87, 2913 (1987)] is found to be slighly off the linear geometry and is separated by a saddle from the autodetachment region. The autodetachment region is directly accessible from the OH-+H asymptote. For the molecular geometries in the autodetachment region and in its vicinity we also performed fixed-nuclei electron-molecule scattering calculations using the R-matrix method. Tuning of consistency of a description of the correlation energy in both the multireference CI and R-matrix calculations is discussed. Two models of the correlation energy within the R-matrix method that are consistent with the quantum chemistry calculations are found. Both models yield scattering quantities in a close agreement. The results of this work will allow a consistent formulation of the nonlocal resonance model of the water anion in a future publication. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  2. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  3. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  4. Stable and highly persistent quinoxaline-centered metalloorganic radical anions: preparation, structural, spectroscopic, and computational investigations.

    PubMed

    Choua, Sylvie; Djukic, Jean-Pierre; Dalléry, Jérôme; Bieber, André; Welter, Richard; Gisselbrecht, Jean-Paul; Turek, Philippe; Ricard, Louis

    2009-01-05

    features suggested by structural analysis. Single-point calculation using the B3LYP functional and various basis sets [LANL2DZ, 6-31G(d), 6-311+G(d), and 6-311+G(2d,p)] provided us with values of anisotropic g tensors and hyperfine coupling constants consistent with those determined experimentally. It is inferred from this study that the two metal centers bound to the nitrogen atoms of the quinoxalyl core contribute in the lowering of the HOMO-LUMO gap in the neutral species. The triple-decker arrangement, which combines chelation of the metal, steric protection, and encapsulation of the central quinoxalyl core, is a stabilizing factor that provides a long-lived character to the radical-anionic species.

  5. Fe doping and anion defects in bismuth pyrochlore photocatalysts

    NASA Astrophysics Data System (ADS)

    Mayfield, Cedric; Barker, David; Subramanian, Vaidyananthan; Huda, Muhammad

    2014-03-01

    To understand the change in photocatalytic properties of Bi2Ti2O7\\ after incorporating localized Fe 3d electrons, the electronic properties and formation energies of anion defects and cation substitutions have been systematically studied by first principles density functional theory. We have found for each type of doping, intrinsic or extrinsic, structural distortions are localized to the defect site. For the intrinsic defects, O vacancies (Ovac) are relatively shallow donors compared to O interstitials (Oint) . For the extrinsic defects, Fe substitutions at the Bi sites (FeBi) are more stable than Fe substitutions at the Ti sites (FeTi) , however they both promote the acceptor defect levels which are critical for band gap engineering. Complex doping (combined intrinsic and extrinsic doping) was also considered to examine the defect correlations at first nearest neighbor to third nearest neighbor distances. A detailed electronic structure analysis will be presented for both pristine and doped Bi2Ti2O7. National Science Foundation.

  6. Donnan membrane technique (DMT) for anion measurement.

    PubMed

    Vega, Flora Alonso; Weng, Liping; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

    2010-04-01

    Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl(-), 1-2 days for NO(3)(-), 1-4 days for SO(4)(2-) and SeO(4)(2-), and 1-14 days for H(2)PO(4)(-) in a background of 2-200 mM KCl or K(2)SO(4). The strongest effect of ionic strength on equilibrium time is found for H(2)PO(4)(-), followed by SO(4)(2-) and SeO(4)(2-), and then by Cl(-) and NO(3)(-). The negatively charged organic particles of fulvic and humic acids do not pass the membrane. Two approaches for the measurement of different anion species of the same element, such as SeO(4)(2-) and HSeO(3)(-), using DMT are proposed and tested. These two approaches are based on transport kinetics or response to ionic strength difference. A transport model that was developed previously for cation DMT is applied in this work to analyze the rate-limiting step in the anion DMT. In the absence of mobile/labile complexes, transport tends to be controlled by diffusion in solution at a low ionic strength, whereas at a higher ionic strength, diffusion in the membrane starts to control the transport.

  7. Ferrocenylbenzobisimidazoles for recognition of anions and cations.

    PubMed

    Alfonso, María; Tárraga, Alberto; Molina, Pedro

    2013-07-01

    The preparation of 2,7-disubstituted benzobisimidazoles decorated with substituents displaying different electrooptical properties is described. The presence of redox, chromogenic, and fluorescent groups at the heteroaromatic core, which acts as ditopic binding site, made these receptors potential candidates as multichannel probes for ions. The triad 4 behaves as a selective redox and fluorescent chemosensor for HSO4(-) and Hg(2+) ions, whereas receptor 5 acts as a redox and chromogenic chemosensor molecule for AcO(-) and SO4(2-) anions. The change in the absorption spectra is accompanied by a color change from yellow to orange, while sensing of Zn(2+), Hg(2+), and Pb(2+) cations is carried out only by electrochemical techniques. Receptor 6 exhibits a remarkable cathodic shift of the oxidation wave only in the presence of AcO(-), H2PO4(-), and HP2O7(3-) anions, whereas addition of Pb(2+) induces an anodic shift. A new low energy band in the absorption spectra, which is responsible for the color change from colorless to pale yellow, and an important increase of the monomer emission band is observed only in the presence of H2PO4(-), and HP2O7(3-) anions. The most salient feature of the receptor 6 is its ability to act as a multichannel (redox, chromogenic, and fluorescent) chemodosimeter for Cu(2+), and Hg(2+) metal cations.

  8. Several hemicyanine dyes as fluorescence chemosensors for cyanide anions

    NASA Astrophysics Data System (ADS)

    Liang, Muhan; Wang, Kangnan; Guan, Ruifang; Liu, Zhiqiang; Cao, Duxia; Wu, Qianqian; Shan, Yanyan; Xu, Yongxiao

    2016-05-01

    Four hemicyanine dyes as chemosensors for cyanide anions were synthesized easily. Their photophysical properties and recognition properties for cyanide anions were investigated. The results indicate that all the dyes can recognize cyanide anions with obvious color, absorption and fluorescence change. The recognition mechanism analysis basing on in situ 1H NMR and Job plot data indicates that to the compounds with hydroxyl group, the recognition mechanism is intramolecular hydrogen bonding interaction. However, to the compounds without hydroxyl group, cyanide anion is bonded to carbon-carbon double bond in conjugated bridge and induces N+ CH3 to neutral NCH3. Fluorescence of the compounds is almost quenched upon the addition of cyanide anions.

  9. SOUTHWEST REGIONAL GAP LAND COVER

    EPA Science Inventory

    The Gap Analysis Program is a national inter-agency program that maps the distribution

    of plant communities and selected animal species and compares these distributions with land

    stewardship to identify gaps in biodiversity protection. GAP uses remote satellite imag...

  10. Skills Gaps in Australian Firms

    ERIC Educational Resources Information Center

    Lindorff, Margaret

    2011-01-01

    This paper reports the results of a survey of more than 2000 managers examining perceptions of skills gaps in a range of Australian firms. It finds that three quarters report a skills gap, and almost one third report skills gaps across the whole organisation. Firm size and industry differences exist in perceptions of the effect of the skills gap…

  11. GABA signalling modulates plant growth by directly regulating the activity of plant-specific anion transporters.

    PubMed

    Ramesh, Sunita A; Tyerman, Stephen D; Xu, Bo; Bose, Jayakumar; Kaur, Satwinder; Conn, Vanessa; Domingos, Patricia; Ullah, Sana; Wege, Stefanie; Shabala, Sergey; Feijó, José A; Ryan, Peter R; Gilliham, Matthew; Gillham, Matthew

    2015-07-29

    The non-protein amino acid, gamma-aminobutyric acid (GABA) rapidly accumulates in plant tissues in response to biotic and abiotic stress, and regulates plant growth. Until now it was not known whether GABA exerts its effects in plants through the regulation of carbon metabolism or via an unidentified signalling pathway. Here, we demonstrate that anion flux through plant aluminium-activated malate transporter (ALMT) proteins is activated by anions and negatively regulated by GABA. Site-directed mutagenesis of selected amino acids within ALMT proteins abolishes GABA efficacy but does not alter other transport properties. GABA modulation of ALMT activity results in altered root growth and altered root tolerance to alkaline pH, acid pH and aluminium ions. We propose that GABA exerts its multiple physiological effects in plants via ALMT, including the regulation of pollen tube and root growth, and that GABA can finally be considered a legitimate signalling molecule in both the plant and animal kingdoms.

  12. The global drug gap.

    PubMed

    Reich, M R

    2000-03-17

    Global inequities in access to pharmaceutical products exist between rich and poor countries because of market and government failures as well as huge income differences. Multiple policies are required to address this global drug gap for three categories of pharmaceutical products: essential drugs, new drugs, and yet-to-be-developed drugs. Policies should combine "push" approaches of subsidies to support targeted drug development, "pull" approaches of financial incentives such as market guarantees, and "process" approaches aimed at improved institutional capacity. Constructive solutions are needed that can both protect the incentives for research and development and reduce the inequities of access.

  13. Mind the gap.

    SciTech Connect

    Bhagwat, M. S.; Krassnigg, A.; Maris, P.; Roberts, C. D.; Physics; Univ. Graz; Univ. of Pittsburgh

    2007-03-01

    In this summary of the application of Dyson-Schwinger equations to the theory and phenomenology of hadrons, some deductions following from a nonperturbative, symmetry-preserving truncation are highlighted, notable amongst which are results for pseudoscalar mesons. We also describe inferences from the gap equation relating to the radius of convergence of a chiral expansion, applications to heavy-light and heavy-heavy mesons, and quantitative estimates of the contribution of quark orbital angular momentum in pseudoscalar mesons; and recapitulate upon studies of nucleon electromagnetic form factors.

  14. Anion order in perovskites: a group-theoretical analysis.

    PubMed

    Talanov, M V; Shirokov, V B; Talanov, V M

    2016-03-01

    Anion ordering in the structure of cubic perovskite has been investigated by the group-theoretical method. The possibility of the existence of 261 ordered low-symmetry structures, each with a unique space-group symmetry, is established. These results include five binary and 14 ternary anion superstructures. The 261 idealized anion-ordered perovskite structures are considered as aristotypes, giving rise to different derivatives. The structures of these derivatives are formed by tilting of BO6 octahedra, distortions caused by the cooperative Jahn-Teller effect and other physical effects. Some derivatives of aristotypes exist as real substances, and some as virtual ones. A classification of aristotypes of anion superstructures in perovskite is proposed: the AX class (the simultaneous ordering of A cations and anions in cubic perovskite structure), the BX class (the simultaneous ordering of B cations and anions) and the X class (the ordering of anions only in cubic perovskite structure). In most perovskites anion ordering is accompanied by cation ordering. Therefore, the main classes of anion order in perovskites are the AX and BX classes. The calculated structures of some anion superstructures are reported. Comparison of predictions and experimentally investigated anion superstructures shows coherency of theoretical and experimental results.

  15. Membrane process for separating contaminant anions from aqueous solutions of valuable metal anions

    SciTech Connect

    Hepworth, M.T.; Laferty, J.M.

    1980-11-18

    An aqueous solution of at least one valuable oxyanion containing molybdenum, tungsten, vanadium, or uranium is refined to lower the content of contaminant anions such as PO/sub 4//sup -3/, SO/sub 4//sup -2/, NO/sub 3//sup -/, Cl/sup -/, ClO/sub 3//sup -/, and ClO/sub 4//sup -/, by subjecting the solution to electrolysis at a ph of from 0.5 to 4.0 between a cation-permselective membrane and an anion-permselective membrane having tertiary amine or quaternary ammonium anion exchange groups, to cause contaminant anions to pass from the solution into the anolyte. Ammonium molybdates, tungstates, vanadates, and uranates are formed from the thus-refined solution by subjecting it to a second stage of electrolysis at a ph of at least 7 between a cation-permselective membrane and an anion-permselective membrane to cause valuable oxyanions to pass from the solution into an anolyte which comprises an aqueous solution of ammonia and to form the desired ammonium compound.

  16. The benzene radical anion: A computationally demanding prototype for aromatic anions

    SciTech Connect

    Bazante, Alexandre P. Bartlett, Rodney J.; Davidson, E. R.

    2015-05-28

    The benzene radical anion is studied with ab initio coupled-cluster theory in large basis sets. Unlike the usual assumption, we find that, at the level of theory investigated, the minimum energy geometry is non-planar with tetrahedral distortion at two opposite carbon atoms. The anion is well known for its instability to auto-ionization which poses computational challenges to determine its properties. Despite the importance of the benzene radical anion, the considerable attention it has received in the literature so far has failed to address the details of its structure and shape-resonance character at a high level of theory. Here, we examine the dynamic Jahn-Teller effect and its impact on the anion potential energy surface. We find that a minimum energy geometry of C{sub 2} symmetry is located below one D{sub 2h} stationary point on a C{sub 2h} pseudo-rotation surface. The applicability of standard wave function methods to an unbound anion is assessed with the stabilization method. The isotropic hyperfine splitting constants (A{sub iso}) are computed and compared to data obtained from experimental electron spin resonance experiments. Satisfactory agreement with experiment is obtained with coupled-cluster theory and large basis sets such as cc-pCVQZ.

  17. Disorders of Carbohydrate Metabolism

    MedlinePlus

    ... Metabolic Disorders Disorders of Carbohydrate Metabolism Disorders of Amino Acid Metabolism Disorders of Lipid Metabolism Carbohydrates are sugars. ... Metabolic Disorders Disorders of Carbohydrate Metabolism Disorders of Amino Acid Metabolism Disorders of Lipid Metabolism NOTE: This is ...

  18. Detection of Perchlorate Anion on Functionalized Silver Colloids Using Surface-Enhanced Raman Scattering

    SciTech Connect

    Tio, J.; Wang, W.; Gu, B.

    2005-01-01

    Perchlorate anion interferes with the uptake of iodide by the human thyroid gland and consequently disrupts the regulation of metabolism. Chronic exposure to high levels of perchlorate may lead to the formation of thyroid gland tumors. Although the Environmental Protection Agency (EPA) has not set a maximum contaminant level (MCL) for perchlorate, a draft drinking water range of 4-18 ppb based on 2 liter daily consumption of water has been established. The current EPA approved method for detecting perchlorate uses ion chromatography which has a detection limit of ~1ppb and involves lengthy analytical time in the laboratory. A unique combination of the surface-enhanced Raman scattering (SERS) effect and the bifunctional anion exchange resin’s high selectivity may provide an alternative way to detect perchlorate at such low concentrations and with high specificity. SERS, which uses laser excitation of adsorbed perchlorate anions on silver nanoparticles, has been shown to detect perchlorate anions at concentrations as low as 50 ppb. Normal micro-Raman analysis of perchlorate sorbed onto the resin beads has detected an even lower concentration of 10 ppb. In an effort to integrate these two effects, silver nanoparticles were coated with N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, a functional group similar to that found on the resin bead, and subsequently inserted into different perchlorate concentration environments. This method has resulted in perchlorate detection down to ~10 ppb and a more consistent detection of perchlorate anion at ~50 ppb than that of earlier methods. As suggested by the direct insertion of functionalized silver colloids into perchlorate samples, this technique may potentially allow for the development of a probe using on-site Raman spectrometry to detect significantly low concentrations of perchlorate in situ rather than in the laboratory.

  19. Multiple Electrolyte and Metabolic Emergencies in a Single Patient

    PubMed Central

    Cadacio, Caprice; Pham, Phuong-Thu; Bhasin, Ruchika; Kamarzarian, Anita

    2017-01-01

    While some electrolyte disturbances are immediately life-threatening and must be emergently treated, others may be delayed without immediate adverse consequences. We discuss a patient with alcoholism and diabetes mellitus type 2 who presented with volume depletion and multiple life-threatening electrolyte and metabolic derangements including severe hyponatremia (serum sodium concentration [SNa] 107 mEq/L), hypophosphatemia (“undetectable,” <1.0 mg/dL), and hypokalemia (2.2 mEq/L), moderate diabetic ketoacidosis ([DKA], pH 7.21, serum anion gap [SAG] 37) and hypocalcemia (ionized calcium 4.0 mg/dL), mild hypomagnesemia (1.6 mg/dL), and electrocardiogram with prolonged QTc. Following two liters of normal saline and associated increase in SNa by 4 mEq/L and serum osmolality by 2.4 mosm/Kg, renal service was consulted. We were challenged with minimizing the correction of SNa (or effective serum osmolality) to avoid the osmotic demyelinating syndrome while replacing volume, potassium, phosphorus, calcium, and magnesium and concurrently treating DKA. Our management plan was further complicated by an episode of significant aquaresis. A stepwise approach was strategized to prioritize and correct all disturbances with considerations that the treatment of one condition could affect or directly worsen another. The current case demonstrates that a thorough understanding of electrolyte physiology is required in managing complex electrolyte disturbances to avoid disastrous outcomes. PMID:28255480

  20. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions.

    PubMed

    Zhang, Zhan; Kim, Dong Sub; Lin, Chung-Yon; Zhang, Huacheng; Lammer, Aaron D; Lynch, Vincent M; Popov, Ilya; Miljanić, Ognjen Š; Anslyn, Eric V; Sessler, Jonathan L

    2015-06-24

    Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions.

  1. Cation/Anion Substitution in Cu2ZnSnS4 for Improved Photovoltaic Performance

    NASA Astrophysics Data System (ADS)

    Ananthoju, Balakrishna; Mohapatra, Jeotikanta; Jangid, Manoj K.; Bahadur, D.; Medhekar, N. V.; Aslam, M.

    2016-10-01

    Cations and anions are replaced with Fe, Mn, and Se in CZTS in order to control the formations of the secondary phase, the band gap, and the micro structure of Cu2ZnSnS4. We demonstrate a simplified synthesis strategy for a range of quaternary chalcogenide nanoparticles such as Cu2ZnSnS4 (CZTS), Cu2FeSnS4 (CFTS), Cu2MnSnS4 (CMTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S0.5Se0.5)4 (CZTSSe) by thermolysis of metal chloride precursors using long chain amine molecules. It is observed that the crystal structure, band gap and micro structure of the CZTS thin films are affected by the substitution of anion/cations. Moreover, secondary phases are not observed and grain sizes are enhanced significantly with selenium doping (grain size ~1 μm). The earth-abundant Cu2MSnS4/Se4 (M = Zn, Mn and Fe) nanoparticles have band gaps in the range of 1.04–1.51 eV with high optical-absorption coefficients (~104 cm‑1) in the visible region. The power conversion efficiency of a CZTS solar cell is enhanced significantly, from 0.4% to 7.4% with selenium doping, within an active area of 1.1 ± 0.1 cm2. The observed changes in the device performance parameters might be ascribed to the variation of optical band gap and microstructure of the thin films. The performance of the device is at par with sputtered fabricated films, at similar scales.

  2. Cation/Anion Substitution in Cu2ZnSnS4 for Improved Photovoltaic Performance

    PubMed Central

    Ananthoju, Balakrishna; Mohapatra, Jeotikanta; Jangid, Manoj K.; Bahadur, D.; Medhekar, N. V.; Aslam, M.

    2016-01-01

    Cations and anions are replaced with Fe, Mn, and Se in CZTS in order to control the formations of the secondary phase, the band gap, and the micro structure of Cu2ZnSnS4. We demonstrate a simplified synthesis strategy for a range of quaternary chalcogenide nanoparticles such as Cu2ZnSnS4 (CZTS), Cu2FeSnS4 (CFTS), Cu2MnSnS4 (CMTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S0.5Se0.5)4 (CZTSSe) by thermolysis of metal chloride precursors using long chain amine molecules. It is observed that the crystal structure, band gap and micro structure of the CZTS thin films are affected by the substitution of anion/cations. Moreover, secondary phases are not observed and grain sizes are enhanced significantly with selenium doping (grain size ~1 μm). The earth-abundant Cu2MSnS4/Se4 (M = Zn, Mn and Fe) nanoparticles have band gaps in the range of 1.04–1.51 eV with high optical-absorption coefficients (~104 cm−1) in the visible region. The power conversion efficiency of a CZTS solar cell is enhanced significantly, from 0.4% to 7.4% with selenium doping, within an active area of 1.1 ± 0.1 cm2. The observed changes in the device performance parameters might be ascribed to the variation of optical band gap and microstructure of the thin films. The performance of the device is at par with sputtered fabricated films, at similar scales. PMID:27748406

  3. Cation/Anion Substitution in Cu2ZnSnS4 for Improved Photovoltaic Performance.

    PubMed

    Ananthoju, Balakrishna; Mohapatra, Jeotikanta; Jangid, Manoj K; Bahadur, D; Medhekar, N V; Aslam, M

    2016-10-17

    Cations and anions are replaced with Fe, Mn, and Se in CZTS in order to control the formations of the secondary phase, the band gap, and the micro structure of Cu2ZnSnS4. We demonstrate a simplified synthesis strategy for a range of quaternary chalcogenide nanoparticles such as Cu2ZnSnS4 (CZTS), Cu2FeSnS4 (CFTS), Cu2MnSnS4 (CMTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S0.5Se0.5)4 (CZTSSe) by thermolysis of metal chloride precursors using long chain amine molecules. It is observed that the crystal structure, band gap and micro structure of the CZTS thin films are affected by the substitution of anion/cations. Moreover, secondary phases are not observed and grain sizes are enhanced significantly with selenium doping (grain size ~1 μm). The earth-abundant Cu2MSnS4/Se4 (M = Zn, Mn and Fe) nanoparticles have band gaps in the range of 1.04-1.51 eV with high optical-absorption coefficients (~10(4) cm(-1)) in the visible region. The power conversion efficiency of a CZTS solar cell is enhanced significantly, from 0.4% to 7.4% with selenium doping, within an active area of 1.1 ± 0.1 cm(2). The observed changes in the device performance parameters might be ascribed to the variation of optical band gap and microstructure of the thin films. The performance of the device is at par with sputtered fabricated films, at similar scales.

  4. Dietary Fiber Gap and Host Gut Microbiota.

    PubMed

    Han, Meng; Wang, C; Liu, Ping; Li, Defa; Li, Yuan; Ma, Xi

    2017-02-20

    Accumulating evidence are dramatically increasing access to the facts that the gut microbiota plays a pivotal role in host metabolism and health, which revealed the possibility of a plethora of associations between gut bacteria and human diseases. Several functional roles carried out by a major class of host's diet, such as fiber. Fiber is the main source of microbiota-accessible carbohydrate in the diet of humans. In modern diet, it is difficult to intake dietary fiber as enough as recommended standard. The low-fiber diet in the modern life, known as fiber gap, can trigger to a substantial depletion of the human gut microbiota diversity and beneficial metabolites. The short-chain fatty acids are regarded as one of the major microbial metabolites of dietary fibers, which can improve intestinal mucosal immunity, as well as to be a source of energy for the liver. Thus, the loss of microbiota diversity has a potential negative function to various aspects of host health. Actually, the real "fiber gap" for ideal health and maintaining microbial diversity might be even seriously than currently appreciated. Herein, we briefly discuss the interactions between gut microbiota and the host diet, focusing specifically on the low-fiber diet. Gut bacteria in the context of the development of host low-fiber diets, which may lead to health and disorders, particularly include metabolic syndrome and obesity-related disease, IBD liver, disease, and colorectal cancer.

  5. Small Multiples with Gaps.

    PubMed

    Meulemans, Wouter; Dykes, Jason; Slingsby, Aidan; Turkay, Cagatay; Wood, Jo

    2017-01-01

    Small multiples enable comparison by providing different views of a single data set in a dense and aligned manner. A common frame defines each view, which varies based upon values of a conditioning variable. An increasingly popular use of this technique is to project two-dimensional locations into a gridded space (e.g. grid maps), using the underlying distribution both as the conditioning variable and to determine the grid layout. Using whitespace in this layout has the potential to carry information, especially in a geographic context. Yet, the effects of doing so on the spatial properties of the original units are not understood. We explore the design space offered by such small multiples with gaps. We do so by constructing a comprehensive suite of metrics that capture properties of the layout used to arrange the small multiples for comparison (e.g. compactness and alignment) and the preservation of the original data (e.g. distance, topology and shape). We study these metrics in geographic data sets with varying properties and numbers of gaps. We use simulated annealing to optimize for each metric and measure the effects on the others. To explore these effects systematically, we take a new approach, developing a system to visualize this design space using a set of interactive matrices. We find that adding small amounts of whitespace to small multiple arrays improves some of the characteristics of 2D layouts, such as shape, distance and direction. This comes at the cost of other metrics, such as the retention of topology. Effects vary according to the input maps, with degree of variation in size of input regions found to be a factor. Optima exist for particular metrics in many cases, but at different amounts of whitespace for different maps. We suggest multiple metrics be used in optimized layouts, finding topology to be a primary factor in existing manually-crafted solutions, followed by a trade-off between shape and displacement. But the rich range of possible

  6. Metabolism in Fungal Pathogenesis

    PubMed Central

    Ene, Iuliana V.; Brunke, Sascha; Brown, Alistair J.P.; Hube, Bernhard

    2014-01-01

    Fungal pathogens must assimilate local nutrients to establish an infection in their mammalian host. We focus on carbon, nitrogen, and micronutrient assimilation mechanisms, discussing how these influence host–fungus interactions during infection. We highlight several emerging trends based on the available data. First, the perturbation of carbon, nitrogen, or micronutrient assimilation attenuates fungal pathogenicity. Second, the contrasting evolutionary pressures exerted on facultative versus obligatory pathogens have led to contemporary pathogenic fungal species that display differing degrees of metabolic flexibility. The evolutionarily ancient metabolic pathways are conserved in most fungal pathogen, but interesting gaps exist in some species (e.g., Candida glabrata). Third, metabolic flexibility is generally essential for fungal pathogenicity, and in particular, for the adaptation to contrasting host microenvironments such as the gastrointestinal tract, mucosal surfaces, bloodstream, and internal organs. Fourth, this metabolic flexibility relies on complex regulatory networks, some of which are conserved across lineages, whereas others have undergone significant evolutionary rewiring. Fifth, metabolic adaptation affects fungal susceptibility to antifungal drugs and also presents exciting opportunities for the development of novel therapies. PMID:25190251

  7. Gap Opening in 3D: Single-planet Gaps

    NASA Astrophysics Data System (ADS)

    Fung, Jeffrey; Chiang, Eugene

    2016-12-01

    Giant planets can clear deep gaps when embedded in 2D (razor-thin) viscous circumstellar disks. We show by direct simulation that giant planets are just as capable of carving out gaps in 3D. Surface density maps are similar between 2D and 3D, even in detail. In particular, the scaling {{{Σ }}}{gap}\\propto {q}-2 of gap surface density with planet mass, derived from a global “zero-dimensional” balance of Lindblad and viscous torques, applies equally well to results obtained at higher dimensions. Our 3D simulations reveal extensive, near-sonic, meridional flows both inside and outside the gaps; these large-scale circulations might bear on disk compositional gradients, in dust or other chemical species. At high planet mass, gap edges are mildly Rayleigh unstable and intermittently shed streams of material into the gap—less so in 3D than in 2D.

  8. The organic anion transporter (OAT) family: a systems biology perspective.

    PubMed

    Nigam, Sanjay K; Bush, Kevin T; Martovetsky, Gleb; Ahn, Sun-Young; Liu, Henry C; Richard, Erin; Bhatnagar, Vibha; Wu, Wei

    2015-01-01

    The organic anion transporter (OAT) subfamily, which constitutes roughly half of the SLC22 (solute carrier 22) transporter family, has received a great deal of attention because of its role in handling of common drugs (antibiotics, antivirals, diuretics, nonsteroidal anti-inflammatory drugs), toxins (mercury, aristolochic acid), and nutrients (vitamins, flavonoids). Oats are expressed in many tissues, including kidney, liver, choroid plexus, olfactory mucosa, brain, retina, and placenta. Recent metabolomics and microarray data from Oat1 [Slc22a6, originally identified as NKT (novel kidney transporter)] and Oat3 (Slc22a8) knockouts, as well as systems biology studies, indicate that this pathway plays a central role in the metabolism and handling of gut microbiome metabolites as well as putative uremic toxins of kidney disease. Nuclear receptors and other transcription factors, such as Hnf4α and Hnf1α, appear to regulate the expression of certain Oats in conjunction with phase I and phase II drug metabolizing enzymes. Some Oats have a strong selectivity for particular signaling molecules, including cyclic nucleotides, conjugated sex steroids, odorants, uric acid, and prostaglandins and/or their metabolites. According to the "Remote Sensing and Signaling Hypothesis," which is elaborated in detail here, Oats may function in remote interorgan communication by regulating levels of signaling molecules and key metabolites in tissues and body fluids. Oats may also play a major role in interorganismal communication (via movement of small molecules across the intestine, placental barrier, into breast milk, and volatile odorants into the urine). The role of various Oat isoforms in systems physiology appears quite complex, and their ramifications are discussed in the context of remote sensing and signaling.

  9. The Gap-Tpc

    NASA Astrophysics Data System (ADS)

    Rossi, B.; Anastasio, A.; Boiano, A.; Catalanotti, S.; Cocco, A. G.; Covone, G.; Di Meo, P.; Longo, G.; Vanzanella, A.; Walker, S.; Wang, H.; Wang, Y.; Fiorillo, G.

    2016-02-01

    Several experiments have been conducted worldwide, with the goal of observing low-energy nuclear recoils induced by WIMPs scattering off target nuclei in ultra-sensitive, low-background detectors. In the last few decades noble liquid detectors designed to search for dark matter in the form of WIMPs have been extremely successful in improving their sensitivities and setting the best limits. One of the crucial problems to be faced for the development of large size (multi ton-scale) liquid argon experiments is the lack of reliable and low background cryogenic PMTs: their intrinsic radioactivity, cost, and borderline performance at 87 K rule them out as a possible candidate for photosensors. We propose a brand new concept of liquid argon-based detector for direct dark matter search: the Geiger-mode Avalanche Photodiode Time Projection Chamber (GAP-TPC) optimized in terms of residual radioactivity of the photosensors, energy and spatial resolution, light and charge collection efficiency.

  10. Undecidability of the spectral gap.

    PubMed

    Cubitt, Toby S; Perez-Garcia, David; Wolf, Michael M

    2015-12-10

    The spectral gap--the energy difference between the ground state and first excited state of a system--is central to quantum many-body physics. Many challenging open problems, such as the Haldane conjecture, the question of the existence of gapped topological spin liquid phases, and the Yang-Mills gap conjecture, concern spectral gaps. These and other problems are particular cases of the general spectral gap problem: given the Hamiltonian of a quantum many-body system, is it gapped or gapless? Here we prove that this is an undecidable problem. Specifically, we construct families of quantum spin systems on a two-dimensional lattice with translationally invariant, nearest-neighbour interactions, for which the spectral gap problem is undecidable. This result extends to undecidability of other low-energy properties, such as the existence of algebraically decaying ground-state correlations. The proof combines Hamiltonian complexity techniques with aperiodic tilings, to construct a Hamiltonian whose ground state encodes the evolution of a quantum phase-estimation algorithm followed by a universal Turing machine. The spectral gap depends on the outcome of the corresponding 'halting problem'. Our result implies that there exists no algorithm to determine whether an arbitrary model is gapped or gapless, and that there exist models for which the presence or absence of a spectral gap is independent of the axioms of mathematics.

  11. Infared Spectroscopy of Discrete Uranyl Anion Complexes

    SciTech Connect

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-24

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30–40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.

  12. Photoelectron spectroscopy of pyrene anion clusters: Autodetachment via excited states of anion and intermolecular interactions in anion clusters

    NASA Astrophysics Data System (ADS)

    Kim, Jeong Hyun; Lee, Sang Hak; Song, Jae Kyu

    2009-03-01

    This study examined the anion clusters of pyrene (Py) by mass spectrometry, photoelectron spectroscopy, and theoretical calculations. The photoelectron spectra of Pyn- (n =1-4) were obtained at various photon energies. A change in photodetachment wavelength resulted in a large change in the relative intensities of vibrational progression in the photoelectron spectra. It is proposed that the observed modulation of the Franck-Condon factors by the different photon energies reflects autodetachment via the excited states of anion. The photoelectron spectra of Pyn- at 355 nm showed a broad band structure between the S0 and T1 states, which is also due to the autodetachment via a Feshbach resonance state. The photoelectron spectra of Py2- suggest the presence of a unique dimeric interaction between the two pyrene moieties, whereas the spectral features of Py3- are similar to those of Py1-. The stable structures of Py2- and Py3- obtained by density functional theory calculations support the experimental findings, where different intermolecular interactions govern the stabilization of these two species.

  13. Hydrogen sulfide anion regulates redox signaling via electrophile sulfhydration

    PubMed Central

    Nishida, Motohiro; Sawa, Tomohiro; Kitajima, Naoyuki; Ono, Katsuhiko; Inoue, Hirofumi; Ihara, Hideshi; Motohashi, Hozumi; Yamamoto, Masayuki; Suematsu, Makoto; Kurose, Hitoshi; van der Vliet, Albert; Freeman, Bruce A; Shibata, Takahiro; Uchida, Koji; Kumagai, Yoshito; Akaike, Takaaki

    2014-01-01

    An emerging aspect of redox signaling is the pathway mediated by electrophilic byproducts, such as nitrated cyclic nucleotide (for example, 8-nitroguanosine 3′,5′-cyclic monophosphate (8-nitro-cGMP)) and nitro or keto derivatives of unsaturated fatty acids, generated via reactions of inflammation-related enzymes, reactive oxygen species, nitric oxide and secondary products. Here we report that enzymatically generated hydrogen sulfide anion (HS−) regulates the metabolism and signaling actions of various electrophiles. HS− reacts with electrophiles, best represented by 8-nitro-cGMP, via direct sulfhydration and modulates cellular redox signaling. The relevance of this reaction is reinforced by the significant 8-nitro-cGMP formation in mouse cardiac tissue after myocardial infarction that is modulated by alterations in HS− biosynthesis. Cardiac HS−, in turn, suppresses electrophile-mediated H-Ras activation and cardiac cell senescence, contributing to the beneficial effects of HS− on myocardial infarction–associated heart failure. Thus, this study reveals HS−-induced electrophile sulfhydration as a unique mechanism for regulating electrophile-mediated redox signaling. PMID:22772154

  14. Preparation of high purity egg phosvitin using anion exchange chromatography.

    PubMed

    Ren, Jiandong; Wu, Jianping

    2014-09-01

    Egg yolk phosvitin serves as a warehouse to provide metal ions for embryo development. It is significant for mineral metabolism study and also of great potential to be developed into functional foods with mineral absorption promoting ability. In this study, phosvitin was first extracted from yolk granules using 10% NaCl, dialysed and then adjusted to various pHs to remove impurities. The purity of phosvitin extracts was increased from 54.5% to 63.7% at decreasing pH from 8.0 to 5.5, and started to decrease afterwards. Both the yield and recovery were significantly decreased at decreasing pHs, especially at pHs close to its pI (pH 4.0), indicating the occurrence of co-precipitation of phosvitin with HDL. The extract prepared at pH 8.0 showed the highest recovery of 82.7%; its purity was increased from 54.5% to 97.1% by anion exchange chromatography, with a recovery of 42.0%. This simple method could be scaled up for industrial production.

  15. Probes for anionic cell surface detection

    DOEpatents

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  16. Anionic States of LiFLi

    DTIC Science & Technology

    1994-04-22

    EUIYCASFCTO 9 SECURITT12b CLSIIAIONT0.RIMITTION CODE TRC UNIDCLASIFEDT HCAS SIFIAPRO ED UNCPBICR LEASSEFIEDUNITE SALE IT.OO.0S50 DItTRdarIO Ior UNLIMITED-89 13...core Is atomic orbitals were doubly occupied in every configuration state function (CSF). The neglected core-core and core- valence correlation...has 2s and 2p valence orbitals to use but H has only Is valence orbitals. B. The Anion The ground electronic state of LiFLi- has a linear equilibrium

  17. An innovative anion regulation strategy for energy bands of semiconductors: a case from Bi2O3 to Bi2O(OH)2SO4.

    PubMed

    Tian, Hao; Teng, Fei; Xu, Juan; Lou, Sunqi; Li, Na; Zhao, Yunxuan; Chen, Mindong

    2015-01-19

    How to develop a new, efficient photo catalyst is still a big challenge to us. A suitable band gap is the key for light absorption of semiconductor. Herein, an innovative anion intercalation strategy is, for the first time, developed to regulate the energy band of semiconductor. Typically, we introduce a layered sulfate compound (Bi2O(OH)2SO4) as a new photo catalyst, which has not been known before. Both partial density of states (PDOS) and total density of states (TDOS) have demonstrated that compared with Bi2O3 (2.85 eV), the band gap of Bi2O(OH)2SO4 has been widened to 4.18 eV by the intercalation of sulfate anion. Moreover, the band gap width of oxyacid salt compound is mainly predominated by the number of the outmost electrons (NOE) of central atom of anion. This study suggests that new photo catalysts can be developed by grouping anions with the existing oxides or sulfides.

  18. An Innovative Anion Regulation Strategy for Energy Bands of Semiconductors: A Case from Bi2O3 to Bi2O(OH)2SO4

    PubMed Central

    Tian, Hao; Teng, Fei; Xu, Juan; Lou, Sunqi; Li, Na; Zhao, Yunxuan; Chen, Mindong

    2015-01-01

    How to develop a new, efficient photo catalyst is still a big challenge to us. A suitable band gap is the key for light absorption of semiconductor. Herein, an innovative anion intercalation strategy is, for the first time, developed to regulate the energy band of semiconductor. Typically, we introduce a layered sulfate compound (Bi2O(OH)2SO4) as a new photo catalyst, which has not been known before. Both partial density of states (PDOS) and total density of states (TDOS) have demonstrated that compared with Bi2O3 (2.85 eV), the band gap of Bi2O(OH)2SO4 has been widened to 4.18 eV by the intercalation of sulfate anion. Moreover, the band gap width of oxyacid salt compound is mainly predominated by the number of the outmost electrons (NOE) of central atom of anion. This study suggests that new photo catalysts can be developed by grouping anions with the existing oxides or sulfides. PMID:25597769

  19. [Application of high performance anion exchange chromatography for trace analysis of polarizable anions].

    PubMed

    Mo, Shumin; Liang, Lina; Cai, Yaqi; Mou, Shifen; Wen, Meijuan

    2005-11-01

    Polarizable anions such as Br-, S2O3(2-), I- and SCN- were separated using 45 mmol/L sodium hydroxide solution as the mobile phase on a high hydrophilic IonPac AS16 column. With a pulsed amperometric detector, the detection limits were 0.5, 0.2, 0.05 and 2 microg/L (25.0 microL injected, signal-to-noise ratio of 3) for Br-, S2O3(2-), I- and SCN. The relative standard deviation (RSD) range of trace anions was from 0.8% to 3.7% (n = 9). Under the same chromatographic conditions, these anions were also determined using a suppressed conductivity detector and the detection limits were 1, 1, 2 and 10 microg/L (25 microL injected, signal-to-noise ratio of 3), respectively. The RSD range was from 0.9% to 4.7% (n = 9). Comparing a pulsed amperometric detector with a conductivity detector, the former is 2 to 40 times more sensitive than the latter. For the determination of polarizable anions, a pulsed amperometric detector has higher selectivity, precision and sensitivity.

  20. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    NASA Astrophysics Data System (ADS)

    Wang, Lai-Sheng

    2015-07-01

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

  1. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    SciTech Connect

    Wang, Lai-Sheng

    2015-07-28

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

  2. Functional anion concept: effect of fluorine anion on hydrogen storage of sodium alanate.

    PubMed

    Yin, Li-Chang; Wang, Ping; Kang, Xiang-Dong; Sun, Cheng-Hua; Cheng, Hui-Ming

    2007-03-28

    Doping NaAlH(4) with Ti-catalyst has produced a promising hydrogen storage system that can be reversibly operated at moderate temperature conditions. Of the various dopant precursors, TiCl(3) was well recognized due to its pronounced catalytic effect on the reversible dehydrogenation processes of sodium aluminium hydrides. Quite recently we experimentally found that TiF(3) was even better than TiCl(3) in terms of the critical hydrogen storage properties of the doped hydrides, in particular the dehydriding performance at Na(3)AlH(6)/NaH + Al step at moderate temperature. We present here the DFT calculation results of the TiF(3) or TiCl(3) doped Na(3)AlH(6). Our computational studies have demonstrated that F(-) and Cl(-) anions differ substantially from each other with regard to the state and function in the doped sodium aluminium hydride. In great contrast to the case of chloride doping where Cl(-) anion constitutes the "dead weight" NaCl, the fluoride doping results in a substitution of H(-) by F(-) anion in the hydride lattice and accordingly, a favorable thermodynamics adjustment. These results well explain the observed dehydriding performance associated with TiF(3)/TiCl(3)-doping. More significantly, the coupled computational and experimental efforts allow us to put forward a "functional anion" concept. This renews the current mechanism understanding in the catalytically enhanced sodium alanate.

  3. The roles of anion channels in Arabidopsis immunity

    PubMed Central

    Guo, Wei; Wang, Chengcheng; Zuo, Zhangli; Qiu, Jin-Long

    2014-01-01

    Anion efflux is one of the most immediate responses of plant cells to pathogen attacks, suggesting that anion channels may play a role in plant defense. Recently we reported that the chloride channel AtCLCd negatively regulates Arabidopsis pathogen-associated molecular pattern-triggered immunity (PTI), probably by affecting trafficking of the pattern recognition receptors (PRRs). Since AtCLCd is localized to the trans-Golgi network, it is not likely to be directly involved in anion flux across the plasma membrane. Here, we used a pharmacological approach to explore further the function of plasma membrane-localized R-type and S-type anion channels in plant immunity. We found that the R-type and S-type anion channels play opposite roles in Arabidopsis innate immunity. Inhibition of the R-type anion channels enhances, whereas inhibition of the S-type channels inhibits PTI and effector-triggered immunity (ETI). PMID:25763497

  4. Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions.

    PubMed

    Jia, Tiezheng; Zhang, Mengnan; Jiang, Hui; Wang, Carol Y; Walsh, Patrick J

    2015-11-04

    A unique palladium-catalyzed arylation of alkyl sulfenate anions is introduced that affords aryl alkyl sulfoxides in high yields. Due to the base sensitivity of the starting sulfoxides, sulfenate anion intermediates, and alkyl aryl sulfoxide products, the use of a mild method to generate alkyl sulfenate anions was crucial to the success of this process. Thus, a fluoride triggered elimination strategy was employed with alkyl 2-(trimethylsilyl)ethyl sulfoxides to liberate the requisite alkyl sulfenate anion intermediates. In the presence of palladium catalysts with bulky monodentate phosphines (SPhos and Cy-CarPhos) and aryl bromides or chlorides, alkyl sulfenate anions were readily arylated. Moreover, the thermal fragmentation and the base promoted elimination of alkyl sulfoxides was overridden. The alkyl sulfenate anion arylation exhibited excellent chemoselectivity in the presence of functional groups, such as anilines and phenols, which are also known to undergo palladium catalyzed arylation reactions.

  5. Process for removing sulfate anions from waste water

    DOEpatents

    Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

    1997-01-01

    A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

  6. Zero-point energy effects in anion solvation shells.

    PubMed

    Habershon, Scott

    2014-05-21

    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  7. Photoelectron Spectroscopy and Theoretical Studies of Anion-pi Interactions: Binding Strength and Anion Specificity

    SciTech Connect

    Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.

    2015-01-01

    Proposed in theory and confirmed to exist, anion–π interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, intrinsic anion–π interaction strengths that are free from complications of condensed phases’ environments, have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl⁻, Br⁻, I⁻, linear thiocyanate SCN⁻, trigonal planar nitrate NO₃⁻, pyramidic iodate IO₃⁻, and tetrahedral sulfate SO₄²⁻). The binding energies of the resultant gaseous 1:1 complexes (1•Cl⁻,1•Br⁻, 1•I⁻, 1•SCN⁻, 1•NO₃⁻, 1•IO₃⁻ and 1•SO₄²⁻) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion specific effects. The binding strengths of Cl⁻, NO₃⁻, IO₃⁻ with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal/mol, but only about 40% of that between 1 and SO₄²⁻. Quantum chemical calculations reveal that all anions reside in the center of the cavity of 1 with anion–π binding motif in the complexes’ optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and natural bond orbital charge distribution analysis further support anion–π binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work

  8. Development of an In Silico Metabolic Simulator and Searchable Metabolism Database for Chemical Risk Assessments

    EPA Science Inventory

    The US EPA is faced with long lists of chemicals that need to be assessed for hazard, and a gap in evaluating chemical risk is accounting for metabolic activation resulting in increased toxicity. The goals of this project are to develop a capability to predict metabolic maps of x...

  9. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  10. Anion photoelectron spectroscopy of radicals and clusters

    SciTech Connect

    Travis, Taylor R.

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  11. Isatin phenylhydrazones: anion enhanced photochromic behaviour.

    PubMed

    Cigáň, M; Jakusová, K; Gáplovský, M; Filo, J; Donovalová, J; Gáplovský, A

    2015-11-01

    The photochemical properties of two basic easily synthesized isatin N(2)-phenylhydrazones were investigated. Contrary to the corresponding isatin N(2)-diphenylhydrazones, only Z-isomers were isolated from the reaction mixtures during the synthesis due to their stabilization by intramolecular hydrogen bonding. Although the presence of the C=N double bond creates conditions for the formation of a simple on-off photoswitch, the low photochemical quantum yield and particularly the low switching amplitude in absorbance hamper their photochromic applications. However, the addition of strongly basic anions to phenylhydrazone solutions leads to isatin NH group deprotonation and creates a new diazene T-type Vis-Vis photochromic system with sufficiently separated absorption maxima. Interestingly, although the thermally stable A-form is also photostable in ambient light, its irradiation with a stronger LED source leads to thermally unstable B-form formation which rapidly isomerizes back to the corresponding A-form. The process is reversible and switching cycles can be repeated in both directions. The important advantages of this two-component organic chromophore-inorganic anion photochromic system are its easy synthesis, easy handling due to its insensitivity to room light, easy further structural modification and reversibility. The corresponding photochemical quantum yield, however, remains relatively low (Φ ∼ 0.001). The theoretically calculated properties are in agreement with the obtained experimental results and support the proposed reaction mechanism.

  12. Isobar Separator for Anions: Current status

    NASA Astrophysics Data System (ADS)

    Alary, Jean-François; Javahery, Gholamreza; Kieser, William; Zhao, Xiao-Lei; Litherland, Albert; Cousins, Lisa; Charles, Christopher

    2015-10-01

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of 36S from 36Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion-molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  13. Porating anion-responsive copolymeric gels.

    PubMed

    England, Dustin; Yan, Feng; Texter, John

    2013-09-24

    A polymerizable ionic liquid surfactant, 1-(11-acryloyloxyundecyl)-3-methylimidiazolium bromide (ILBr), was copolymerized with methyl methacrylate (MMA) in aqueous microemulsions at 30% (ILBr w/w) and various water to MMA ratios. The ternary phase diagram of the ILBr/MMA/water system was constructed at 25 and 60 °C. Homopolymers and copolymers of ILBr and MMA were produced by thermally initiated chain radical microemulsion polymerization at various compositions in bicontinuous and reverse microemulsion subdomains. Microemulsion polymerization reaction products varied from being gel-like to solid, and these materials were analyzed by thermal and scanning electron microscopy methods. Microemulsion polymerized materials were insoluble in all solvents tested, consistent with light cross-linking. Ion exchange between Br(-) and PF6(-) in these copolymeric materials resulted in the formation of open-cell porous structures in some of these materials, as was confirmed by scanning electron microscopy (SEM). Several compositions illustrate the capture of prepolymerization nanoscale structure by thermally initiated polymerization, expanding the domain of compositions exhibiting this feat and yet to be demonstrated in any other system. Regular cylindrical pores in interpenetrating ILBr-co-MMA and PMMA networks are produced by anion exchange in the absence of templates. A percolating cluster/bicontinuous transition is "captured" by SEM after using anion exchange to visualize the mixed cluster/pore morphology. Some design principles for achieving this capture and for obtaining stimuli responsive solvogels are articulated, and the importance of producing solvogels in capturing the nanoscale is highlighted.

  14. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  15. Gap and stripline combined monitor

    DOEpatents

    Yin, Y.

    1984-02-16

    A combined gap and stripline monitor device for measuring the intensity and position of a charged particle beam bunch in a beam pipe of a synchrotron radiation facility. The monitor has first and second beam pipe portions with an axial gap therebetween. An outer pipe cooperates with the first beam pipe portion to form a gap enclosure, while inner strips cooperate with the first beam pipe portion to form a stripline monitor, with the stripline length being the same as the gap enclosure length.

  16. Axial gap rotating electrical machine

    DOEpatents

    None

    2016-02-23

    Direct drive rotating electrical machines with axial air gaps are disclosed. In these machines, a rotor ring and stator ring define an axial air gap between them. Sets of gap-maintaining rolling supports bear between the rotor ring and the stator ring at their peripheries to maintain the axial air gap. Also disclosed are wind turbines using these generators, and structures and methods for mounting direct drive rotating electrical generators to the hubs of wind turbines. In particular, the rotor ring of the generator may be carried directly by the hub of a wind turbine to rotate relative to a shaft without being mounted directly to the shaft.

  17. Gap and stripline combined monitor

    DOEpatents

    Yin, Y.

    1986-08-19

    A combined gap and stripline monitor device for measuring the intensity and position of a charged particle beam bunch in a beam pipe of a synchrotron radiation facility is disclosed. The monitor has first and second beam pipe portions with an axial gap therebetween. An outer pipe cooperates with the first beam pipe portion to form a gap enclosure, while inner strips cooperate with the first beam pipe portion to form a stripline monitor, with the stripline length being the same as the gap enclosure length. 4 figs.

  18. A model for underpotential deposition in the presence of anions

    NASA Astrophysics Data System (ADS)

    Giménez, M. C.; Ramirez-Pastor, A. J.; Leiva, E. P. M.

    2010-05-01

    A simple model to study the effect of on top coadsorption of anions in underpotential deposition is formulated. It considers a lattice-gas model with pair potential interactions between nearest neighbors. As test system, the electrodeposition of silver on gold is studied by means of grand canonical Monte Carlo simulations. The influence of anions on the adsorption isotherms is analyzed. It is found that as the interaction between silver atoms and anions increases, the monolayer adsorbs at more negative chemical potentials. For large interactions between silver atoms and anions, a expanded structure occurs for the silver monolayer.

  19. Inhibition of nuclear waste solutions containing multiple aggressive anions

    SciTech Connect

    Congdon, J.W.

    1988-05-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions; however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion.

  20. Monitoring trace anion contamination in disk drive components.

    PubMed

    Kaiser, Edward; Rohrer, Jeff; Campbell, Faye

    2003-05-16

    Ion chromatography was used to determine trace anionic contamination on the surface of hard disk drive components. These contaminants can have a detrimental effect on device reliability and yield. Disk drive components were soaked in deionized water and these extracts were analyzed for anions. The anions fluoride, acetate, formate, acrylate, methacrylate, chloride, nitrite, bromide, nitrate, benzoate, sulfate, oxalate, phthalate and phosphate were separated on a high-performance anion-exchange column and determined at concentrations less than 1 microg/l with suppressed conductivity detection. The extract solutions were analyzed either by injecting 1 ml or by preconcentrating 5 ml. We evaluated the performance of both methods.

  1. Purification Or Organic Acids Using Anion Exchange Chromatography.

    DOEpatents

    Ponnampalam; Elankovan

    2001-09-04

    Disclosed is a cost-effective method for purifying and acidifying carboxylic acids, including organic acids and amino acids. The method involves removing impurities by allowing the anionic form of the carboxylic acid to bind to an anion exchange column and washing the column. The carboxylic anion is displaced as carboxylic acid by washing the resin with a strong inorganic anion. This method is effective in removing organic carboxylic acids and amino acids from a variety of industrial sources, including fermentation broths, hydrolysates, and waste streams.

  2. Anion-Channel Blockers Inhibit S-Type Anion Channels and Abscisic Acid Responses in Guard Cells.

    PubMed Central

    Schwartz, A.; Ilan, N.; Schwarz, M.; Scheaffer, J.; Assmann, S. M.; Schroeder, J. I.

    1995-01-01

    The effects of anion-channel blockers on light-mediated stomatal opening, on the potassium dependence of stomatal opening, on stomatal responses to abscisic acid (ABA), and on current through slow anion channels in the plasma membrane of guard cells were investigated. The anion-channel blockers anthracene-9-carboxylic acid (9-AC) and niflumic acid blocked current through slow anion channels of Vicia faba L. guard cells. Both 9-AC and niflumic acid reversed ABA inhibition of stomatal opening in V. faba L. and Commelina communis L. The anion-channel blocker probenecid also abolished ABA inhibition of stomatal opening in both species. Additional tests of 9-AC effects on stomatal aperture in Commelina revealed that application of this anion-channel blocker allowed wide stomatal opening under low (1 mM) KCI conditions and increased the rate of stomatal opening under both low and high (100 mM) KCI conditions. These results indicate that anion channels can function as a negative regulator of stomatal opening, presumably by allowing anion efflux and depolarization, which prohibits ion up-take in guard cells. Furthermore, 9-AC prevented ABA induction of stomatal closure. A model in which ABA activation of anion channels contributes a rate-limiting mechanism during ABA-induced stomatal closure and inhibition of stomatal opening is discussed. PMID:12228619

  3. Anion-Channel Blockers Inhibit S-Type Anion Channels and Abscisic Acid Responses in Guard Cells.

    PubMed

    Schwartz, A.; Ilan, N.; Schwarz, M.; Scheaffer, J.; Assmann, S. M.; Schroeder, J. I.

    1995-10-01

    The effects of anion-channel blockers on light-mediated stomatal opening, on the potassium dependence of stomatal opening, on stomatal responses to abscisic acid (ABA), and on current through slow anion channels in the plasma membrane of guard cells were investigated. The anion-channel blockers anthracene-9-carboxylic acid (9-AC) and niflumic acid blocked current through slow anion channels of Vicia faba L. guard cells. Both 9-AC and niflumic acid reversed ABA inhibition of stomatal opening in V. faba L. and Commelina communis L. The anion-channel blocker probenecid also abolished ABA inhibition of stomatal opening in both species. Additional tests of 9-AC effects on stomatal aperture in Commelina revealed that application of this anion-channel blocker allowed wide stomatal opening under low (1 mM) KCI conditions and increased the rate of stomatal opening under both low and high (100 mM) KCI conditions. These results indicate that anion channels can function as a negative regulator of stomatal opening, presumably by allowing anion efflux and depolarization, which prohibits ion up-take in guard cells. Furthermore, 9-AC prevented ABA induction of stomatal closure. A model in which ABA activation of anion channels contributes a rate-limiting mechanism during ABA-induced stomatal closure and inhibition of stomatal opening is discussed.

  4. Do CH-Anion and Anion-π Interactions Alter the Mechanism of 2:1 Host-Guest Complexation in Arylethynyl Monourea Anion Receptors?

    PubMed

    Eytel, Lisa M; Gilbert, Annie K; Görner, Paul; Zakharov, Lev N; Johnson, Darren W; Haley, Michael M

    2017-03-23

    Selective tuning of arylethynyl urea scaffolds for anionic guests requires an understanding of preferred binding motifs of the host-guest interaction. To investigate the binding preference of receptors without a pre-organized binding pocket, two electron-deficient phenylacetylene receptors with a single urea moiety have been prepared and were found to bind halides as 2:1 host-guest complexes that feature key CH-anion or anion-π interactions. These supporting interactions also appear to influence the mechanism of the 2:1 binding event.

  5. Systems genetics of mineral metabolism.

    PubMed

    Fleet, James C; Replogle, Rebecca; Salt, David E

    2011-03-01

    Minerals are essential and toxic elements that have an impact on human health. Although we have learned a tremendous amount about the metabolism, biological roles, and health effects of minerals with the tools of biochemistry, cell biology, and molecular genetics, there are gaps in our knowledge of mineral biology that will benefit from new approaches. Forward genetics, whereby variations in phenotypes are mapped to natural genetic variation in the genome, has been successfully used to increase our understanding of many biologically important traits but has not yet been used extensively for mineral metabolism. In addition, the well-appreciated existence of interactions between minerals justifies a broader, systems approach to the study of mineral metabolism, i.e., ionomics. This short review will explain the value of forward genetics and ionomics as tools for exploring mammalian mineral metabolism.

  6. Measuring the Gap

    PubMed Central

    She, Xinshu; Zhao, Deqing; Scholnick, Jenna

    2016-01-01

    China is a large country where rapid development is accompanied by growing inequalities. How economic inequalities translate to health inequalities is unknown. Baseline health assessment is lacking among rural Chinese children. We aimed at assessing baseline student health of rural Chinese children and comparing them with those of urban children of similar ages. A cross-sectional study was conducted using the 2003 Global School-Based Student Health Survey among 100 students Grade 4 to 6 from rural Guizhou, China. Results were summarized and compared with public data from urban Beijing using multivariate logistic regression models. Rural children are more likely to not wash their hands before a meal (odds ratio [OR] = 5.71, P < .01) and after using the toilet (OR = 5.41, P < .01). They are more likely to feel sick or to get into trouble after drinking (OR = 7.28, P < .01). They are more likely to have used drugs (OR = 8.54, P < .01) and to have no close friends (OR = 8.23, P < .01). An alarming percentage of rural (8.22%) and urban (14.22%) children have had suicidal ideation in the past year (OR = 0.68, P > .05). Rural parents are more likely to not know their children’s whereabouts (OR = 1.81, P < .05). Rural children are more than 4 times likely to have serious injuries (OR = 4.64, P < .01) and to be bullied (OR = 4.01, P < .01). In conclusion, school-age rural Chinese children exhibit more health risk behaviors and fewer protective factors at baseline compared to their urban counterparts. Any intervention aimed at improving child health should take this distributive gap into consideration. PMID:27335999

  7. GAP Analysis Bulletin Number 15

    USGS Publications Warehouse

    Maxwell, Jill; Gergely, Kevin; Aycrigg, Jocelyn; Canonico, Gabrielle; Davidson, Anne; Coffey, Nicole

    2008-01-01

    The Mission of the Gap Analysis Program (GAP) is to promote conservation by providing broad geographic information on biological diversity to resource managers, planners, and policy makers who can use the information to make informed decisions. As part of the National Biological Information Infrastructure (NBII) ?a collaborative program to provide increased access to data and information on the nation?s biological resources--GAP data and analytical tools have been used in hundreds of applications: from basic research to comprehensive state wildlife plans; from educational projects in schools to ecoregional assessments of biodiversity. The challenge: keeping common species common means protecting them BEFORE they become threatened. To do this on a state or regional basis requires key information such as land cover descriptions, predicted distribution maps for native animals, and an assessment of the level of protection currently given to those plants and animals. GAP works cooperatively with Federal, state, and local natural resource professionals and academics to provide this kind of information. GAP activities focus on the creation of state and regional databases and maps that depict patterns of land management, land cover, and biodiversity. These data can be used to identify ?gaps? in conservation--instances where an animal or plant community is not adequately represented on the existing network of conservation lands. GAP is administered through the U.S. Geological Survey. Through building partnerships among disparate groups, GAP hopes to foster the kind of collaboration that is needed to address conservation issues on a broad scale. For more information, contact: John Mosesso National GAP Director 703-648-4079 Kevin Gergely National GAP Operations Manager 208-885-3565

  8. Once upon anion: a tale of photodetachment.

    PubMed

    Lineberger, W Carl

    2013-01-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, "with a little help from my friends." Actually, it was so much more than a little help!

  9. Once upon Anion: A Tale of Photodetachment

    NASA Astrophysics Data System (ADS)

    Lineberger, W. Carl

    2013-04-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!

  10. Structural evolution of small ruthenium cluster anions

    SciTech Connect

    Waldt, Eugen; Hehn, Anna-Sophia; Ahlrichs, Reinhart; Kappes, Manfred M.; Schooss, Detlef

    2015-01-14

    The structures of ruthenium cluster anions have been investigated using a combination of trapped ion electron diffraction and density functional theory computations in the size range from eight to twenty atoms. In this size range, three different structural motifs are found: Ru{sub 8}{sup −}–Ru{sub 12}{sup −} have simple cubic structures, Ru{sub 13}{sup −}–Ru{sub 16}{sup −} form double layered hexagonal structures, and larger clusters form close packed motifs. For Ru{sub 17}{sup −}, we find hexagonal close packed stacking, whereas octahedral structures occur for Ru{sub 18}{sup −}–Ru{sub 20}{sup −}. Our calculations also predict simple cubic structures for the smaller clusters Ru{sub 4}{sup −}–Ru{sub 7}{sup −}, which were not accessible to electron diffraction measurements.

  11. Anion channelrhodopsins for inhibitory cardiac optogenetics

    PubMed Central

    Govorunova, Elena G.; Cunha, Shane R.; Sineshchekov, Oleg A.; Spudich, John L.

    2016-01-01

    Optical control of the heart muscle is a promising strategy for cardiology because it is more specific than traditional electrical stimulation, and allows a higher temporal resolution than pharmacological interventions. Anion channelrhodopsins (ACRs) from cryptophyte algae expressed in cultured neonatal rat ventricular cardiomyocytes produced inhibitory currents at less than one-thousandth of the light intensity required by previously available optogenetic tools, such as the proton pump archaerhodopsin-3 (Arch). Because of their greater photocurrents, ACRs permitted complete inhibition of cardiomyocyte electrical activity under conditions in which Arch was inefficient. Most importantly, ACR expression allowed precisely controlled shortening of the action potential duration by switching on the light during its repolarization phase, which was not possible with previously used optogenetic tools. Optical shortening of cardiac action potentials may benefit pathophysiology research and the development of optogenetic treatments for cardiac disorders such as the long QT syndrome. PMID:27628215

  12. Metabolic myopathies

    NASA Technical Reports Server (NTRS)

    Martin, A.; Haller, R. G.; Barohn, R.; Blomqvist, C. G. (Principal Investigator)

    1994-01-01

    Metabolic myopathies are disorders of muscle energy production that result in skeletal muscle dysfunction. Cardiac and systemic metabolic dysfunction may coexist. Symptoms are often intermittent and provoked by exercise or changes in supply of lipid and carbohydrate fuels. Specific disorders of lipid and carbohydrate metabolism in muscle are reviewed. Evaluation often requires provocative exercise testing. These tests may include ischemic forearm exercise, aerobic cycle exercise, and 31P magnetic resonance spectroscopy with exercise.

  13. Anion-promoted cation motion and conduction in zeolites.

    PubMed

    Jordan, Edgar; Bell, Robert G; Wilmer, Dirk; Koller, Hubert

    2006-01-18

    The motion of sodium cations in sodalite and cancrinite has been investigated by force field calculations, solid-state NMR, and impedance spectroscopy. Special emphasis is dedicated to the influence of anions on sodium mobilities. Local cation motion is promoted when they interact with anions. However, not all systems with high local mobilities exhibit good ion conductivities, as cooperativity of the motion appears to be an important factor, as well. The activation barrier for local sodium motion (calculations) and long-range transport (dc conductivities) is lowered in sodalite when halogenide anions, Cl(-), Br(-), or I(-), are present. The activation barriers increase with increasing size of the anion and decreasing coordination in the transition state. On the basis of (23)Na solid-state NMR data, all the sodium ions in the dense sodalite structure are rather rigid up to 470 K. All the cations in chromate sodalite, and Na(+) in the small cancrinite epsilon-cages without anion interactions, show a restricted local motion at higher temperatures. There is a selective high local motion of Na(+) in the neighborhood of chromate anions in the more open channel system of cancrinite. These results suggest that sodium migration can be enhanced, at least locally, in open channel systems by anion interactions. A dynamics coupling between anion reorientation and cation mobility was not observed.

  14. Trifluoromethylsulfonyl derivatives of benzofuroxane and their anionic sigma-complexes

    SciTech Connect

    Yagupol'skii, L.M.; Gogoman, I.V.; Shchupak, G.M.; Boiko, V.N.

    1986-09-10

    Syntheses are reported for 4-nitro-6-trifluoromethylsulfonyl- and 4,6-bis(trifluoromethylsulfonyl)benzofuroxanes and their anionic sigma-complexes with hydroxide and methylate anions. In contrast to its 4,6-dinitro analog, 4,6-bis(trifluoromethylsulfonyl)benzofuroxane forms stable sigma-complexes with sodium acetate and sodium azide and has higher acidity by an order of magnitude.

  15. 8. VIEW OF GLOVE BOXES USED IN THE ANION EXCHANGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    8. VIEW OF GLOVE BOXES USED IN THE ANION EXCHANGE PROCESS. THE ANION EXCHANGE PROCESS PURIFIED AND CONCENTRATED PLUTONIUM-BEARING NITRIC ACID SOLUTIONS TO MAKE THEM ACCEPTABLE AS FEED FOR CONVERSION TO METAL. (6/20/60) - Rocky Flats Plant, Plutonium Recovery & Fabrication Facility, North-central section of plant, Golden, Jefferson County, CO

  16. Extraction of monoclonal antibodies (IgG1) using anionic and anionic/nonionic reverse micelles.

    PubMed

    George, Daliya A; Stuckey, David C

    2010-01-01

    Purification schemes for antibody production based on affinity chromatography are trying to keep pace with increases in cell culture expression levels and many current research initiatives are focused on finding alternatives to chromatography for the purification of Monoclonal antibodies (MAbs). In this article, we have investigated an alternative separation technique based on liquid-liquid extraction called the reverse micellar extraction. We extracted MAb (IgG1) using reverse micelles of an anionic surfactant, sodium bis 2-ethyl-hexyl sulfosuccinate (AOT) and a combination of anionic (AOT) and nonionic surfactants (Brij-30, Tween-85, Span-85) using isooctane as the solvent system. The extraction efficiency of IgG1 was studied by varying parameters, such as pH of the aqueous phase, cation concentration, and type and surfactant concentration. Using the AOT/Isooctane reverse micellar system, we could achieve good overall extraction of IgG1 (between 80 and 90%), but only 30% of the bioactivity of IgG1 could be recovered at the end of the extraction by using its binding to affinity chromatography columns as a surrogate measure of activity. As anionic surfactants were suspected as being one of the reasons for the reduced activity, we decided to combine a nonionic surfactant with an anionic surfactant and then study its effect on the extraction efficiency and bioactivity. The best results were obtained using an AOT/Brij-30/Isooctane reverse micellar system, which gave an overall extraction above 90 and 59% overall activity recovery. An AOT/Tween-85/Isooctane reverse micellar system gave an overall extraction of between 75 and 80% and overall activity recovery of around 40-45%. The results showed that the activity recovery of IgG1 can be significantly enhanced using different surfactant combination systems, and if the recovery of IgG1 can be further enhanced, the technique shows considerable promise for the downstream purification of MAbs.

  17. Cesium Platinide Hydride 4Cs2 Pt⋅CsH: An Intermetallic Double Salt Featuring Metal Anions.

    PubMed

    Smetana, Volodymyr; Mudring, Anja-Verena

    2016-11-14

    With Cs9 Pt4 H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs9 Pt4 H exhibits a complex crystal structure containing Cs(+) cations, Pt(2-) and H(-) anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the "alloy" cesium-platinum, or better cesium platinide, Cs2 Pt, and the salt cesium hydride CsH according to Cs9 Pt4 H≡4 Cs2 Pt⋅CsH.

  18. Cesium Platinide Hydride 4Cs 2 Pt-CsH: An Intermetallic Double Salt Featuring Metal Anions

    SciTech Connect

    Smetana, Volodymyr; Mudring, Anja-Verena

    2016-10-24

    With Cs9Pt4H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs9Pt4H exhibits a complex crystal structure containing Cs+ cations, Pt2- and H- anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the “alloy” cesium–platinum, or better cesium platinide, Cs2Pt, and the salt cesium hydride CsH according to Cs9Pt4H≡4 Cs2Pt∙CsH.

  19. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Moyer, Bruce a.; Bostick, Debra A.; Fowler, Christopher J.; Kang, Hyun-Ah; Ruas, Alexandre; Delmau, Laetitia H.; Haverlock, Tamara J.; Llinares, Jose M.; Hossain, Alamgir; Kang, S. O.; Bowman-James, Kristin; Shriver, James A.; Marquez, Manuel; Sessler, Jonathan L.

    2005-09-22

    The major thrust of this project led by the University of Kansas (Prof. Kristin Bowman-Jones) entails the exploration of the principles of recognition and separation of sulfate by the design, synthesis, and testing of novel sulfate extractants. A key science need for the cleanup of tank wastes at Hanford has been identified in developing methods to separate those bulk waste components that have low solubilities in borosilicate glass. Sulfate has been identified as a particularly difficult and expensive problem in that its concentration in the waste is relatively high, its solubility in glass is especially low, and it interferes with the performance of both vitrification equipment and the glass waste form. The new extractants will be synthesized by the University of Kansas and the University of Texas, Austin. Oak Ridge National Laboratory (ORNL) is subjecting the new extractants to experiments that will determine their properties and effectiveness in separating sulfate from the major competing anions in the waste, especially nitrate. Such experiments will entail primarily liquid-liquid extraction. Current efforts focus on exciting new systems in which the anion receptors act as synergists for anion exchange.

  20. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis.

    PubMed

    Song, Hyun-Ouk; Ryu, Jae-Sook

    2013-08-01

    Neutrophils are the predominant inflammatory cells found in vaginal discharges of patients infected with Trichomonas vaginalis. In this study, we examined superoxide anion (O2 (.-)) production by neutrophils activated by T. vaginalis. Human neutrophils produced superoxide anions when stimulated with either a lysate of T. vaginalis, its membrane component (MC), or excretory-secretory product (ESP). To assess the role of trichomonad protease in production of superoxide anions by neutrophils, T. vaginalis lysate, ESP, and MC were each pretreated with a protease inhibitor cocktail before incubation with neutrophils. Superoxide anion production was significantly decreased by this treatment. Trichomonad growth was inhibited by preincubation with supernatants of neutrophils incubated for 3 hr with T. vaginalis lysate. Furthermore, myeloperoxidase (MPO) production by neutrophils was stimulated by live trichomonads. These results indicate that the production of superoxide anions and MPO by neutrophils stimulated with T. vaginalis may be a part of defense mechanisms of neutrophils in trichomoniasis.

  1. An ab initio study on anionic aerogen bonds

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Mohammadian-Sabet, Fariba

    2017-01-01

    An ab initio study is carried out to investigate the anionic aerogen bonds in complexes of KrO3, XeO3 and XeOF2 with F-, Cl-, Br-, CN-, NC-, N3-, SH-, SCN-, NCS-, OH- and OCH3- anions. All of the anionic aerogen bonds analyzed here have a partial covalent character. Charge transfer from the anion to the Kr-O or Xe-O σ∗ orbital stabilizes these complexes and leads to a sizable redshift in the corresponding stretching frequencies. The J(Kr-O) or J(Xe-O) spin-spin coupling constants can be regarded as a useful tool for the characterization of strength of the anionic aerogen-bonded complexes.

  2. Enhanced anion binding by heteroatom replacement in bambusurils.

    PubMed

    Solel, Ephrath; Singh, Mandeep; Reany, Ofer; Keinan, Ehud

    2016-05-11

    This study was driven by the hypothesis that heteroatom replacement in bambusurils could significantly modify their anion binding properties. Indeed, calculations with various glycoluril and bambusuril analogs predict that such replacements significantly alter their molecular electrostatic potential and binding properties. Both polarization and electrostatic interactions contribute to anion binding, leading to a general trend of affinity among the neutral molecules: X = S > O > NH. In bambusurils the heteroatom replacement at the portal carbonyls affect the induced dipole more significantly than replacements at the equatorial carbonyls. The stronger polarization and stronger anion binding manifest the increased aptitude of the portal heteroatoms as electron sinks. Notably, this study predicts that protonated aza-bambusurils would not only bind multiple anions along their main axis, but could also function as synthetic anion channels.

  3. Double-hole codoped huge-gap semiconductor ZrO2 for visible-light photocatalysis.

    PubMed

    Wang, Jiajun; Huang, Jing; Meng, Jie; Li, Qunxiang; Yang, Jinlong

    2016-06-29

    Double-hole doping is an effective approach to engineer the band structures of semiconductors for enhancing the photoelectrochemical performance. Here, we explore the anionic monodoping (i.e. N, C, and P) and codoping (i.e. N + N, C + S, and N + P pairs) effects on the electronic structures and photocatalytic activities of ZrO2 by performing extensive density functional theory calculations. Upon anionic monodoping, several unoccupied impurity states appear within the band gap, which may trap the photogenerated carriers and then reduce the photocatalytic efficiency. Remarkably, double-hole doping via introducing three anionic (N + N), (C + S), and (N + P) codoping pairs in ZrO2 can not only effectively narrow the band gap, but can also create several fully filled delocalized intermediate bands for preventing the recombination of the photogenerated electron-hole pairs. Moreover, the band edge positions matching well with the redox potentials of water and the improved visible light absorption ability indicate that the three examined codoped ZrO2 systems are promising photocatalysts for visible light water splitting. In short, double-hole doping via anionic pairs provides an effective path to tune the huge-gap semiconductor band structures and to develop high efficient catalysts for solar-driven water splitting.

  4. Pneumatic gap sensor and method

    DOEpatents

    Bagdal, Karl T.; King, Edward L.; Follstaedt, Donald W.

    1992-01-01

    An apparatus and method for monitoring and maintaining a predetermined width in the gap between a casting nozzle and a casting wheel, wherein the gap is monitored by means of at least one pneumatic gap sensor. The pneumatic gap sensor is mounted on the casting nozzle in proximity to the casting surface and is connected by means of a tube to a regulator and a transducer. The regulator provides a flow of gas through a restictor to the pneumatic gap sensor, and the transducer translates the changes in the gas pressure caused by the proximity of the casting wheel to the pneumatic gap sensor outlet into a signal intelligible to a control device. The relative positions of the casting nozzle and casting wheel can thereby be selectively adjusted to continually maintain a predetermined distance between their adjacent surfaces. The apparatus and method enables accurate monitoring of the actual casting gap in a simple and reliable manner resistant to the extreme temperatures and otherwise hostile casting environment.

  5. Pneumatic gap sensor and method

    DOEpatents

    Bagdal, K.T.; King, E.L.; Follstaedt, D.W.

    1992-03-03

    An apparatus and method for monitoring and maintaining a predetermined width in the gap between a casting nozzle and a casting wheel, wherein the gap is monitored by means of at least one pneumatic gap sensor. The pneumatic gap sensor is mounted on the casting nozzle in proximity to the casting surface and is connected by means of a tube to a regulator and a transducer. The regulator provides a flow of gas through a restictor to the pneumatic gap sensor, and the transducer translates the changes in the gas pressure caused by the proximity of the casting wheel to the pneumatic gap sensor outlet into a signal intelligible to a control device. The relative positions of the casting nozzle and casting wheel can thereby be selectively adjusted to continually maintain a predetermined distance between their adjacent surfaces. The apparatus and method enables accurate monitoring of the actual casting gap in a simple and reliable manner resistant to the extreme temperatures and otherwise hostile casting environment. 6 figs.

  6. Selectivity control in synergistic liquid-liquid anion exchange of univalent anions via structure-specific cooperativity between quaternary ammonium cations and anion receptors.

    PubMed

    Borman, Christopher J; Bonnesen, Peter V; Moyer, Bruce A

    2012-10-02

    Two anion receptors enhance liquid-liquid anion exchange when added to quaternary alkylammonium chloride anion exchangers, but with a striking dependence on the structure of the alkylammonium cation that suggests a supramolecular cooperative effect. Two anion receptors were investigated, meso-octamethylcalix[4]pyrrole (C4P) and the bisthiourea tweezer 1,1'-(propane-1,3-diyl)bis(3-(4-sec-butylphenyl)thiourea (BTU). Whereas synergism is comparatively weak when either methyltri(C(8,10))alkylammonium chloride (Aliquat 336) or tetraheptylammonium chloride is used with the BTU receptor, synergism between C4P and Aliquat 336 is so pronounced that anion exchange prefers chloride over more extractable nitrate and trifluoroacetate, effectively overcoming the ubiquitous Hofmeister bias. A thermochemical analysis of synergistic anion exchange has been provided for the first time, resulting in the estimation of binding constants for C4P with the ion pairs of A336(+) with Cl(-), Br(-), OAc(F3)(-), NO(3)(-), and I(-).

  7. Effect of the synergistic anion on electron paramagnetic resonance spectra of iron-transferrin anion complexes is consistent with bidentate binding of the anion.

    PubMed Central

    Dubach, J; Gaffney, B J; More, K; Eaton, G R; Eaton, S S

    1991-01-01

    Continuous wave (cw) X-band EPR spectra at approximately 90 K were obtained for iron-transferrin-anion complexes with 18 anions. Each anion had a carboxylate group and at least one other polar moiety. As the second polar group was varied from hydroxyl to carbonyl to amine to carboxylate, the EPR spectra changed from a dominant signal at g' approximately 4.3 with a second smaller peak at g' approximately 9 to a broad signal with intensity between g' approximately 5 and 7. Computer simulation indicated that the changes in the EPR spectra were due to changes in the zero field splitting parameter ratio, E/D, from approximately 1/3 for carbonate anion to approximately 0.04 for malonate anion. Observation of iron-13C coupling in the electron spin echo envelope modulation (ESEEM) for iron transferrin [1-13C]pyruvate indicated that the carboxylate group was bound to the iron. It is proposed that all of the anions behave as bidentate ligands, with coordination to the iron through both the carboxylate and proximal groups, and the carboxyl group serves as a bridge between the iron and a positively charged group on the protein. PMID:1651123

  8. Electronic characterization of defects in narrow gap semiconductors

    NASA Technical Reports Server (NTRS)

    Patterson, James D.

    1994-01-01

    We use a Green's function technique to calculate the position of deep defects in narrow gap semiconductors. We consider substitutional (including antisite), vacancy, and interstitial (self and foreign) deep defects. We also use perturbation theory to look at the effect of nonparabolic bands on shallow defect energies and find nonparabolicity can increase the binding by 10 percent or so. We consider mercury cadmium telluride (MCT), mercury zinc telluride (MZT), and mercury zinc selenide (MZS). For substitutional and interstitial defects we look at the situation with and without relaxation. For substitutional impurities in MCT, MZT, and MZS, we consider x (the concentration of Cd or Zn) in the range 0.1 less than x less than 0.3 and also consider appropriate x so E(sub g) = 0.1 eV for each of the three compounds. We consider several cation site s-like deep levels and anion site p-like levels. For E(sub g) = 0.1 eV, we also consider the effects of relaxation. Similar comments apply to the interstitial deep levels whereas no relaxation is considered for the ideal vacancy model. Relaxation effects can be greater for the interstitial than the substitutional cases. Specific results are given in figures and tables and comparison to experiment is made in a limited number of cases. We find, for example, that I, Se, S, Rn, and N are possible cation site, s-like deep levels in MCT and Zn and Mg are for anion site, p-like levels (both levels for substitutional cases). The corresponding cation and anion site levels for interstitial deep defects are (Au, Ag, Hg, Cd, Cu, Zn) and (N, Ar, O, F). For the substitutional cases we have some examples of relaxation moving the levels into the band gap, whereas for the interstitial case we have examples where relaxation moves it out of the band gap. Future work involves calculating the effects of charge state interaction and seeing the effect of relaxation on vacancy levels.

  9. Electronic materials with a wide band gap: recent developments

    PubMed Central

    Klimm, Detlef

    2014-01-01

    The development of semiconductor electronics is reviewed briefly, beginning with the development of germanium devices (band gap E g = 0.66 eV) after World War II. A tendency towards alternative materials with wider band gaps quickly became apparent, starting with silicon (E g = 1.12 eV). This improved the signal-to-noise ratio for classical electronic applications. Both semiconductors have a tetrahedral coordination, and by isoelectronic alternative replacement of Ge or Si with carbon or various anions and cations, other semiconductors with wider E g were obtained. These are transparent to visible light and belong to the group of wide band gap semiconductors. Nowadays, some nitrides, especially GaN and AlN, are the most important materials for optical emission in the ultraviolet and blue regions. Oxide crystals, such as ZnO and β-Ga2O3, offer similarly good electronic properties but still suffer from significant difficulties in obtaining stable and technologically adequate p-type conductivity. PMID:25295170

  10. Gallium based low-interaction anions

    DOEpatents

    King, Wayne A.; Kubas, Gregory J.

    2000-01-01

    The present invention provides: a composition of the formula M.sup.+x (Ga(Y).sub.4.sup.-).sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; a composition of the formula (R).sub.x Q.sup.+ Ga(Y).sub.4.sup.- where Q is selected from the group consisting of carbon, nitrogen, sulfur, phosphorus and oxygen, each R is a ligand selected from the group consisting of alkyl, aryl, and hydrogen, x is an integer selected from the group consisting of 3 and 4 depending upon Q, and each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; an ionic polymerization catalyst composition including an active cationic portion and a gallium based weakly coordinating anion; and bridged anion species of the formula M.sup.+x.sub.y [X(Ga(Y.sub.3).sub.z ].sup.-y.sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, X is a bridging group between two gallium atoms, y is an integer selected from the group consisting 1 and 2, z is an integer of at least 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide.

  11. GAP Analysis. Bulletin Number 11

    DTIC Science & Technology

    2002-01-01

    Lucas jack pine that is the habitat but rather (say) jack pine in which tree dynamics, and the test of accuracy was done at a time of high popu... testing are elaborated by Krohn [1996]). stresses) killed the birds that would have occupied them, in which Commission error (predicting the presence...thereby destroying the dove-arable correlation that would which GAP has historically been based should lead it to accept any have underlain a GAP assessment

  12. Eight electrode optical readout gap

    DOEpatents

    Boettcher, Gordon E.; Crain, Robert W.

    1985-01-01

    A protective device for a plurality of electrical circuits includes a pluity of isolated electrodes forming a gap with a common electrode. An output signal, electrically isolated from the circuits being monitored, is obtained by a photosensor viewing the discharge gap through an optical window. Radioactive stabilization of discharge characteristics is provided for slowly changing voltages and carbon tipped dynamic starters provide desirable discharge characteristics for rapidly varying voltages. A hydrogen permeation barrier is provided on external surfaces of the device.

  13. Extended negative dietary cation-anion difference feeding does not negatively affect postpartum performance of multiparous dairy cows.

    PubMed

    Weich, W; Block, E; Litherland, N B

    2013-09-01

    Low postpartum blood calcium remains one of the largest constraints to postpartum feed intake, milk yield, and energy balance in transitioning dairy cows. Supplemental dietary anions decrease the dietary cation-anion difference (DCAD) and reduce the risk for postpartum hypocalcemia. Prepartum management strategies aiming to minimize social stress and diet changes have resulted in a need to explore the effects of extended exposure to a negative DCAD (>21 d) diet. Holstein and Holstein-cross dairy cows (n=60) were assigned to 1 of 3 treatments 42 d before expected calving to evaluate effects of supplying anions for 21 or 42 d during the dry period on energy status, postpartum production, and Ca homeostasis. Treatments included (1) a control diet (CON; DCAD=12 mEq/100 g of DM), (2) a 21-d negative DCAD diet (21-ND; DCAD=12 and -16 mEq/100 g of DM), and (3) a 42-d negative DCAD diet (42-ND; DCAD=-16 mEq/100 g of DM). Cows fed CON were fed positive DCAD prepartum for 42 d. Cows fed 21-ND received the positive DCAD (12 mEq/100 g of DM) diet for the first 21 d of the dry period and the anionic diet (-16 mEq/100 g of DM) from d 22 until calving. Cows fed 42-ND received the anionic diet for the entire dry period. Control and anionic diets were formulated by using 2 isonitrogenous protein mixes: (1) 97.5% soybean meal and (2) 52.8% BioChlor (Church & Dwight Co. Inc.), 45.8% soybean meal. Supplementing anions induced a mild metabolic acidosis, reducing urine pH for 21-ND and 42-ND compared with CON. Prepartum DMI was not different among treatments. Postpartum DMI was higher for 21-ND compared with CON (20.8 vs. 18.1±1.1 kg/d), and 42-ND had similar DMI compared with 21-ND. During the first 56 d of lactation 21-ND had greater average milk production compared with CON (44.8 vs. 39.2±2.1 kg/d). Average milk production by 42-ND was similar to 21-ND. Postpartum total blood Ca concentration was greater for 42-ND. Cows fed anionic diets prepartum tended to have lower lipid

  14. Globins Scavenge Sulfur Trioxide Anion Radical*

    PubMed Central

    Gardner, Paul R.; Gardner, Daniel P.; Gardner, Alexander P.

    2015-01-01

    Ferrous myoglobin was oxidized by sulfur trioxide anion radical (STAR) during the free radical chain oxidation of sulfite. Oxidation was inhibited by the STAR scavenger GSH and by the heme ligand CO. Bimolecular rate constants for the reaction of STAR with several ferrous globins and biomolecules were determined by kinetic competition. Reaction rate constants for myoglobin, hemoglobin, neuroglobin, and flavohemoglobin are large at 38, 120, 2,600, and ≥ 7,500 × 106 m−1 s−1, respectively, and correlate with redox potentials. Measured rate constants for O2, GSH, ascorbate, and NAD(P)H are also large at ∼100, 10, 130, and 30 × 106 m−1 s−1, respectively, but nevertheless allow for favorable competition by globins and a capacity for STAR scavenging in vivo. Saccharomyces cerevisiae lacking sulfite oxidase and deleted of flavohemoglobin showed an O2-dependent growth impairment with nonfermentable substrates that was exacerbated by sulfide, a precursor to mitochondrial sulfite formation. Higher O2 exposures inactivated the superoxide-sensitive mitochondrial aconitase in cells, and hypoxia elicited both aconitase and NADP+-isocitrate dehydrogenase activity losses. Roles for STAR-derived peroxysulfate radical, superoxide radical, and sulfo-NAD(P) in the mechanism of STAR toxicity and flavohemoglobin protection in yeast are suggested. PMID:26381408

  15. Lysozyme binding onto cat-anionic vesicles.

    PubMed

    Bonincontro, A; Spigone, E; Ruiz Peña, M; Letizia, C; La Mesa, C

    2006-12-15

    Mixing aqueous sodium dodecylsulfate with cetyltrimethylammonium bromide solutions in mole ratios close to (1.7/1.0) allows the formation of cat-anionic vesicles with an excess of negative charges on the outer surface. The vesicular dispersions are mixed with lysozyme, and interact electrostatically with the positive charges on the protein, forming lipo-plexes. Dielectric relaxation, zeta-potential, and light scattering indicate the occurrence of interactions between vesicles and the protein. According to CD, the vesicle-adsorbed protein retains its native conformation. Binding and surface saturation, inferred by dielectric relaxation and zeta-potential, fulfil a charge neutralisation stoichiometry. Adsorbed lysozyme promotes the vesicle clustering and is concomitant with the lipo-plexes flocculation. Above the charge neutralisation threshold, lysozyme in excess remains dispersed in molecular form. Attempts were made to determine in what conditions protein release from the vesicles occurs. Accordingly, the full neutralisation of sodium dodecylsulfate in excess by cetyltrimethylammonium bromide ensures the lipo-plexes break-up, the precipitation of the mixed surfactants and the protein release in native form.

  16. Globins Scavenge Sulfur Trioxide Anion Radical.

    PubMed

    Gardner, Paul R; Gardner, Daniel P; Gardner, Alexander P

    2015-11-06

    Ferrous myoglobin was oxidized by sulfur trioxide anion radical (STAR) during the free radical chain oxidation of sulfite. Oxidation was inhibited by the STAR scavenger GSH and by the heme ligand CO. Bimolecular rate constants for the reaction of STAR with several ferrous globins and biomolecules were determined by kinetic competition. Reaction rate constants for myoglobin, hemoglobin, neuroglobin, and flavohemoglobin are large at 38, 120, 2,600, and ≥ 7,500 × 10(6) m(-1) s(-1), respectively, and correlate with redox potentials. Measured rate constants for O2, GSH, ascorbate, and NAD(P)H are also large at ∼100, 10, 130, and 30 × 10(6) m(-1) s(-1), respectively, but nevertheless allow for favorable competition by globins and a capacity for STAR scavenging in vivo. Saccharomyces cerevisiae lacking sulfite oxidase and deleted of flavohemoglobin showed an O2-dependent growth impairment with nonfermentable substrates that was exacerbated by sulfide, a precursor to mitochondrial sulfite formation. Higher O2 exposures inactivated the superoxide-sensitive mitochondrial aconitase in cells, and hypoxia elicited both aconitase and NADP(+)-isocitrate dehydrogenase activity losses. Roles for STAR-derived peroxysulfate radical, superoxide radical, and sulfo-NAD(P) in the mechanism of STAR toxicity and flavohemoglobin protection in yeast are suggested.

  17. Anionic biopolymers as blood flow sensors.

    PubMed

    Siegel, G; Walter, A; Kauschmann, A; Malmsten, M; Buddecke, E

    1996-01-01

    The finding of flow-dependent vasodilation rests on the basic observation that with an increase in blood flow the vessels become wider, with a decrease the vascular smooth muscle cells contract. Proteoheparan sulphate could be the sensor macromolecule at the endothelial cell membrane-blood interface, that reacts on the shear stress generated by the flowing blood, and that informs and regulates the vascular smooth muscle cells via a signal transduction chain. This anionic biopolyelectrolyte possesses viscoelastic and specific ion binding properties which allow a change of its configuration in dependence on shear stress and electrostatic charge density. The blood flow sensor undergoes a conformational transition from a random coil to an extended filamentous state with increasing flow, whereby Na+ ions from the blood are bound. Owing to the intramolecular elastic recoil forces of proteoheparan sulphate the slowing of a flow rate causes an entropic coiling, the expulsion of Na+ ions and thus an interruption of the signal chain. Under physiological conditions, the conformation and Na+ binding proved to be extremely Ca(2+)-sensitive while K+ and Mg2+ ions play a minor role for the susceptibility of the sensor. Via counterion migration of the bound Na+ ions along the sensor glycosaminoglycan side chains and following Na+ passage through an unspecific ion channel in the endothelial cell membrane, the signal transduction chain leads to a membrane depolarization with Ca2+ influx into the cells. This stimulates the EDRF/NO production and release from the endothelial cells. The consequence is vasodilation.

  18. Neptunium Valence Chemistry in Anion Exchange Processing

    SciTech Connect

    KYSER, EDWARD

    2003-02-01

    The current anion resin in use in HB-Line Phase II, Reillex{trademark} HPQ, was tested in the laboratory under expected plant conditions for Np processing and was found to load between 50 and 70 g Np per liter of resin. Losses varied from 0.2 to 15 percent depending on a number of parameters. Hydrazine in the feed at 0.02 to 0.05 M appeared to keep the Np from oxidizing and increasing the losses within four to seven days after the FS addition. Losses of up to three percent were observed five days after FS addition when hydrazine was not used in the feed, compared with 0.3 percent when the feed was loaded immediately after FS addition. Based on these test results the following processing conditions are recommended: (1) Feed conditions: 8 M HNO{sub 3}, 0.02 M hydrazine, 0.05 M excess FS, less than 5 days storage of solution after FS addition. (2) Wash conditions: 100 liters of 8 M HNO{sub 3}, no FS, no hydrazine. (3) Elution conditions: 0.17 M HNO{sub 3}, 0.05 M hydrazine, no FS. (4) Precipitation feed conditions: 0.03 M excess ascorbic acid, no additional hydrazine, no FS, precipitation within three days.

  19. Anion binding to the ubiquitin molecule.

    PubMed Central

    Makhatadze, G. I.; Lopez, M. M.; Richardson, J. M.; Thomas, S. T.

    1998-01-01

    Effects of different salts (NaCl, MgCl2, CaCl2, GdmCl, NaBr, NaClO4, NaH2PO4, Na2SO4) on the stability of the ubiquitin molecule at pH 2.0 have been studied by differential scanning calorimetry, circular dichroism, and Tyr fluorescence spectroscopies. It is shown that all of the salts studied significantly increase the thermostability of the ubiquitin molecule, and that this stabilization can be interpreted in terms of anion binding. Estimated thermodynamic parameters of binding for Cl- show that this binding is relatively weak (Kd = 0.15 M) and is characterized by a negative enthalpy of -15 kJ/mol per site. Particularly surprising was the observed stabilizing effect of GdmCl through the entire concentration range studied (0.01-2 M), however, to a lesser extent than stabilization by NaCl. This stabilizing effect of GdmCl appears to arise from the binding of Cl- ions. Analysis of the observed changes in the stability of the ubiquitin molecule in the presence of GdmCl can be adequately described by combining the thermodynamic model of denaturant binding with Cl- binding effects. PMID:9541401

  20. Four imidazolium iodocuprates based on anion-π and π-π interactions: Structural and spectral modulation

    NASA Astrophysics Data System (ADS)

    Liu, Fang; Hao, Pengfei; Yu, Tanlai; Guan, Qi; Fu, Yunlong

    2016-09-01

    Four imidazolium iodocuprates, [(1,3-dimethylimidazole)(Cu2I3)]n (1), [(1,2,3-trimethylimidazole)(Cu2I3)]n (2), [(1,3-dimethylimidazole)(Cu3I5)]n (3) and [(1,3-dimethylbenzimidazole)(CuI2)]n (4) have been solvothermally synthesized and optically characterized. Results exhibit that cationic spatial orientation, anion-π and π-π interactions are beneficial to structural diversity and band gap modulation of iodocuprate hybrids. The UV-vis diffuse reflectance spectra show that compounds 1-4 are potential semiconductor materials.

  1. Rotational auto-detachment of dipole-bound anions

    NASA Astrophysics Data System (ADS)

    Ard, S. G.; Compton, R. N.; Garrett, W. R.

    2016-04-01

    Rotational auto-detachment of acetonitrile, trimethyl-acetonitrile, acetone, and cyclobutanone dipole-bound anions was studied under varying conditions in a Rydberg electron transfer (RET) time-of-flight apparatus. Varying amounts of auto-detachment was observed for anions with similar electron affinity and dipole moment, but different moments of inertia. These results were found to be consistent with predictions based on the calculated rotational spectra for these anions, highlighting the importance of critical binding properties in understanding the stability and lifetime of dipole bound systems.

  2. Survey of organic acid eluents for anion chromatography

    SciTech Connect

    Book, D.E.

    1981-10-01

    Of all the potential eluents surveyed (including aromatic, sulfonic, phosphonic, among other acids), only the carboxylic acids and the nitrophenols are recommended as eluents for anion chromatography. The concentration of the eluent should be in the range 5 x 10/sup -5/ to 1 x 10/sup -3/ M. The eluent should have the same charge as inorganic anions, a higher charge than organic acid samples. Choice of eluents for separation of halides, chloride and sulfate, multivalent inorganic anions, small alkyl acids, and aromatic acids is discussed. (DLC)

  3. Postsynaptic Deregulation in GAP-43 Heterozygous Mouse Barrel Cortex

    PubMed Central

    Kelly, Emily A.; Tremblay, Marie-Ève; McCasland, James S.

    2010-01-01

    Formation of whisker-related barrels in primary somatosensory cortex (S1) requires communication between presynaptic thalamocortical afferents (TCAs) and postsynaptic cortical neurons. GAP-43 is crucially involved in targeting TCAs to postsynaptic S1 neurons but its influence on the interactions between these 2 elements has not been explored. Here, we tested the hypothesis that reduced early expression of presynaptic GAP-43 (GAP-43 heterozygous [HZ] mice) alters postsynaptic differentiation of barrel cells. We found a transient increase in cytochrome oxidase staining between P6 and P14 in HZ animals, indicative of increased metabolic activity in barrel cortex during this time. Golgi impregnation and microtubule-associated protein 2 immunohistochemistry showed anomalous dendritic patterning in GAP-43 HZ cortex at P5, with altered dendritic length and branching and abnormal retention of dendrites that extend into developing septa. This deficiency was no longer apparent at P7, suggesting partial recovery of dendritic pruning processes. Finally, we showed early defects in synaptogenesis from P4 to P5 with increased colocalization of NR1 and GluR1 staining in HZ mice. By P7, this colocalization had normalized to wild type levels. Taken together, our findings suggest abnormal postsynaptic differentiation in GAP-43 HZ cortex during early barrel development, followed by adaptive compensation and partial phenotypic rescue. PMID:19915093

  4. Vibrational investigations of guanine, thioguanine and their singly charged cations and anions

    NASA Astrophysics Data System (ADS)

    Singh, R.; Yadav, R. A.

    2017-01-01

    The complete vibrational studies have been done with help of quantum mechanics for the neutral Guanine (Gua) and Thioguanine (TGua) molecules and their singly charged cations and anions employing the B3LYP/6-311++G** method. Neutral Thioguanine and cations of Guanine and Thioguanine show planar structures and belong to Cs point group symmetry while the neutral Guanine and anions of Guanine and Thioguanine possess non-planar structure with C1 point group symmetry. Vibrational studies of ionic radicals of Gua and its thio- derivative are not available in literatures. Such extensive studies have been attempted for the first time. The normal modes of all the species have been assigned on the basis using potential energy distributions (PEDs) using GAR2PED software. The PEDs have also been calculated to make a conspicuous assignment as animation available in GaussView is not a guarantee for correct normal mode assignment. Charge transfer occurs in the molecule have been shown by the calculated highest occupied molecular orbital—lowest unoccupied molecular orbital (HOMO-LUMO) energies. The mapping of electron density iso-surface with electrostatic potential, has been carried out to get the information about the size, shape, charge density distribution and site of chemical reactivity of the molecule. The electronic properties HOMO and LUMO energies have been measured. The energy gap from HOMO to LUMO of the Gua is 5.0547 eV and TGua 4.0743 eV.

  5. Stabilizers for GAP and GAP-based Propellants Interim Report

    DTIC Science & Technology

    2008-10-09

    the m j o r deconposit inn pathways of GAP and U P prope l lan ts i n o r d e r to i n p r o w long term storage stabi l i ty. Model c- s inw...la t i ng t h e ut ido-bear ing frmctional units of GAP ( a z i d e adjacent t o po lye ther k k b o n e , az ide sd jacent t o terminal...binder i n prope l lan t -ag ing studies has varied accord2~g t o the to t of GAP used. This v a r i a b i l i t y my k linked to residual i n p

  6. Metabolic neuropathies

    MedlinePlus

    ... Severe infection throughout the body ( sepsis ) Thyroid disease Vitamin deficiencies (including vitamins B12 , B6 , E , and B1 ) Some ... best treatment is to correct the metabolic problem. Vitamin deficiencies are treated with diet or with vitamins by ...

  7. Superoxide Anion Radical Production in the Tardigrade Paramacrobiotus richtersi, the First Electron Paramagnetic Resonance Spin-Trapping Study.

    PubMed

    Savic, Aleksandar G; Guidetti, Roberto; Turi, Ana; Pavicevic, Aleksandra; Giovannini, Ilaria; Rebecchi, Lorena; Mojovic, Milos

    2015-01-01

    Anhydrobiosis is an adaptive strategy that allows withstanding almost complete body water loss. It has been developed independently by many organisms belonging to different evolutionary lines, including tardigrades. The loss of water during anhydrobiotic processes leads to oxidative stress. To date, the metabolism of free radicals in tardigrades remained unclear. We present a method for in vivo monitoring of free radical production in tardigrades, based on electron paramagnetic resonance and spin-trap DEPMPO, which provides simultaneous identification of various spin adducts (i.e., different types of free radicals). The spin trap can be easily absorbed in animals, and tardigrades stay alive during the measurements and during 24-h monitoring after the treatment. The results show that hydrated specimens of the tardigrade Paramacrobiotus richtersi produce the pure superoxide anion radical ((•)O2(-)). This is an unexpected result, as all previously examined animals and plants produce both superoxide anion radical and hydroxyl radical ((•)OH) or exclusively hydroxyl radical.

  8. Crop yield gaps in Cameroon.

    PubMed

    Yengoh, Genesis T; Ardö, Jonas

    2014-03-01

    Although food crop yields per hectare have generally been increasing in Cameroon since 1961, the food price crisis of 2008 and the ensuing social unrest and fatalities raised concerns about the country's ability to meet the food needs of its population. This study examines the country's potential for increasing crop yields and food production to meet this food security challenge. Fuzzy set theory is used to develop a biophysical spatial suitability model for different crops, which in turn is employed to ascertain whether crop production is carried out in biophysically suited areas. We use linear regression to examine the trend of yield development over the last half century. On the basis of yield data from experimental stations and farmers' fields we assess the yield gap for major food crops. We find that yields have generally been increasing over the last half century and that agricultural policies can have significant effects on them. To a large extent, food crops are cultivated in areas that are biophysically suited for their cultivation, meaning that the yield gap is not a problem of biophysical suitability. Notwithstanding, there are significantly large yield gaps between actual yields on farmers' farms and maximum attainable yields from research stations. We conclude that agronomy and policies are likely to be the reasons for these large yield gaps. A key challenge to be addressed in closing the yield gaps is that of replenishing and properly managing soil nutrients.

  9. Explaining the Gender Wealth Gap

    PubMed Central

    Ruel, Erin; Hauser, Robert M.

    2013-01-01

    To assess and explain the United States’ gender wealth gap, we use the Wisconsin Longitudinal Study to examine wealth accumulated by a single cohort over 50 years by gender, by marital status, and limited to the respondents who are their family’s best financial reporters. We find large gender wealth gaps between currently married men and women, and never-married men and women. The never-married accumulate less wealth than the currently married, and there is a marital disruption cost to wealth accumulation. The status-attainment model shows the most power in explaining gender wealth gaps between these groups explaining about one-third to one-half of the gap, followed by the human-capital explanation. In other words, a lifetime of lower earnings for women translates into greatly reduced wealth accumulation. A gender wealth gap remains between married men and women after controlling for the full model that we speculate may be related to gender differences in investment strategies and selection effects. PMID:23264038

  10. Field induced gap infrared detector

    NASA Technical Reports Server (NTRS)

    Elliott, C. Thomas (Inventor)

    1990-01-01

    A tunable infrared detector which employs a vanishing band gap semimetal material provided with an induced band gap by a magnetic field to allow intrinsic semiconductor type infrared detection capabilities is disclosed. The semimetal material may thus operate as a semiconductor type detector with a wavelength sensitivity corresponding to the induced band gap in a preferred embodiment of a diode structure. Preferred semimetal materials include Hg(1-x)Cd(x)Te, x is less than 0.15, HgCdSe, BiSb, alpha-Sn, HgMgTe, HgMnTe, HgZnTe, HgMnSe, HgMgSe, and HgZnSe. The magnetic field induces a band gap in the semimetal material proportional to the strength of the magnetic field allowing tunable detection cutoff wavelengths. For an applied magnetic field from 5 to 10 tesla, the wavelength detection cutoff will be in the range of 20 to 50 micrometers for Hg(1-x)Cd(x)Te alloys with x about 0.15. A similar approach may also be employed to generate infrared energy in a desired band gap and then operating the structure in a light emitting diode or semiconductor laser type of configuration.

  11. An anion channel in Arabidopsis hypocotyls activated by blue light

    NASA Technical Reports Server (NTRS)

    Cho, M. H.; Spalding, E. P.; Evans, M. L. (Principal Investigator)

    1996-01-01

    A rapid, transient depolarization of the plasma membrane in seedling stems is one of the earliest effects of blue light detected in plants. It appears to play a role in transducing blue light into inhibition of hypocotyl (stem) elongation, and perhaps other responses. The possibility that activation of a Cl- conductance is part of the depolarization mechanism was raised previously and addressed here. By patch clamping hypocotyl cells isolated from dark-grown (etiolated) Arabidopsis seedlings, blue light was found to activate an anion channel residing at the plasma membrane. An anion-channel blocker commonly known as NPPB 15-nitro-2-(3-phenylpropylamino)-benzoic acid] potently and reversibly blocked this anion channel. NPPB also blocked the blue-light-induced depolarization in vivo and decreased the inhibitory effect of blue light on hypocotyl elongation. These results indicate that activation of this anion channel plays a role in transducing blue light into growth inhibition.

  12. Is Nitrate Anion Photodissociation Mediated by Singlet-Triplet Absorption?

    PubMed

    Svoboda, Ondřej; Slavíček, Petr

    2014-06-05

    Photolysis of the nitrate anion is involved in the oxidation processes in the hydrosphere, cryosphere, and stratosphere. While it is known that the nitrate photolysis in the long-wavelength region proceeds with a very low quantum yield, the mechanism of the photodissociation remains elusive. Here, we present the quantitative modeling of singlet-singlet and singlet-triplet absorption spectra in the atmospherically relevant region around 300 nm, and we argue that a spin-forbidden transition between the singlet ground state and the first triplet state contributes non-negligibly to the nitrate anion photolysis. We further propose that the nitrate anion excited into the first singlet excited state relaxes nonradiatively into its ground state. The full understanding of the nitrate anion photolysis can improve modeling of the asymmetric solvation in the atmospheric processes, e.g., photolysis on the surfaces of ice or snow.

  13. New stationary phase for anion-exchange chromatography.

    PubMed

    Auler, Lúcia M L A; Silva, César R; Collins, Kenneth E; Collins, Carol H

    2005-05-06

    This work describes the preparation of an anion-exchange phase based on silica, using a two-step modification process. First, 10 microm Davisil silica particles were silanized with chloropropyltrimethoxysilane to yield chloropropyl silica. The modified silica was then reacted with pyridine to produce positively charged propylpyridinium groups on the surface, the anion-exchange sites. The phase was characterized by thermogravimetric analysis and infrared and solid state 13C and 29Si NMR spectroscopies. HPLC separations of common inorganic anions, including chloride, nitrite, bromide and nitrate, were performed using 150 x 3.9 HPLC columns packed with the phase, using a phthalate buffer solution as mobile phase with non-suppressed conductivity detection. Efficiency and resolution were calculated and the results show that the new phase has significant promise for the analysis of these anions in environmental samples.

  14. An anion channel in Arabidopsis hypocotyls activated by blue light.

    PubMed Central

    Cho, M H; Spalding, E P

    1996-01-01

    A rapid, transient depolarization of the plasma membrane in seedling stems is one of the earliest effects of blue light detected in plants. It appears to play a role in transducing blue light into inhibition of hypocotyl (stem) elongation, and perhaps other responses. The possibility that activation of a Cl- conductance is part of the depolarization mechanism was raised previously and addressed here. By patch clamping hypocotyl cells isolated from dark-grown (etiolated) Arabidopsis seedlings, blue light was found to activate an anion channel residing at the plasma membrane. An anion-channel blocker commonly known as NPPB 15-nitro-2-(3-phenylpropylamino)-benzoic acid] potently and reversibly blocked this anion channel. NPPB also blocked the blue-light-induced depolarization in vivo and decreased the inhibitory effect of blue light on hypocotyl elongation. These results indicate that activation of this anion channel plays a role in transducing blue light into growth inhibition. PMID:8755616

  15. Anion-cation induction coupling in organic superconductors

    NASA Astrophysics Data System (ADS)

    Castet, F.; Ducasse, L.; Fritsch, A.

    2000-06-01

    Within the framework of the valence bond/Hartree-Fock (VB/HF) formalism, [Castet et al., J. Phys. I (France) 6, 583 (1996); L. Ducasse et al., Synth. Metals 85, 1627 (1997); F. Castet et al., Chem. Phys. 232, 37 (1998); Synth. Metals 103, 1799 (1999)] anion-cation induction interactions are evaluated in organic superconductors derived from the Bechgaard salts. The calculation scheme is based on an extension of the VB/HF model, so as to incorporate the effect of the distinct anion polarization states in the calculation of the VB Hamiltonian matrix elements. The induction mechanism involves a charge displacement on the counteranions in the electrostatic field of adjacent positively charged organic molecules. Anion-cation interactions are calculated for the β-BEDTTTF2I3 structure [A. J. Schultz et al., J. Am. Chem Soc. 108, 7853 (1986)], which involves highly polarizable anions.

  16. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    NASA Astrophysics Data System (ADS)

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W.; Kiran, Boggavarapu; Bowen, Kit H.

    2016-10-01

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H- and CAl5-7H2- found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  17. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions.

    PubMed

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W; Kiran, Boggavarapu; Bowen, Kit H

    2016-10-21

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H(-) and CAl5-7H2(-) found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  18. Characterization of a Saturated and Flexible Aliphatic Polyol Anion Receptor

    SciTech Connect

    Shokri, Alireza; Schmidt, Jacob C.; Wang, Xue B.; Kass, Steven R.

    2012-10-17

    Nature employs flexible molecules to bind anions in a variety of physiologically important processes whereas supramolecular chemists have been designing rigid substrates that minimize or eliminate intramolecular hydrogen bond interactions to carry out anion recogni-tion. Herein, the association of a flexible polyhydroxy alkane with chloride ion is described and the bound re-ceptor is characterized by infrared and photoelectron spectroscopy in the gas phase, computations, and its bind-ing constant as a function of temperature in acetonitrile.

  19. Gas-Grain Models for Interstellar Anion Chemistry

    NASA Technical Reports Server (NTRS)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  20. Boron compounds as anion binding agents for nonaqueous battery electrolytes

    DOEpatents

    Lee, Hung Sui; Yang, Xia-Oing; McBreen, James; Xiang, Caili

    2000-02-08

    Novel fluorinated boron-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boron-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boron-based anion receptors include borane and borate compounds bearing different fluorinated alkyl and aryl groups.

  1. GAS-GRAIN MODELS FOR INTERSTELLAR ANION CHEMISTRY

    SciTech Connect

    Cordiner, M. A.; Charnley, S. B.

    2012-04-20

    Long-chain hydrocarbon anions C{sub n}H{sup -} (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n{sub H{sub 2}}{approx}>10{sup 5} cm{sup -3}). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C{sub 6}H{sup -} anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C{sub 6}O, C{sub 7}O, HC{sub 6}O, and HC{sub 7}O, the abundances of which depend on the assumed branching ratios for associative electron detachment.

  2. ABORT GAP CLEANING IN RHIC.

    SciTech Connect

    DREES,A.; AHRENS,L.; III FLILLER,R.; GASSNER,D.; MCINTYRE,G.T.; MICHNOFF,R.; TRBOJEVIC,D.

    2002-06-03

    During the RHIC Au-run in 2001 the 200 MHz storage cavity system was used for the first time. The rebucketing procedure caused significant beam debunching in addition to amplifying debunching due to other mechanisms. At the end of a four hour store, debunched beam could account for approximately 30%-40% of the total beam intensity. Some of it will be in the abort gap. In order to minimize the risk of magnet quenching due to uncontrolled beam losses at the time of a beam dump, a combination of a fast transverse kicker and copper collimators were used to clean the abort gap. This report gives an overview of the gap cleaning procedure and the achieved performance.

  3. Virtual gap dielectric wall accelerator

    DOEpatents

    Caporaso, George James; Chen, Yu-Jiuan; Nelson, Scott; Sullivan, Jim; Hawkins, Steven A

    2013-11-05

    A virtual, moving accelerating gap is formed along an insulating tube in a dielectric wall accelerator (DWA) by locally controlling the conductivity of the tube. Localized voltage concentration is thus achieved by sequential activation of a variable resistive tube or stalk down the axis of an inductive voltage adder, producing a "virtual" traveling wave along the tube. The tube conductivity can be controlled at a desired location, which can be moved at a desired rate, by light illumination, or by photoconductive switches, or by other means. As a result, an impressed voltage along the tube appears predominantly over a local region, the virtual gap. By making the length of the tube large in comparison to the virtual gap length, the effective gain of the accelerator can be made very large.

  4. Hemibonding of hydroxyl radical and halide anion in aqueous solution.

    PubMed

    Yamaguchi, Makoto

    2011-12-29

    Molecular geometries and properties of the possible reaction products between the hydroxyl radical and the halide anions in aqueous solution were investigated. The formation of two-center three-electron bonding (hemibonding) between the hydroxyl radical and halide anions (Cl, Br, I) was examined by density functional theory (DFT) calculation with a range-separated hybrid (RSH) exchange-correlation functional. The long-range corrected hybrid functional (LC-ωPBE), which have given quantitatively satisfactory results for odd electron systems and excited states, was examined by test calculations for dihalogen radical anions (X(2)(-); X = Cl, Br, I) and hydroxyl radical-water clusters. Equilibrium geometries with hemibonding between the hydroxyl radical and halide anions were located by including four hydrogen-bonded water molecules. Excitation energies and oscillator strengths of σ-σ* transitions calculated by the time-dependent DFT method showed good agreement with observed values. Calculated values of the free energy of reaction on the formation of hydroxyl halide radical anion from the hydroxyl radical and halide anion were endothermic for chloride but exothermic for bromide and iodide, which is consistent with experimental values of equilibrium constants.

  5. Grain boundary mobility in anion doped MgO

    NASA Technical Reports Server (NTRS)

    Kapadia, C. M.; Leipold, M. H.

    1973-01-01

    Certain anions OH(-), F(-) and Gl(-) are shown to enhance grain growth in MgO. The magnitude of their effect decreases in the order in which the anions are listed and depends on their location (solid-solution, second phase) in the MgO lattice. As most anions exhibit relatively high vapor pressures at sintering temperatures, they retard densification and invariably promote residual porosity. The role of anions on grain growth rates was studied in relation to their effect on pore mobility and pore removal; the atomic process controlling the actual rates was determined from observed kinetics in conjunction with the microstructural features. With respect to controlling mechanisms, the effects of all anions are not the same. OH(-) and F(-) control behavior through creation of a defect structure and a grain boundary liquid phase while Cl(-) promotes matter transport within pores by evaporation-condensation. Studies on an additional anion, S to the minus 2nd power gave results which were no different from undoped MgO, possibly because of evaporative losses during hot pressing. Hence, the effect of sulphur is negligible or undetermined.

  6. Counterion-mediated pattern formation in membranes containing anionic lipids

    PubMed Central

    Slochower, David R.; Wang, Yu-Hsiu; Tourdot, Richard W.; Radhakrishnan, Ravi; Janmey, Paul A.

    2014-01-01

    Most lipid components of cell membranes are either neutral, like cholesterol, or zwitterionic, like phosphatidylcholine and sphingomyelin. Very few lipids, such as sphingosine, are cationic at physiological pH. These generally interact only transiently with the lipid bilayer, and their synthetic analogs are often designed to destabilize the membrane for drug or DNA delivery. However, anionic lipids are common in both eukaryotic and prokaryotic cell membranes. The net charge per anionic phospholipid ranges from −1 for the most abundant anionic lipids such has phosphatidylserine, to near −7 for phosphatidylinositol 3,4,5 trisphosphate, although the effective charge depends on many environmental factors. Anionic phospholipids and other negatively charged lipids such as lipopolysaccharides are not randomly distributed in the lipid bilayer, but are highly restricted to specific leaflets of the bilayer and to regions near transmembrane proteins or other organized structures within the plane of the membrane. This review highlights some recent evidence that counterions, in the form of monovalent or divalent metal ions, polyamines, or cationic protein domains, have a large influence of the lateral distribution of anionic lipids within the membrane, and that lateral demixing of anionic lipids has effects on membrane curvature and protein function that are important for biological control. PMID:24556233

  7. Want to Close the Achievement Gap? Close the Teaching Gap

    ERIC Educational Resources Information Center

    Darling-Hammond, Linda

    2015-01-01

    For years now, educators have looked to international tests as a yardstick to measure how well students from the United States are learning compared with their peers. The answer has been: not so well. The United States has been falling further behind other nations and has struggled with a large achievement gap. Federal policy under No Child Left…

  8. Folk Belief Theory, the Rigor Gap, and the Achievement Gap

    ERIC Educational Resources Information Center

    Torff, Bruce

    2014-01-01

    Folk belief theory is suggested as a primary cause for the persistence of the achievement gap. In this research-supported theory, culturally specified folk beliefs about learning and teaching prompt educators to direct more rigorous curriculum to high-advantage students but not to low-advantage students, resulting in impoverished pedagogy in…

  9. Stacked insulator induction accelerator gaps

    SciTech Connect

    Houck, T.I.; Westenskow, G.A.; Kim, J.S.; Eylon, S.; Henestroza, E.; Yu, S.S.; Vanecek, D.

    1997-05-01

    Stacked insulators, with alternating layers of insulating material and conducting film, have been shown to support high surface electrical field stresses. We have investigated the application of the stacked insulator technology to the design of induction accelerator modules for the Relativistic-Klystron Two-Beam Accelerator program. The rf properties of the accelerating gaps using stacked insulators, particularly the impedance at frequencies above the beam pipe cutoff frequency, are investigated. Low impedance is critical for Relativistic-Klystron Two-Beam Accelerator applications where a high current, bunched beam is trsnsported through many accelerating gaps. An induction accelerator module designs using a stacked insulator is presented.

  10. SIMULATING METABOLISM OF XENOBIOTIC CHEMICALS AS A PREDICTOR OF TOXICITY

    EPA Science Inventory

    EPA is faced with long lists of chemicals that need to be assessed for hazard. A major gap in evaluating chemical risk is accounting for metabolic activation resulting in increased toxicity. The goals of this project are to develop a capability to forecast the metabolism of xenob...

  11. Origins of electronic band gap reduction in Cr/N codoped TiO2.

    PubMed

    Parks Cheney, C; Vilmercati, P; Martin, E W; Chiodi, M; Gavioli, L; Regmi, M; Eres, G; Callcott, T A; Weitering, H H; Mannella, N

    2014-01-24

    Recent studies indicated that noncompensated cation-anion codoping of wide-band-gap oxide semiconductors such as anatase TiO2 significantly reduces the optical band gap and thus strongly enhances the absorption of visible light [W. Zhu et al., Phys. Rev. Lett. 103, 226401 (2009)]. We used soft x-ray spectroscopy to fully determine the location and nature of the impurity levels responsible for the extraordinarily large (∼1 eV) band gap reduction of noncompensated codoped rutile TiO2. It is shown that Cr/N codoping strongly enhances the substitutional N content, compared to single element doping. The band gap reduction is due to the formation of Cr 3d3 levels in the lower half of the gap while the conduction band minimum is comprised of localized Cr 3d and delocalized N 2p states. Band gap reduction and carrier delocalization are critical elements for efficient light-to-current conversion in oxide semiconductors. These findings thus raise the prospect of using codoped oxide semiconductors with specifically engineered electronic properties in a variety of photovoltaic and photocatalytic applications.

  12. Equine digital veins are more sensitive to superoxide anions than digital arteries.

    PubMed

    Lapo, Rock Allister; Gogny, Marc; Chatagnon, Gérard; Lalanne, Valérie; Harfoush, Khaled; Assane, Moussa; Desfontis, Jean-Claude; Mallem, Mohamed Yassine

    2014-10-05

    This work was designed to investigate (i) the effect of superoxide dismutase (SOD) inhibition on endothelial function and (ii) the free radical-induced endothelial dysfunction in equine digital veins (EDVs) and equine digital arteries (EDAs) isolated from healthy horses. EDV and EDA rings were suspended in a 5 ml organ bath containing Krebs solution. After a 60 min equilibration period, EDV and EDA rings were contracted with phenylephrine. Then, cumulative concentration-response curves (CCRCs) to acetylcholine were performed. In both EDVs and EDAs, acetylcholine (1 nM to 10 µM) produced concentration-dependent relaxation. We investigated the influence of SOD inhibition by diethyldithiocarbamate (DETC; 100 µM), a CuZnSOD inhibitor, on EDAs and EDVs relaxant responses to acetylcholine. Acetylcholine -mediated relaxation was impaired by DETC only in EDVs. SOD activity assayed by a xanthine-xanthine oxidase method was higher in EDAs compared with EDVs (P<0.05). CCRCs to acetylcholine established in the presence of pyrogallol (30 µM) or homocysteine (20 µM), two superoxide anions generating systems showed that in both EDVs and EDAs, the acetylcholine-mediated relaxation was significantly impaired by pyrogallol and homocysteine. This impairment was more pronounced in EDVs than in EDAs. Moreover, the pyrogallol-induced impairment of acetylcholine-mediated relaxation was potentiated by DETC to a greater extent in EDVs. We concluded that due to the lower activity of SOD, EDVs are more sensitive to superoxide anions than EDAs. So, any alteration of superoxide anions metabolism is likely to have a more important impact on venous rather than arterial relaxation.

  13. Study of electron transition energies between anions and cations in spinel ferrites using differential UV-vis absorption spectra

    NASA Astrophysics Data System (ADS)

    Xue, L. C.; Wu, L. Q.; Li, S. Q.; Li, Z. Z.; Tang, G. D.; Qi, W. H.; Ge, X. S.; Ding, L. L.

    2016-07-01

    It is very important to determine electron transition energies (Etr) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV-vis absorption spectra using the curve (αhν)2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV-vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (Etr) between the anions and cations, Fe2+ and Fe3+ at the (A) and [B] sites and Ni2+ at the [B] sites for the (A)[B]2O4 spinel ferrite samples CoxNi0.7-xFe2.3O4 (0.0≤x≤0.3), CrxNi0.7Fe2.3-xO4 (0.0≤x≤0.3) and Fe3O4. We suggest that the differential UV-vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

  14. Multiple input electrode gap controller

    DOEpatents

    Hysinger, C.L.; Beaman, J.J.; Melgaard, D.K.; Williamson, R.L.

    1999-07-27

    A method and apparatus for controlling vacuum arc remelting (VAR) furnaces by estimation of electrode gap based on a plurality of secondary estimates derived from furnace outputs. The estimation is preferably performed by Kalman filter. Adaptive gain techniques may be employed, as well as detection of process anomalies such as glows. 17 figs.

  15. Featured Image: Simulating Planetary Gaps

    NASA Astrophysics Data System (ADS)

    Kohler, Susanna

    2017-03-01

    The authors model of howthe above disk would look as we observe it in a scattered-light image. The morphology of the gap can be used to estimate the mass of the planet that caused it. [Dong Fung 2017]The above image from a computer simulation reveals the dust structure of a protoplanetary disk (with the star obscured in the center) as a newly formed planet orbits within it. A recent study by Ruobing Dong (Steward Observatory, University of Arizona) and Jeffrey Fung (University of California, Berkeley) examines how we can determine mass of such a planet based on our observations of the gap that the planet opens in the disk as it orbits. The authors models help us to better understand how our observations of gaps might change if the disk is inclined relative to our line of sight, and how we can still constrain the mass of the gap-opening planet and the viscosity of the disk from the scattered-light images we have recently begun to obtain of distant protoplanetary disks. For more information, check out the paper below!CitationRuobing Dong () and Jeffrey Fung () 2017 ApJ 835 146. doi:10.3847/1538-4357/835/2/146

  16. Multiple input electrode gap controller

    DOEpatents

    Hysinger, Christopher L.; Beaman, Joseph J.; Melgaard, David K.; Williamson, Rodney L.

    1999-01-01

    A method and apparatus for controlling vacuum arc remelting (VAR) furnaces by estimation of electrode gap based on a plurality of secondary estimates derived from furnace outputs. The estimation is preferably performed by Kalman filter. Adaptive gain techniques may be employed, as well as detection of process anomalies such as glows.

  17. Large gap magnetic suspension system

    NASA Technical Reports Server (NTRS)

    Abdelsalam, Moustafa K.; Eyssa, Y. M.

    1991-01-01

    The design of a large gap magnetic suspension system is discussed. Some of the topics covered include: the system configuration, permanent magnet material, levitation magnet system, superconducting magnets, resistive magnets, superconducting levitation coils, resistive levitation coils, levitation magnet system, and the nitrogen cooled magnet system.

  18. The Widening Income Achievement Gap

    ERIC Educational Resources Information Center

    Reardon, Sean F.

    2013-01-01

    Has the academic achievement gap between high-income and low-income students changed over the last few decades? If so, why? And what can schools do about it? Researcher Sean F. Reardon conducted a comprehensive analysis of research to answer these questions and came up with some striking findings. In this article, he shows that income-related…

  19. Literary Gaps Invite Creative Interaction.

    ERIC Educational Resources Information Center

    Watson, Jerry J.

    Literary gaps were identified by Wolfgang Iser in 1974 as "vacant pages" that invite the reader to reflect and enter into the text thereby motivating students to experience the text as reality. Arthur Applebee, in 1979, identified three categories to distinguish children's types of interaction with stories: (1) the complexity of literary…

  20. Electrolyte and Metabolic Disturbances in Ebola Patients during a Clinical Trial, Guinea, 2015

    PubMed Central

    Bah, Elhadj Ibrahima; Haba, Nyankoye; Delamou, Alexandre; Camara, Bienvenu Salim; Olivier, Kadio Jean-Jacques; De Clerck, Hilde; Nordenstedt, Helena; Semple, Malcolm G.; Van Herp, Michel; Buyze, Jozefien; De Crop, Maaike; Van Den Broucke, Steven; Lynen, Lutgarde; De Weggheleire, Anja

    2016-01-01

    By using data from a 2015 clinical trial on Ebola convalescent-phase plasma in Guinea, we assessed the prevalence of electrolyte and metabolic abnormalities at admission and their predictive value to stratify patients into risk groups. Patients underwent testing with a point-of-care device. We used logistic regression to construct a prognostic model and summarized the predictive value with the area under the receiver operating curve. Abnormalities were common among patients, particularly hypokalemia, hypocalcemia, hyponatremia, raised creatinine, high anion gap, and anemia. Besides age and PCR cycle threshold value, renal dysfunction, low calcium levels, and low hemoglobin levels were independently associated with increased risk for death. A prognostic model using all 5 factors was highly discriminatory (area under the receiver operating curve 0.95; 95% CI 0.90–0.99) and enabled the definition of risk criteria to guide targeted care. Most patients had a very low (<5%) or very high (>80%) risk for death. PMID:27869610

  1. Metabolic Electron Attachment as a Primary Mechanism For Toxicity Potentials of Halocarbons.

    PubMed

    Balasubramanian, Krishnan; Basak, Subhash C

    2016-01-01

    We have carried out systematic large-basis set quantum chemical computations at Møller- Plesset second-order perturbation (MP2) and couple cluster singles + doubles CCSD and CCSD(T)with triples correction levels of theories on a set of 55 halogenated carbons in the Crebelli toxicological dataset. We have computed a number of electronic properties at optimized geometries such as vertical electron affinities, HOMO-LUMO gaps, dipole moments, etc. We have provided insights into the mechanism of toxicity through electron attachment in metabolic pathways by binding to an electron donating enzyme in hepatocytes. The electron transfer from the enzyme to the halocarbon is accompanied by bond elongation resulting in autodetachment as evidenced from potential energy surfaces of the anion and neutral molecule. The autodetachment process leads to production of highly reactive free radicals, which cause tissue damage, and prolonged exposure can result in hepatocellular carcinoma depending on the hydrogen extraction propensity of the free radical and vertical electron affinity of the neutral halocarbon.

  2. Anion transport by the cochlear motor protein prestin.

    PubMed

    Schänzler, Michael; Fahlke, Christoph

    2012-01-15

    Prestin is a member of the SLC26 solute carrier family and functions as a motor protein in cochlear outer hair cells. While other SLC26 homologues were demonstrated to transport a wide variety of anions, no electrogenic transport activity has been assigned so far to mammalian prestin. We here use heterologous expression in mammalian cells, patch clamp recordings and measurements of expression levels of individual cells to study anion transport by rat prestin. We demonstrated that cells expressing rat prestin exhibit SCN(-) currents that are proportional to the number of prestin molecules. Variation of the SCN(-) concentration resulted in changes of the current reversal potential that obey the Nernst equation indicating that SCN(-) transport is not stoichiometrically coupled to other anions. Application of external SCN(-) causes large increases of anion currents, but only minor changes in non-linear charge movements suggesting that only a very small percentage of prestin molecules function as SCN(-) transporters under these conditions. Unitary current amplitudes are below the resolution limit of noise analysis and thus much smaller than expected for pore-mediated anion transport. A comparison with a non-mammalian prestin from D. rerio - recently shown to function as Cl(-)/SO(4)(2-) antiporter - and an SLC26 anion channel, human SLC26A7, revealed that SCN(-) transport is conserved in these distinct members of the SLC26 family. We conclude that mammalian prestin is capable of mediating electrogenic anion transport and suggest that SLC26 proteins converting membrane voltage oscillations into conformational changes and those functioning as channels or transporters share certain transport capabilities.

  3. Discovery of Interstellar Anions in Cepheus and Auriga

    NASA Technical Reports Server (NTRS)

    Cordiner, M. A.; Charnely, S. B.; Buckle, J. V.; Walsh, C.

    2011-01-01

    We report the detection of microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H in the star-forming region LI251 A (in Cepheus), and the pre-stellar core LI512 (in Auriga). The carbon chain-bearing species C4H, HC3N, HC5N, HC7N, and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for LI5l2. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

  4. The role of catalyst precursor anions in coal gasification

    SciTech Connect

    Abotsi, G.M.K.

    1992-08-28

    The aims of the proposed project are to enrich our understanding of the roles of various aqueous soluble catalyst precursor anions on the surface electrical properties of coal and to ascertain the influence of the surface charge on the adsorption, dispersion, and activities of calcium and potassium. These goals will be achieved by impregnating a North Dakota lignite (PSOC 1482) and its demineralized derivative with calcium or potassium catalyst precursors containing acetate (CH{sub 3}COO{sup {minus}}), chloride (Cl{sup {minus}}), nitrate (NO{sub 3}{sup {minus}}), sulfate (SO{sub 4}{sup 2{minus}}), and carbonate (CO{sub 3}{sup 2{minus}}) anions. Catalyst loading will be conducted under well-controlled conditions of solution pH and ionic strength. In the last quarter, the surface charge properties of the coal was determined as a function of acetate (CH{sub 3}COO{sup {minus}}), chloride (Cl{sup {minus}}), nitrate (NO{sup 3}{sup {minus}}), carbonate (CO{sub 3}{sup 2{minus}}) or sulfate (SO{sub 4}{sup 2{minus}})concentration using the respective potassium salts of these anions. In general, low anion concentrations (10{sup {minus}3} or 10{sup {minus}2} mol/L) had little effect on the zeta potentials of the coals. However, the surface charge densities of the coal become less negative at 10-1 mol/L of the nitrate, carbonate or sulfate anions. These trends suggest that the surface charge density of the coal is controlled by the adsorption of potassium ions (K{sup +}) onto the coal particles. The net negative charge on the coal panicles creates a repulsive force between the anions and the coal surface and prevents the anions from exerting any significant effect on the coal's electrokinetic properties.

  5. DISCOVERY OF INTERSTELLAR ANIONS IN CEPHEUS AND AURIGA

    SciTech Connect

    Cordiner, M. A.; Charnley, S. B.; Buckle, J. V.; Walsh, C.; Millar, T. J.

    2011-04-01

    We report the detection of microwave emission lines from the hydrocarbon anion C{sub 6}H{sup -} and its parent neutral C{sub 6}H in the star-forming region L1251A (in Cepheus), and the pre-stellar core L1512 (in Auriga). The carbon-chain-bearing species C{sub 4}H, HC{sub 3}N, HC{sub 5}N, HC{sub 7}N, and C{sub 3}S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC{sub 3}N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for L1512. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

  6. The Gamma Gap and All-Cause Mortality

    PubMed Central

    Juraschek, Stephen P.; Moliterno, Alison R.; Checkley, William; Miller, Edgar R.

    2015-01-01

    Background The difference between total serum protein and albumin, i.e. the gamma gap, is a frequently used clinical screening measure for both latent infection and malignancy. However, there are no studies defining a positive gamma gap. Further, whether it is an independent risk factor of mortality is unknown. Methods and Findings This study examined the association between gamma gap, all-cause mortality, and specific causes of death (cardiovascular, cancer, pulmonary, or other) in 12,260 participants of the National Health and Nutrition Examination Survey (NHANES) from 1999–2004. Participants had a comprehensive metabolic panel measured, which was linked with vital status data from the National Death Index. Cause of death was based on ICD10 codes from death certificates. Analyses were performed with Cox proportional hazards models adjusted for mortality risk factors. The mean (SE) age was 46 (0.3) years and the mean gamma gap was 3.0 (0.01) g/dl. The population was 52% women and 10% black. During a median follow-up period of 4.8 years (IQR: 3.3 to 6.2 years), there were 723 deaths. The unadjusted 5-year cumulative incidences across quartiles of the gamma gap (1.7–2.7, 2.8–3.0, 3.1–3.2, and 3.3–7.9 g/dl) were 5.7%, 4.2%, 5.5%, and 7.8%. After adjustment for risk factors, participants with a gamma gap of ≥3.1 g/dl had a 30% higher risk of death compared to participants with a gamma gap <3.1 g/dl (HR: 1.30; 95%CI: 1.08, 1.55; P = 0.006). Gamma gap (per 1.0 g/dl) was most strongly associated with death from pulmonary causes (HR 2.22; 95%CI: 1.19, 4.17; P = 0.01). Conclusions The gamma gap is an independent risk factor for all-cause mortality at values as low as 3.1 g/dl (in contrast to the traditional definition of 4.0 g/dl), and is strongly associated with death from pulmonary causes. Future studies should examine the biologic pathways underlying these associations. PMID:26629820

  7. Gaps"

    ERIC Educational Resources Information Center

    What Works Clearinghouse, 2013

    2013-01-01

    This study investigated the effect of daily quizzes on the performance of college students. Students in an introductory psychology course used their own wireless-enabled devices to take short Internet-based quizzes at the beginning of every class. The quiz items were drawn approximately equally from material covered in the readings and the…

  8. Genome scale metabolic reconstruction of Chlorella variabilis for exploring its metabolic potential for biofuels.

    PubMed

    Juneja, Ankita; Chaplen, Frank W R; Murthy, Ganti S

    2016-08-01

    A compartmentalized genome scale metabolic network was reconstructed for Chlorella variabilis to offer insight into various metabolic potentials from this alga. The model, iAJ526, was reconstructed with 1455 reactions, 1236 metabolites and 526 genes. 21% of the reactions were transport reactions and about 81% of the total reactions were associated with enzymes. Along with gap filling reactions, 2 major sub-pathways were added to the model, chitosan synthesis and rhamnose metabolism. The reconstructed model had reaction participation of 4.3 metabolites per reaction and average lethality fraction of 0.21. The model was effective in capturing the growth of C. variabilis under three light conditions (white, red and red+blue light) with fair agreement. This reconstructed metabolic network will serve an important role in systems biology for further exploration of metabolism for specific target metabolites and enable improved characteristics in the strain through metabolic engineering.

  9. Crystal structure, conformation, vibration and optical band gap analysis of bis[ rac-propranolol nitrate

    NASA Astrophysics Data System (ADS)

    Franklin, S.; Balasubramanian, T.; Nehru, K.; Kim, Youngmee

    2009-06-01

    The crystal structure of the title rac-propranolol salt, CHNO2+·NO3-, consists of two protonated propranolol residues and nitrate anions. Three virtually flat fragments, characteristics of most of the β-adrenolytics with oxy-methylene bridge are present in both the cations (A and B). The plane of the propranolol chain is twisted with respect to the plane of the aromatic ring in both the cations. Present study investigates the conformation and hydrogen bonding interactions, which play an important role in biological functions. A gauche conformation is observed for the oxo-methylene bridge of cation A, while a trans conformation prevails in cation B. These conformations are found in majority of β-blockers. Presence of twenty intermolecular hydrogen bonds mediating through the anions stabilizes the crystal packing. Vibration analysis and earlier theoretical predictions complement the structure analysed. From the UV-Vis spectral analysis for the crystal, the optical band gap is found to be Eg = 5.12 eV, where as the chloride salt has Eg = 3.81 eV. The increase in the band gap may be attributed by the increase in the number of intermolecular hydrogen bonds. Good optical transmittance in the entire visible region and the direct band gap property suggest that it is a suitable candidate for optical applications in UV region.

  10. Metabolic Analysis

    NASA Astrophysics Data System (ADS)

    Tolstikov, Vladimir V.

    Analysis of the metabolome with coverage of all of the possibly detectable components in the sample, rather than analysis of each individual metabolite at a given time, can be accomplished by metabolic analysis. Targeted and/or nontargeted approaches are applied as needed for particular experiments. Monitoring hundreds or more metabolites at a given time requires high-throughput and high-end techniques that enable screening for relative changes in, rather than absolute concentrations of, compounds within a wide dynamic range. Most of the analytical techniques useful for these purposes use GC or HPLC/UPLC separation modules coupled to a fast and accurate mass spectrometer. GC separations require chemical modification (derivatization) before analysis, and work efficiently for the small molecules. HPLC separations are better suited for the analysis of labile and nonvolatile polar and nonpolar compounds in their native form. Direct infusion and NMR-based techniques are mostly used for fingerprinting and snap phenotyping, where applicable. Discovery and validation of metabolic biomarkers are exciting and promising opportunities offered by metabolic analysis applied to biological and biomedical experiments. We have demonstrated that GC-TOF-MS, HPLC/UPLC-RP-MS and HILIC-LC-MS techniques used for metabolic analysis offer sufficient metabolome mapping providing researchers with confident data for subsequent multivariate analysis and data mining.

  11. Metabolic Disorders

    MedlinePlus

    ... affect the breakdown of amino acids, carbohydrates, or lipids. Another group, mitochondrial diseases, affects the parts of the cells that produce the energy. You can develop a metabolic disorder when some organs, such as your liver or pancreas, become diseased or do not function ...

  12. Metabolic Syndrome

    MedlinePlus

    Metabolic syndrome is a group of conditions that put you at risk for heart disease and diabetes. These conditions are High blood pressure High blood glucose, or blood sugar, levels High levels of triglycerides, a type of fat, in your blood Low levels ...

  13. The Significance of Strong Ion Gap for Predicting Return of Spontaneous Circulation in Patients with Cardiopulmonary Arrest

    PubMed Central

    Kaneko, Minoru; Hagiwara, Shuichi; Aoki, Makoto; Murata, Masato; Nakajima, Jun; Oshima, Kiyohiro

    2017-01-01

    Abstract Useful parameters that can predict return of spontaneous circulation (ROSC) in patients with cardiopulmonary arrest (CPA) have not been established. We previously reported the usefulness of anion gap (AG) and albumin-corrected anion gap (ACAG) calculated from a blood sample obtained on arrival at the hospital for the prediction of ROSC. Otherwise, it has been reported that strong ion gap (SIG), which shows the difference between the levels of fully dissociated cations and anions in the serum, is useful to predict the prognosis of critically ill patients. This was a prospective and observational clinical study. Patients with CPA transferred to the emergency department of our hospital between January 2013 and December 2014 were evaluated. Patients were divided into two groups: patients who obtained ROSC [ROSC(+) group] and those who did not [ROSC(−) group]. We compared AG, ACAG and SIG between the two groups. A total of 170 patients were enrolled. Fifty patients were included in the ROSC(+) group, and the remaining 120 in the ROSC(−) group. Both AG and ACAG were significantly better in the ROSC(+) group; however, there was no significant difference in SIG between the two groups. The area under the receiver operating characteristic curves (AUC) for ROSC of both AG and ACAG were almost the same (0.72 and 0.708, respectively); the AUC of SIG (0.57) was inferior to those of AG and ACAG. Our results suggest that AG and ACAG can better predict ROSC following cardiopulmonary resuscitation (CPR) compared with SIG.

  14. Emplacement Gantry Gap Analysis Study

    SciTech Connect

    R. Thornley

    2005-05-27

    To date, the project has established important to safety (ITS) performance requirements for structures, systems, and components (SSCs) based on the identification and categorization of event sequences that may result in a radiological release. These performance requirements are defined within the ''Nuclear Safety Design Bases for License Application'' (NSDB) (BSC 2005 [DIRS 171512], Table A-11). Further, SSCs credited with performing safety functions are classified as ITS. In turn, assurance that these SSCs will perform as required is sought through the use of consensus codes and standards. This gap analysis is based on the design completed for license application only. Accordingly, identification of ITS SSCs beyond those defined within the NSDB are based on designs that may be subject to further development during detail design. Furthermore, several design alternatives may still be under consideration to satisfy certain safety functions, and final selection will not be determined until further design development has occurred. Therefore, for completeness, alternative designs currently under consideration will be discussed throughout this study. This gap analysis will evaluate each code and standard identified within the ''Emplacement Gantry ITS Standards Identification Study'' (BSC 2005 [DIRS 173586]) to ensure each ITS performance requirement is fully satisfied. When a performance requirement is not fully satisfied, a gap is highlighted. This study will identify requirements to supplement or augment the code or standard to meet performance requirements. Further, this gap analysis will identify nonstandard areas of the design that will be subject to a design development plan. Nonstandard components and nonstandard design configurations are defined as areas of the design that do not follow standard industry practices or codes and standards. Whereby, assurance that an SSC will perform as required may not be readily sought though the use of consensus standards. This

  15. Air Gap Effects in LX-17

    SciTech Connect

    Souers, P C; Ault, S; Avara, R; Bahl, K L; Boat, R; Cunningham, B; Gidding, D; Janzen, J; Kuklo, D; Lee, R; Lauderbach, L; Weingart, W C; Wu, B; Winer, K

    2005-09-26

    Three experiments done over twenty years on gaps in LX-17 are reported. For the detonation front moving parallel to the gaps, jets of gas products were seen coming from the gaps at velocities greater than the detonation velocity. A case can be made that the jet velocity increased with gap thickness but the data is scattered. For the detonation front moving transverse to the gap, time delays were seen. The delays roughly increase with gap width, going from 0-70 ns at 'zero gap' to around 300 ns at 0.5-1 mm gap. Larger gaps of up to 6 mm width almost certainly stopped the detonation, but this was not proved. Real-time resolution of the parallel jets and determination of the actual re-detonation or failure in the transverse case needs to be done in future experiments.

  16. REACTIVITY OF ANIONS IN INTERSTELLAR MEDIA: DETECTABILITY AND APPLICATIONS

    SciTech Connect

    Senent, M. L.; Hochlaf, M. E-mail: hochlaf@univ-mlv.fr

    2013-05-01

    We propose a general rule to distinguish between detectable and undetectable astronomical anions. We believe that only few anions live long enough in the interstellar medium and thus can be detected. Our method is based on quantum mechanical calculations capable of describing accurately the evolution of electronic states during chemical processes. The still not fully understood reactivity at low temperatures is discussed considering non-adiabatic effects. The role of excited states has usually been neglected in previous works which basically focused on the ground electronic state for interpretations of experimental observations. Here, we deal with unsaturated carbon chains (e.g., C{sub n} H{sup -}), which show a high density of electronic states close to their corresponding ground electronic states, complex molecular dynamics, and non-adiabatic phenomena. Our general rule shows that it is not sufficient that anions exist in the gas phase (in the laboratory) to be present in media such as astrophysical media, since formation and decomposition reactions of these anions may allow the population of anionic electronic states to autodetach, forming neutrals. For C{sub n} H, reactivity depends strongly on n, where long and short chains behave differently. Formation of linear chains is relevant.

  17. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    PubMed

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W

    2015-11-19

    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  18. Vertical detachment energies of anionic thymidine: Microhydration effects

    NASA Astrophysics Data System (ADS)

    Kim, Sunghwan; Schaefer, Henry F.

    2010-10-01

    Density functional theory has been employed to investigate microhydration effects on the vertical detachment energy (VDE) of the thymidine anion by considering the various structures of its monohydrates. Structures were located using a random searching procedure. Among 14 distinct structures of the anionic thymidine monohydrate, the low-energy structures, in general, have the water molecule bound to the thymine base unit. The negative charge developed on the thymine moiety increases the strength of the intermolecular hydrogen bonding between the water and base units. The computed VDE values of the thymidine monohydrate anions are predicted to range from 0.67 to 1.60 eV and the lowest-energy structure has a VDE of 1.32 eV. The VDEs of the monohydrates of the thymidine anion, where the N1H hydrogen of thymine has been replaced by a 2'-deoxyribose ring, are greater by ˜0.30 eV, compared to those of the monohydrates of the thymine anion. The results of the present study are in excellent agreement with the accompanying experimental results of Bowen and co-workers [J. Chem. Phys. 133, 144304 (2010)].

  19. Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

    NASA Technical Reports Server (NTRS)

    West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

    2007-01-01

    We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

  20. Contamination of an anion-exchange membrane by glutathione.

    PubMed

    Gotoh, T; Kikuchi, K

    2000-01-01

    Electrodialysis, which can separate electrolytes under mild conditions by using ion-exchange membranes, is a strong candidate for separation of GSH from yeast extracts, because GSH is unstable and easily oxidized forming a disulfide bond especially under alkali conditions. In this paper, sorption behavior of GSH on an anion-exchange membrane, in the pH 3-6 region that is expected to be the most preferable for its electro-dialytic separation, was examined. Sorption of GSH on a Selemion-AMV anion-exchange membrane was accelerated as the pH of the membrane-contact solution increased, and there was a good correlation between the sorbed amounts and the molar fraction of monovalent anionic species of GSH. However, the amounts of GSH desorbed from the membrane by a NaCl desorbing solution were much lower than the initial sorbed amounts, and the difference between them was enlarged with increasing pH. The GSH which was lost could be recovered by the addition of DTT in the membrane-contact and desorbing solutions. Similar results were also obtained with Cys. We thus concluded that an anion-exchange membrane would be contaminated by thiol compounds, such as GSH and Cys, through oxidative binding of the thiol group with the membrane, the local OH- concentration in which was enhanced due to attraction by the positively charged anion-exchange membrane.

  1. Anion competition for a volume-regulated current.

    PubMed Central

    Levitan, I; Garber, S S

    1998-01-01

    We have examined whether the anionic amino acids, glutamate and aspartate, permeate through the same volume-regulated conductance permeant to Cl- ions. Cell swelling was initiated in response to establishing a whole-cell configuration in the presence of a hyposmotic gradient. Volume-regulated anion currents carried by Cl-, glutamate, or aspartate developed with similar time courses and showed similar voltage-dependent inactivation. Permeability ratios (Paa/PCl) calculated from measured reversal potentials were dependent on the mole fraction ratio (MFR) of the permeant anions ([aa]/([aa] + [Cl-])). MFR was varied from 0.00 to 0.97. As the fraction of amino acid increased, Paa/PCl decreased. Current amplitude was similarly dependent on MFR. These results show that the permeation of anionic amino acids and that of Cl- ions are not independent of each other, indicating that the ion channel underlying the volume-regulated conductance can be occupied by more than one ion at a time. Application of Eyring rate theory indicated that the major barrier to Cl- ion permeation is at the intracellular side of the membrane, and that the major barrier to amino acid permeation is at the extracellular side of the membrane. The interactions between these permeant ions may have a physiological modulatory role in volume regulation through a volume-regulated anion conductance. PMID:9649382

  2. Observational Properties of Protoplanetary Disk Gaps

    NASA Astrophysics Data System (ADS)

    Varnière, Peggy; Bjorkman, J. E.; Frank, Adam; Quillen, Alice C.; Carciofi, A. C.; Whitney, Barbara A.; Wood, Kenneth

    2006-02-01

    We study the effects of an annular gap induced by an embedded protoplanet on disk scattered light images and the infrared spectral energy distribution (SED). We find that the outer edge of a gap is brighter in the scattered light images than a similar location in a gap-free disk. The stellar radiation that would have been scattered by material within the gap is instead scattered by the disk wall at the outer edge of the gap, producing a bright ring surrounding the dark gap in the images. Given sufficient resolution, such gaps can be detected by the presence of this bright ring in scattered light images. A gap in a disk also changes the shape of the SED. Radiation that would have been absorbed by material in the gap is instead reprocessed by the outer gap wall. This leads to a decrease in the SED at wavelengths corresponding to the temperature at the radius of the missing gap material, and to a corresponding flux increase at longer wavelengths corresponding to the temperature of the outer wall. We note, however, that the presence of an annular gap does not change the bolometric IR flux; it simply redistributes the radiation previously produced by material within the gap to longer wavelengths. Although it will be difficult on the basis of the SED alone to distinguish between the presence of a gap and other physical effects, the level of changes can be sufficiently large to be measurable with current instruments (e.g., Spitzer).

  3. ACTION OF SYNTHETIC DETERGENTS ON THE METABOLISM OF BACTERIA.

    PubMed

    Baker, Z; Harrison, R W; Miller, B F

    1941-01-31

    A study of the effects of synthetic detergents and wetting agents on respiration and glycolysis of Gram-positive and Gram-negative microorganisms has led to the following conclusions. 1. All the cationic detergents studied are very effective inhibitors of bacterial metabolism at 1:3000 concentration, and several are equally active at 1:30,000. Few of the anionic detergents inhibit as effectively as the cationic compounds. 2. Gram-positive and Gram-negative microorganisms are equally sensitive to the action of the cationic detergents. On the other hand, all the anionic detergents included in our studies selectively inhibit the metabolism of Gram-positive microorganisms. 3. The inhibitory action of both types of detergents is influenced markedly by hydrogen ion concentration. Cationic detergents exhibit their maximum activity in the alkaline pH range, and the anionic, in the acid range. 4. Studies of homologous series of straight chain alkyl sulfates and sulfoacetates (C(8) to C(18)) demonstrate that maximum inhibition is exerted by the 12, 14, and 16 carbon compounds (lauryl, myristyl, and cetyl). 5. It has been observed that three lauryl esters of amino acids are powerful inhibitors of bacterial metabolism. To our knowledge, the effects on bacterial metabolism of such cationic detergents (without the quaternary ammonium structure) have not been studied previously. Our results demonstrate that other cationic detergents can exhibit an inhibitory activity comparable to quaternary ammonium compounds. 6. Certain detergents stimulate bacterial metabolism at concentrations lower than the inhibiting values. This effect has been found more frequently among the anionic detergents.

  4. Electronic gap sensor and method

    DOEpatents

    Williams, R.S.; King, E.L.; Campbell, S.L.

    1991-08-06

    Disclosed are an apparatus and method for regulating the gap between a casting nozzle and a casting wheel in which the gap between the casting nozzle and the casting wheel is monitored by means of at least one sensing element protruding from the face of the casting nozzle. The sensing element is preferably connected to a voltage source and the casting wheel grounded. When the sensing element contacts the casting wheel, an electric circuit is completed. The completion of the circuit can be registered by an indicator, and the presence or absence of a completed circuit indicates the relative position of the casting nozzle to the casting wheel. The relative positions of the casting nozzle and casting wheel can thereby be selectively adjusted to continually maintain a predetermined distance between their adjacent surfaces. 5 figures.

  5. Electronic gap sensor and method

    DOEpatents

    Williams, Robert S.; King, Edward L.; Campbell, Steven L.

    1991-01-01

    An apparatus and method for regulating the gap between a casting nozzle and a casting wheel in which the gap between the casting nozzle and the casting wheel is monitored by means of at least one sensing element protruding from the face of the casting nozzle. The sensing element is preferably connected to a voltage source and the casting wheel grounded. When the sensing element contacts the casting wheel, an electric circuit is completed. The completion of the circuit can be registered by an indicator, and the presence or absence of a completed circuit indicates the relative position of the casting nozzle to the casting wheel. The relative positions of the casting nozzle and casting wheel can thereby be selectively adjusted to continually maintain a predetermined distance between their adjacent surfaces.

  6. Military Pay Gaps and Caps.

    DTIC Science & Technology

    1994-01-01

    RATIOS AND ENLISTED RECRUIT QUALITY AND RETENTION 27 C. MILITARY-CrVIL SERVICE PAY ADJUSTMENT LINKAGE: LEGISLATIVE BACKGROUND, 1967-1993 30...DECI), which we constructed previously and have updated to include fiscal 1992. We compare pay gaps based on the ECI versus the DECI and present DECI...do. There is no claim that the levels of military and civilian pay are equal at base point. If pay levels are equal at the base point, the divergence

  7. The Fundamental Gap of Simplices

    NASA Astrophysics Data System (ADS)

    Lu, Zhiqin; Rowlett, Julie

    2013-04-01

    The gap function of a domain {Ω subset {R}^n} is ξ(Ω) := d^2 (λ_2 - λ_1) , where d is the diameter of Ω, and λ1 and λ2 are the first two positive Dirichlet eigenvalues of the Euclidean Laplacian on Ω. It was recently shown by Andrews and Clutterbuck (J Amer Math Soc 24:899-916, 2011) that for any convex {Ω subset {R}^n}, ξ(Ω) ≥ 3 π^2 , where the infimum occurs for n = 1. On the other hand, the gap function on the moduli space of n-simplices behaves differently. Our first theorem is a compactness result for the gap function on the moduli space of n-simplices. Next, specializing to n = 2, our second main result proves the recent conjecture of Antunes-Freitas (J Phys A: Math Theor 41(5):055201, 2008) for any triangle {T subset {R}^2}, ξ(T) ≥ 64 π^2/9 , with equality if and only if T is equilateral.

  8. Prometheus and the Keeler gap

    NASA Astrophysics Data System (ADS)

    Tajeddine, Radwan; Nicholson, Phillip D.; Hedman, Matthew M.; French, Richard G.; Tiscareno, Matthew S.; Burns, Joseph A.

    2014-11-01

    Linblad resonances with Saturn’s satellites are located at many radii in the rings. While some cause density or bending waves, others hold gap edges from spreading, like the 2:1 resonance with Mimas located at the B-ring edge, the 7:6 resonance with Janus at the A-ring edge, and the 32:31 resonance with Prometheus at the inner edge of the Keeler gap. The latter is the case of study here.Theoretically, the inner edge of the Keeler gap should have 32 regular sinusoidal lobes, where either the maximum or the minimum radius is expected to be aligned with Prometheus and rotating with its mean motion. We show that such is not the case. Fit of occultation data shows the presence of the 32:31 resonance, however, the fit residuals is as high as the amplitude of the resonance amplitude (about 2 km). Analysis of the ISS data, shows irregularities overlapping the lobes (Tiscareno et al. 2005, DPS), that follow Keplerian motion. These irregularities may be due to clumps of particles with different eccentricities than the rest of the edge particles. This phenomenon may be caused by the resonance, as it has not been observed at other circular edges were no resonance is present at their location. The ISS data also shows that the lobe’s minimum/maximum is not perfectly aligned with the longitude of Prometheus, which may be due to libration about the centre of the resonance.

  9. Effect of anions on the electrochemistry of zinc tetraphenylporphyrin

    SciTech Connect

    Seely, G.R.; Gust, D.; Moore, T.A.; Moore, A.L. )

    1994-10-13

    Accurate measurements of porphyrin redox potentials are essential for the prediction and rationalization of the rates of electron transfer reactions involving these biologically important electron-donating and accepting chromophores. The present work describes a survey of redox potentials of zinc tetraphenylporphyrin obtained by cyclic voltammetry in dichloromethane, with tetrabutylammonium salts containing a variety of anions as electrolytes. Of the anions tested, hexafluorophosphate appears to have the least ability to ligate the metal, so that potentials measured in its presence as electrolyte should most closely approach those of the unligated porphyrin. With perchlorate electrolyte, the potential for one-electron oxidation is approximately 80 mV lower, enough to affect the interpretation of photochemical electron transfer rates. In general, anions bind much more strongly to the cation radical than to zinc tetraphenylporphyrin itself. The use of reference redox systems based on thymoquinone and ferrocene carboxylate enabled comparison of potentials measured with different electrolytes. 30 refs., 2 tabs.

  10. Dissecting Anion Effects in Gold(I)-Catalyzed Intermolecular Cycloadditions

    PubMed Central

    Homs, Anna; Obradors, Carla; Lebœuf, David; Echavarren, Antonio M

    2014-01-01

    From a series of gold complexes of the type [t-BuXPhosAu(MeCN)]X (X=anion), the best results in intermolecular gold(I)-catalyzed reactions are obtained with the complex with the bulky and soft anion BAr4F− [BAr4F−=3,5-bis(trifluoromethyl)phenylborate] improving the original protocols by 10–30% yield. A kinetic study on the [2+2] cycloaddition reaction of alkynes with alkenes is consistent with an scenario in which the rate-determining step is the ligand exchange to generate the (η2-phenylacetylene)gold(I) complex. We have studied in detail the subtle differences that can be attributed to the anion in this formation, which result in a substantial decrease in the formation of unproductive σ,π-(alkyne)digold(I) complexes by destabilizing the conjugated acid formed. PMID:26190958

  11. Cell wall bound anionic peroxidases from asparagus byproducts.

    PubMed

    Jaramillo-Carmona, Sara; López, Sergio; Vazquez-Castilla, Sara; Jimenez-Araujo, Ana; Rodriguez-Arcos, Rocio; Guillen-Bejarano, Rafael

    2014-10-08

    Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

  12. Solubility and transport of cationic and anionic patterned nanoparticles

    NASA Astrophysics Data System (ADS)

    Su, Jiaye; Guo, Hongxia; Olvera de La Cruz, Monica

    2012-02-01

    Diffusion and transport of nanoparticles (NPs) though nanochannels is important for desalination, drug delivery, and biomedicine. Their surface composition dictate their efficiency separating them by reverse osmosis, delivering into into cells, as well as their toxicity. We analyze bulk diffusion and transport through nanochannels of NPs with different hydrophobic-hydrophilic patterns achieved by coating a fraction of the NP sites with positive or negative charges via explicit solvent molecular dynamics simulations. The cationic NPs are more affected by the patterns, less water soluble, and have higher diffusion constants and fluxes than their anionic NPs counterparts. The NP-water interaction dependence on surface pattern and field strength explains these observations. For equivalent patterns, anionic NPs solubilize more than cationic NPs since the Coulomb interaction of free anionic NPs, which are much stronger than hydrophobic NP-water interactions, are about twice that of cationic NPs.

  13. Hydrothermal carbonaceous sphere based stationary phase for anion exchange chromatography.

    PubMed

    Zhao, Qiming; Wu, Shuchao; Zhang, Peimin; Zhu, Yan

    2017-01-15

    Monodisperse carbonaceous spheres produced by the hydrothermal carbonization of sucrose were first applied as green stationary phase for ion chromatography after quaternization. Depending on the polycondensation of methylamine and 1,4-butanediol diglycidyl ether, polymer containing quaternary ammonium groups were facilely grafted onto the surfaces of hydrothermal carbonaceous spheres (HCSs). The quaternized HCSs with different number of polyelectrolyte layers were characterized by scanning electron microscopy, brunauer-emmett-teller, fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis and elemental analysis. The measurements of breakthrough curves demonstrated that more layers of grafted polyelectrolyte resulted in higher anion exchange capacity of stationary phase. With good stability, common inorganic anions, monocarboxylic acids, polarizable anions and carbohydrates were effectively separated on the stationary phases, respectively. The high hydrophilicity of HCS surface afforded excellent peak symmetry for all analytes. Furthermore, high-capacity HCSs stationary phase was successfully applied to detect fluoride in tea samples.

  14. Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions

    PubMed Central

    Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L.

    2016-01-01

    Ion transport–driven instabilities in electrodeposition of metals that lead to morphological instabilities and dendrites are receiving renewed attention because mitigation strategies are needed for improving rechargeability and safety of lithium batteries. The growth rate of these morphological instabilities can be slowed by immobilizing a fraction of anions within the electrolyte to reduce the electric field at the metal electrode. We analyze the role of elastic deformation of the solid electrolyte with immobilized anions and present theory combining the roles of separator elasticity and modified transport to evaluate the factors affecting the stability of planar deposition over a wide range of current densities. We find that stable electrodeposition can be easily achieved even at relatively high current densities in electrolytes/separators with moderate polymer-like mechanical moduli, provided a small fraction of anions are immobilized in the separator. PMID:27453943

  15. Organization and function of anionic phospholipids in bacteria.

    PubMed

    Lin, Ti-Yu; Weibel, Douglas B

    2016-05-01

    In addition to playing a central role as a permeability barrier for controlling the diffusion of molecules and ions in and out of bacterial cells, phospholipid (PL) membranes regulate the spatial and temporal position and function of membrane proteins that play an essential role in a variety of cellular functions. Based on the very large number of membrane-associated proteins encoded in genomes, an understanding of the role of PLs may be central to understanding bacterial cell biology. This area of microbiology has received considerable attention over the past two decades, and the local enrichment of anionic PLs has emerged as a candidate mechanism for biomolecular organization in bacterial cells. In this review, we summarize the current understanding of anionic PLs in bacteria, including their biosynthesis, subcellular localization, and physiological relevance, discuss evidence and mechanisms for enriching anionic PLs in membranes, and conclude with an assessment of future directions for this area of bacterial biochemistry, biophysics, and cell biology.

  16. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    NASA Astrophysics Data System (ADS)

    Ye, Jiesheng; Wang, Aihua; Liu, Chunxi; Chen, Zhijin; Zhang, Na

    2008-07-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (<=20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 ± 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 ± 1.14 mV to -17.16 ± 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 ± 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo.

  17. Infrared Predissociation Spectroscopy of H_2-TAGGED Dicarboxylic Acid Anions

    NASA Astrophysics Data System (ADS)

    Wolk, Arron B.; Kamrath, Michael Z.; Leavitt, Christopher M.; Johnson, Mark A.

    2011-06-01

    Singly charged dicarboxylic acid anions, studied in depth by Wang et al. offer insight into the role of ring strain and conformation on the formation of intramolecular hydrogen bonds. These shared proton bonds, common in proteins and polymer systems, can be crucial in secondary and tertiary structure formation. By tracking the infrared spectra of dicarboxylic acid anions as charge and aliphatic chain length are varied, the tendency of these anions to form ring-like structures with an internally shared proton can be asssesed. To adapt the time-of-flight mass spectrometry/infrared presdissociation experiment to larger systems with significant latent vibrational energy and negligible vapor pressure, an electrospray ionization (ESI)/cryogenic quadrupole trap ion source has been interfaced to the Yale time of flight mass spectrometer. Infrared predissociation spectroscopy is carried out on a series of carboxylate anions cooled to 10K and H_2-tagged in a cryogenic ion trap, underscoring the power of this technique to vibrationally quench and structurally characterize large (> 20 atoms) gaseous ions. This technique recovers sharp transitions (~6 cm^-^1 FWHM) in the linear single photon absorption regime which greatly facilitates comparison with ab initio calculations. The methodology used to condense H_2 on these ions is described, revealing the benefits of a pulsed trapping gas paired with a time delay before ion extraction. The sensitivity of the perturbed H_2 transition to charge center exposure is probed by varying the charge and aliphatic chain length of carboxylate anions. Finally, the structure of four carboxylate anions are characterized using their predissociation spectra. H. K. Woo, X. B. Wang, K. C. Lau and L. S. Wang J. Chem. Phys. A 110, 7801-7805 2006.

  18. Surfactant behavior of "ellipsoidal" dicarbollide anions: a molecular dynamics study.

    PubMed

    Chevrot, G; Schurhammer, R; Wipff, G

    2006-05-18

    We report a molecular dynamics study of cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)X(3))(2)Co](-) (XCD(-)) commonly used in liquid-liquid extraction (X = H, Me, Cl, or Br), showing that these anions, although lacking the amphiphilic topology, behave as anionic surfactants. In pure water, they display "hydrophobic attractions", leading to the formation of aggregates of different sizes and shapes depending on the counterions. When simulated at a water/"oil" interface, the different anions (HCD(-), MeCD(-), CCD(-), and BrCD(-)) are found to be surface active. As a result, the simulated M(n+) counterions (M(n+) = Na(+), K(+), Cs(+), H(3)O(+), UO(2)(2+), Eu(3+)) concentrate on the aqueous side of the interface, forming a "double layer" whose characteristics are modulated by the hydrophobic character of the anion and by M(n+). The highly hydrophilic Eu(3+) or UO(2)(2+) cations that are generally "repelled" by aqueous interfaces are attracted by dicarbollides near the interface, which is crucial as far as the mechanism of assisted cation extraction to the oil phase is concerned. These cations interact with interfacial XCD(-) in their fully hydrated Eu(H(2)O)(9)(3+) and UO(2)(H(2)O)(5)(2+) forms, whereas the less hydrophilic monocharged cations display intimate contacts via their X substituents. The results obtained with the TIP3P and OPLS models for the solvents are confirmed with other water models (TIP5P or a polarizable 4P-Pol water) and with more polar "oil" models. The importance of interfacial phenomena is further demonstrated by simulations with a high oil-water ratio, leading to the formation of a micelle covered with CCD's. We suggest that the interfacial activity of dicarbollides and related hydrophobic anions is an important feature of synergism in liquid-liquid extraction of hard cations (e.g., for nuclear waste partitioning).

  19. Electron localization of anions probed by nitrile vibrations

    DOE PAGES

    Mani, Tomoyasu; Grills, David C.; Newton, Marshall D.; ...

    2015-08-02

    Localization and delocalization of electrons is a key concept in chemistry, and is one of the important factors determining the efficiency of electron transport through organic conjugated molecules, which have potential to act as “molecular wires”. This, in turn, substantially influences the efficiencies of organic solar cells and other molecular electronic devices. It is also necessary to understand the electronic energy landscape and the dynamics of electrons through molecular chain that govern their transport capabilities in one-dimensional conjugated chains so that we can better define the design principles of conjugated molecules for their applications. We show that nitrile ν(C≡N) vibrationsmore » respond to the degree of electron localization in nitrile-substituted organic anions by utilizing time-resolved infrared (TRIR) detection combined with pulse radiolysis. Measurements of a series of aryl nitrile anions allow us to construct a semi-empirical calibration curve between the changes in the ν(C≡N) IR shifts and the changes in the electronic charges from the neutral to the anion states in the nitriles; more electron localization in the nitrile anion results in larger IR shifts. Furthermore, the IR linewidth in anions can report a structural change accompanying changes in the electronic density distribution. Probing the shift of the nitrile ν(C≡N) IR vibrational bands enables us to determine how the electron is localized in anions of nitrile-functionalized oligofluorenes, considered as organic mixed-valence compounds. We estimate the diabatic electron transfer distance, electronic coupling strengths, and energy barriers in these organic mixed-valence compounds. The analysis reveals a dynamic picture, showing that the electron is moving back and forth within the oligomers with a small activation energy of ≤ kBT, likely controlled by the movement of dihedral angles between monomer units. Thus, implications for the electron transport capability

  20. Orientational Jumps in (Acetamide + Electrolyte) Deep Eutectics: Anion Dependence.

    PubMed

    Das, Suman; Biswas, Ranjit; Mukherjee, Biswaroop

    2015-08-27

    All-atom molecular dynamics simulations have been carried out to investigate orientation jumps of acetamide molecules in three different ionic deep eutectics made of acetamide (CH3CONH2) and lithium salts of bromide (Br(–)), nitrate (NO3(–)) and perchlorate (ClO4(–)) at approximately 80:20 mole ratio and 303 K. Orientational jumps have been dissected into acetamide–acetamide and acetamide–ion catagories. Simulated jump characteristics register a considerable dependence on the anion identity. For example, large angle jumps are relatively less frequent in the presence of NO3(–) than in the presence of the other two anions. Distribution of jump angles for rotation of acetamide molecules hydrogen bonded (H-bonded) to anions has been found to be bimodal in the presence of Br(–) and is qualitatively different from the other two cases. Estimated energy barrier for orientation jumps of these acetamide molecules (H-bonded to anions) differ by a factor of ∼2 between NO3(–) and ClO4(–), the barrier height for the latter being lower and ∼0.5kBT. Relative radial and angular displacements during jumps describe the sequence ClO(4)– > NO3(–) > Br(–) and follow a reverse viscosity trend. Jump barrier for acetamide–acetamide pairs reflects weak dependence on anion identity and remains closer to the magnitude (∼0.7kBT) found for orientation jumps in molten acetamide. Jump time distributions exhibit a power law dependence of the type, P(tjump) ∝ A(tjump/τ)(−β), with both β and τ showing substantial anion dependence. The latter suggests the presence of dynamic heterogeneity in these systems and supports earlier conclusions from time-resolved fluorescence measurements.

  1. Electron localization of anions probed by nitrile vibrations

    SciTech Connect

    Mani, Tomoyasu; Grills, David C.; Newton, Marshall D.; Miller, John R.

    2015-08-02

    Localization and delocalization of electrons is a key concept in chemistry, and is one of the important factors determining the efficiency of electron transport through organic conjugated molecules, which have potential to act as “molecular wires”. This, in turn, substantially influences the efficiencies of organic solar cells and other molecular electronic devices. It is also necessary to understand the electronic energy landscape and the dynamics of electrons through molecular chain that govern their transport capabilities in one-dimensional conjugated chains so that we can better define the design principles of conjugated molecules for their applications. We show that nitrile ν(C≡N) vibrations respond to the degree of electron localization in nitrile-substituted organic anions by utilizing time-resolved infrared (TRIR) detection combined with pulse radiolysis. Measurements of a series of aryl nitrile anions allow us to construct a semi-empirical calibration curve between the changes in the ν(C≡N) IR shifts and the changes in the electronic charges from the neutral to the anion states in the nitriles; more electron localization in the nitrile anion results in larger IR shifts. Furthermore, the IR linewidth in anions can report a structural change accompanying changes in the electronic density distribution. Probing the shift of the nitrile ν(C≡N) IR vibrational bands enables us to determine how the electron is localized in anions of nitrile-functionalized oligofluorenes, considered as organic mixed-valence compounds. We estimate the diabatic electron transfer distance, electronic coupling strengths, and energy barriers in these organic mixed-valence compounds. The analysis reveals a dynamic picture, showing that the electron is moving back and forth within the oligomers with a small activation energy of ≤ kBT, likely controlled by the movement of dihedral angles between monomer units. Thus, implications for the electron transport

  2. [Homocysteine metabolism].

    PubMed

    Hashimoto, Takao; Shinohara, Yoshihiko; Hasegawa, Hiroshi

    2007-10-01

    Homocysteine, a sulfur amino acid, is an intermediate metabolite of methionine. In 1969, McCully reported autopsy evidence of extensive arterial thrombosis and atherosclerosis in children with elevated plasma homocysteine concentrations and homocystinuria. On the basis of this observation, he proposed that elevated plasma homocysteine (hyperhomocysteinemia) can cause atherosclerotic vascular disease. Hyperhomocysteinemia is now well established as an independent risk factor for atherosclerotic vascular disease. Mild hyperhomocysteinemia is quite prevalent in the general population. It can be caused by genetic defects in the enzymes involved in homocysteine metabolism or nutritional deficiencies in vitamin cofactors, certain medications or renal disease. An increase of 5 micromol per liter in the plasma homocysteine concentration raises the risk of coronary artery disease by as much as an increase of 20 mg per deciliter in the cholesterol concentration. In this article, we review the biochemical, experimental and clinical studies on hyperhomocysteinemia, with emphasis on the metabolism and pharmacokinetics of homocysteine.

  3. Hybrid functional calculations on the band gap bowing parameters of In x Ga1-x N

    NASA Astrophysics Data System (ADS)

    Mei, Lin; Yixu, Xu; Jianhua, Zhang; Shunqing, Wu; Zizhong, Zhu

    2016-04-01

    The electronic band structures and band gap bowing parameters of In x Ga1-x N are studied by the first-principles method based on the density functional theory. Calculations by employing both the Heyd-Scuseria-Ernzerh of hybrid functional (HSE06) and the Perdew-Burke-Ernzerhof (PBE) one are performed. We found that the theoretical band gap bowing parameter is dependent significantly on the calculation method, especially on the exchange-correlation functional employed in the DFT calculations. The band gap of In x Ga1-x N alloy decreases considerably when the In constituent x increases. It is the interactions of s-s and p-p orbitals between anions and cations that play significant roles in formatting the band gaps bowing. In general, the HSE06 hybrid functional could provide a good alternative to the PBE functional in calculating the band gap bowing parameters. Project supported by the National Natural Science Foundation of China (Nos. 11204257, 21233004) and the China Postdoctoral Science Foundation (No. 2012M511447).

  4. What is Metabolic Syndrome?

    MedlinePlus

    ... from the NHLBI on Twitter. What Is Metabolic Syndrome? Metabolic syndrome is the name for a group of ... that may play a role in causing metabolic syndrome. Outlook Metabolic syndrome is becoming more common due to a ...

  5. Sodium Bicarbonate Therapy in Patients with Metabolic Acidosis

    PubMed Central

    Adeva-Andany, María M.; Fernández-Fernández, Carlos; Mouriño-Bayolo, David; Castro-Quintela, Elvira; Domínguez-Montero, Alberto

    2014-01-01

    Metabolic acidosis occurs when a relative accumulation of plasma anions in excess of cations reduces plasma pH. Replacement of sodium bicarbonate to patients with sodium bicarbonate loss due to diarrhea or renal proximal tubular acidosis is useful, but there is no definite evidence that sodium bicarbonate administration to patients with acute metabolic acidosis, including diabetic ketoacidosis, lactic acidosis, septic shock, intraoperative metabolic acidosis, or cardiac arrest, is beneficial regarding clinical outcomes or mortality rate. Patients with advanced chronic kidney disease usually show metabolic acidosis due to increased unmeasured anions and hyperchloremia. It has been suggested that metabolic acidosis might have a negative impact on progression of kidney dysfunction and that sodium bicarbonate administration might attenuate this effect, but further evaluation is required to validate such a renoprotective strategy. Sodium bicarbonate is the predominant buffer used in dialysis fluids and patients on maintenance dialysis are subjected to a load of sodium bicarbonate during the sessions, suffering a transient metabolic alkalosis of variable severity. Side effects associated with sodium bicarbonate therapy include hypercapnia, hypokalemia, ionized hypocalcemia, and QTc interval prolongation. The potential impact of regular sodium bicarbonate therapy on worsening vascular calcifications in patients with chronic kidney disease has been insufficiently investigated. PMID:25405229

  6. Reorientional dynamics of water molecules in anionic hydration shells

    PubMed Central

    Laage, Damien; Hynes, James T.

    2007-01-01

    Water molecule rotational dynamics within a chloride anion's first hydration shell are investigated through simulations. In contrast to recent suggestions that the ion's hydration shell is rigid during a water's reorientation, we find a labile hydration sphere, consistent with previous assessments of chloride as a weak structure breaker. The nondiffusive reorientation mechanism found involves a hydrogen-bond partner switch with a large amplitude angular jump and the water's departure from the anion's shell. An analytic extended jump model accounts for the simulation results, as well as available NMR and ultrafast spectroscopic data, and resolves the discrepancy between them. PMID:17581877

  7. Mixed anion materials and compounds for novel proton conducting membranes

    DOEpatents

    Poling, Steven Andrew; Nelson, Carly R.; Martin, Steve W.

    2006-09-05

    The present invention provides new amorphous or partially crystalline mixed anion chalcogenide compounds for use in proton exchange membranes which are able to operate over a wide variety of temperature ranges, including in the intermediate temperature range of about 100 .degree. C. to 300.degree. C., and new uses for crystalline mixed anion chalcogenide compounds in such proton exchange membranes. In one embodiment, the proton conductivity of the compounds is between about 10.sup.-8 S/cm and 10.sup.-1 S/cm within a temperature range of between about -60 and 300.degree. C. and a relative humidity of less than about 12%..

  8. Anionic fluoroquinolones as antibacterials against biofilm-producing Pseudomonas aeruginosa.

    PubMed

    Long, Timothy E; Keding, Lexie C; Lewis, Demetria D; Anstead, Michael I; Withers, T Ryan; Yu, Hongwei D

    2016-02-15

    Pseudomonas aeruginosa is a common biofilm-forming bacterial pathogen implicated in diseases of the lungs. The extracellular polymeric substances (EPS) of respiratory Pseudomonas biofilms are largely comprised of anionic molecules such as rhamnolipids and alginate that promote a mucoid phenotype. In this Letter, we examine the ability of negatively-charged fluoroquinolones to transverse the EPS and inhibit the growth of mucoid P. aeruginosa. Anionic fluoroquinolones were further compared with standard antibiotics via a novel microdiffusion assay to evaluate drug penetration through pseudomonal alginate and respiratory mucus from a patient with cystic fibrosis.

  9. Predicting Carbonate Species Ionic Conductivity in Alkaline Anion Exchange Membranes

    DTIC Science & Technology

    2012-06-01

    anion exchange membranes. Andrew M. Kiss, Timothy D . Myles, Kyle N. Grew, Aldo A. Peracchio, George J. Nelson, and Wilson K. S. Chiu University of...Alkaline Anion Exchange Membranes Andrew M. Kiss1, Timothy D . Myles1, Kyle N. Grew2, Aldo A. Peracchio1, George J. Nelson1, and Wilson K. S. Chiu1* 1...Vol. 301, 93-106, 2007. 16. Satterfleld,M.B., Benziger,J.B., J. Phys. Chem. B, Vol. 112,12, 3693 -3704, 2008. 17. Motupally,S., Becker,A.J

  10. Direct Band Gap Wurtzite Gallium Phosphide Nanowires

    PubMed Central

    2013-01-01

    The main challenge for light-emitting diodes is to increase the efficiency in the green part of the spectrum. Gallium phosphide (GaP) with the normal cubic crystal structure has an indirect band gap, which severely limits the green emission efficiency. Band structure calculations have predicted a direct band gap for wurtzite GaP. Here, we report the fabrication of GaP nanowires with pure hexagonal crystal structure and demonstrate the direct nature of the band gap. We observe strong photoluminescence at a wavelength of 594 nm with short lifetime, typical for a direct band gap. Furthermore, by incorporation of aluminum or arsenic in the GaP nanowires, the emitted wavelength is tuned across an important range of the visible light spectrum (555–690 nm). This approach of crystal structure engineering enables new pathways to tailor materials properties enhancing the functionality. PMID:23464761

  11. Closing the Prescription Drug Coverage Gap

    MedlinePlus

    ... coverage gap discount work for brand-name drugs? Companies that make brand-name prescription drugs must sign ... Coverage Gap Discount Program. This program requires the companies to offer discounts on brand-name drugs to ...

  12. Dual-function sRNA encoded peptide SR1P modulates moonlighting activity of B. subtilis GapA

    PubMed Central

    Gimpel, Matthias; Brantl, Sabine

    2016-01-01

    ABSTRACT SR1 is a dual-function sRNA from B. subtilis that acts as a base-pairing regulatory RNA and as a peptide-encoding mRNA. Both functions of SR1 are highly conserved. Previously, we uncovered that the SR1 encoded peptide SR1P binds the glycolytic enzyme GapA resulting in stabilization of gapA mRNA. Here, we demonstrate that GapA interacts with RNases Y and J1, and this interaction was RNA-independent. About 1% of GapA molecules purified from B. subtilis carry RNase J1 and about 2% RNase Y. In contrast to the GapA/RNase Y interaction, the GapA/RNaseJ1 interaction was stronger in the presence of SR1P. GapA/SR1P-J1/Y displayed in vitro RNase activity on known RNase J1 substrates. Moreover, the RNase J1 substrate SR5 has altered half-lives in a ΔgapA strain and a Δsr1 strain, suggesting in vivo functions of the GapA/SR1P/J1 interaction. Our results demonstrate that the metabolic enzyme GapA moonlights in recruiting RNases while GapA bound SR1P promotes binding of RNase J1 and enhances its activity. PMID:27449348

  13. Photoelectron Spectroscopy of Rare-Gas Solvated Nucleobase Anions

    NASA Astrophysics Data System (ADS)

    Buonaugurio, Angela M.; Chen, Jing; Bowen, Kit H.

    2012-06-01

    Gas-phase polar molecular anions [uracil (U^-), thymine (T^-), 1-3 dimethyluracil (DMU^-)] solvated by rare gas atoms were studied by means of negative ion photoelectron spectroscopy. The photoelectron spectrum (PES) of U^-, T^-, and DMU^- each exhibit a distinctive dipole-bound (DB) spectral signature. The spectra of U^-, U^- (Ar)_1,2 and U^- (Kr)_1 also only displayed the DB anion feature. Upon the solvation of more rare gas atoms, the spectra of U^- (Ar)_3, U^- (Kr)_2, and U^- (Xe)1-3 not only retained the DB signature but also exhibited the valence anion features. Moreover, the DB and the valence features shifted together to higher electron binding energies (EBEs) with increasing numbers of rare gas solvent atoms. Therefore, the co-existing DB and the valence anions appeared to be strongly coupled with each other, i.e. they effectively form a single state that is a superposition of both DB and valence anion states. For both U^- and T^- series, the ``onset size" of the Xe, Kr, and Ar solvents for the co-existing of the two anionic states was 1, 2, and 3 respectively. In addition, a minimum of 2 methane (CH_4) molecules or 1 ethane (C_2H_6) molecule were required to induce the coupling between the two states in the T^- series. Thus, the nucleobase anion interaction with non-polar solvent atoms tracks as the sum of the solvent polarizabilities. However for the DMU- series, the DB and the valence anions of DMU^-(Xe)_1, DMU^-(Kr)_2, and DMU^-(Ar)_3 were completely absent in both the mass spectra and the PES. Beyond these ``holes", their PES displayed the similar behaviors to the U^- and T^- series. Extrapolated EA values for these missing species were at or very close to zero, which may explain why they were not seen. However, why this was the case is not clear. With better Franck-Condon overlap between the origins of the NB^- (Rg)_n valence anion and the neutral NB(Rg)n than between those of the NB^- (H2O)n valence anion and the neutral NB(H2O)n, extrapolation of

  14. Gap Year: Time off, with a Plan

    ERIC Educational Resources Information Center

    Torpey, Elka Maria

    2009-01-01

    A gap year allows people to step off the usual educational or career path and reassess their future. According to people who have taken a gap year, the time away can be well worth it. This article can help a person decide whether to take a gap year and how to make the most of his time off. It describes what a gap year is, including its pros and…

  15. Anion-Anion Bonding and Topology in Ternary Iridium Seleno-Stannides.

    PubMed

    Trump, Benjamin A; Tutmaher, Jake A; McQueen, Tyrel M

    2015-12-21

    The synthesis and physical properties of two new and one known Ir-Sn-Se compound are reported. Their crystal structures are elucidated with transmission electron microscopy and powder X-ray diffraction. IrSn0.45Se1.55 is a pyrite phase which consists of tilted corner-sharing IrX6 octahedra with randomly distributed (Sn-Se)(4-) and (Se-Se)(2-) dimers. Ir2Sn3Se3 is a known trigonally distorted skutterudite that consists of cooperatively tilted corner-sharing IrSn3Se3 octahedra with ordered (Sn-Se)2(4-) tetramers. Ir2SnSe5 is a layered, distorted β-MnO2 (pyrolusite) structure consisting of a double IrSe6 octrahedral row, corner sharing in the a direction and edge sharing in the b direction. This distorted pyrolusite contains (Se-Se)(2-) dimers and Se(2-) anions, and each double row is "capped" with a (Sn-Se)n polymeric chain. Resistivity, specific heat, and magnetization measurements show that all three have insulating and diamagnetic behavior, indicative of low-spin 5d(6) Ir(3+). Electronic structure calculations on Ir2Sn3Se3 show a single, spherical, nonspin-orbit split valence band and suggest that Ir2Sn3Se3 is topologically nontrivial under tensile strain due to inversion of Ir-d and Se-p states.

  16. A new anionic exchange stir bar sorptive extraction coating based on monolithic material for the extraction of inorganic anion.

    PubMed

    Huang, Xiaojia; Lin, Jianbing; Yuan, Dongxing

    2010-07-23

    A novel anionic exchange stir bar sorptive extraction (SBSE) coating based on poly(2-(methacryloyloxy)ethyltrimethylammonium chloride-co-divinylbenzene) monolithic material for the extraction of inorganic anion was prepared. The effect of preparation conditions such as ratio of functional monomer to cross-linker, content of porogenic solvent on the extraction efficiencies were investigated in detailed. The monolithic material was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to investigate the extraction capacity of the new coating for inorganic anion, the new SBSE was combined with ionic chromatography with conductivity detection, Br-, NO3-, PO4(3-) and SO4(2-) were selected as detected solutes. Several extractive parameters, including pH value and ionic strength in sample matrix, desorption solvent, extraction and desorption time were optimized. The results showed that strongly ionic strength did not favor the extraction of anlaytes. Under the optimum experimental conditions, low detection limits (S/N=3) and quantification limits (S/N=10) of the proposed method for the target anions were achieved within the range of 0.92-2.62 and 3.03-9.25 microg/L, respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction inorganic anions. Finally, the proposed method was successfully used to detect the two different trademarks of commercial purified water with satisfactory recovery in the range of 70.0-92.6%. To the best of our knowledge, this is the first to use SBSE to enrich inorganic anions.

  17. Extracellular superoxide anion production contributes to the virulence of Xanthomonas oryzae pv. oryzae.

    PubMed

    Li, Xin; Pang, Xinyue; Zhi, Dejuan; Wang, Jinsheng; Li, Minquan; Li, Hongyu

    2009-02-01

    Endogenous superoxide anion production was determined by electron spin resonance in wild-type strains and avrXa7 mutants of Xanthomonas oryzae pv. oryzae. The localization of superoxide anion was carried out in the intra- and extra-cellular fractions. Results showed the presence of superoxide anion in multi-locations of X. oryzae pv. oryzae cells. The extracellular fraction was the major location of superoxide anion production. Furthermore, a positive relationship was shown between the levels of endogenous superoxide anion and the virulence of strains. These indubitable results suggested that the superoxide anion contributes to the virulence of X. oryzae pv. oryzae.

  18. Association between the markers of metabolic acid load and higher all-cause and cardiovascular mortality in a general population with preserved renal function.

    PubMed

    Park, Minseon; Jung, Sung Jae; Yoon, Seoyoung; Yun, Jae Moon; Yoon, Hyung-Jin

    2015-06-01

    Although metabolic acid load has been associated with many well-known risk factors for mortality, its clinical implications are not yet clear. To evaluate the association between biomarkers of metabolic acid load, such as serum bicarbonate, serum anion gap and urine pH and mortality, we analyzed the health records of 31,590 adults who underwent a health screening between January 2001 and December 2010 and had an estimated glomerular filtration rate ⩾60 ml min(-1) per 1.73 m2. Urine pH was measured by a dipstick test performed on fast morning urine sample and categorized as acidic (urine pH ⩽5.5), neutral and alkaline (urine pH ⩾8.0). Using the Cox proportional hazard model, the adjusted hazard ratio (aHR) of all-cause mortality of the lowest quartile of serum bicarbonate was 1.460 (95% confidence interval (CI) 1.068-1.995) compared with the highest quartile, after a median follow-up of 93 months. The aHRs of cardiovascular and cancer mortality of the lowest quartile of serum bicarbonate were 2.647 (95% CI 1.148-6.103) and 1.604 (95% CI 1.024-2.513), respectively, compared with the highest quartile. Acidic and neutral urine pH were significantly associated with a higher all-cause mortality (aHR 2.550, 95% CI 1.316-4.935; aHR 2.376 95% CI 1.254-4.501, respectively), compared with an alkaline urine pH. In conclusion, higher metabolic acid load was associated with an increased all-cause and cardiovascular mortality in a healthy population. The association between metabolic acid load and mortality and the causality of the relationship need to be confirmed.

  19. Closing the Achievement Gap: Four States' Efforts

    ERIC Educational Resources Information Center

    Wixom, Micah Ann

    2015-01-01

    The achievement gap separating economically disadvantaged students from their more advantaged peers disproportionately affects students of color and has been the focus of discussion, research and controversy for more than 40 years. While the gap between black and white students narrowed considerably from the 1950s to the 1980s, that gap has…

  20. Calibration curves for some standard Gap Tests

    SciTech Connect

    Bowman, A.L.; Sommer, S.C.

    1989-01-01

    The relative shock sensitivities of explosive compositions are commonly assessed using a family of experiments that can be described by the generic term ''Gap Test.'' Gap tests include a donor charge, a test sample, and a spacer, or gap, between two explosives charges. The donor charge, gap material, and test dimensions are held constant within each different version of the gap test. The thickness of the gap is then varied to find the value at which 50% of the test samples will detonate. The gap tests measure the ease with a high-order detonation can be established in the test explosive, or the ''detonability,'' of the explosive. Test results are best reported in terms of the gap thickness at the 50% point. It is also useful to define the shock pressure transmitted into the test sample at the detonation threshold. This requires calibrating the gap test in terms of shock pressure in the gap as a function of the gap thickness. It also requires a knowledge of the shock Hugoniot of the sample explosive. We used the 2DE reactive hydrodynamic code with Forest Fire burn rates for the donor explosives to calculate calibration curves for several gap tests. The model calculations give pressure and particle velocity on the centerline of the experimental set-up and provide information about the curvature and pulse width of the shock wave. 10 refs., 1 fig.

  1. Effects of anion supplementation to low-potassium prepartum diets on macromineral status and performance of periparturient dairy cows.

    PubMed

    Ramos-Nieves, J M; Thering, B J; Waldron, M R; Jardon, P W; Overton, T R

    2009-11-01

    prepartum and postpartum periods. Glucose rate of appearance was determined by continuous infusion of 6,6-dideuterated glucose in a subset of cows between 6 and 10 d prepartum (control, n = 12; low DCAD, n = 9) and 7 and 10 d postpartum (control, n = 9; low DCAD, n = 8) periods. Glucose rate of appearance was not affected by treatment during the prepartum or postpartum periods. Overall, anion supplementation of low K diets improved P status during the early postpartum period, but did not affect aspects of energy metabolism or periparturient performance.

  2. Regulation of an ATP-conductive large-conductance anion channel and swelling-induced ATP release by arachidonic acid

    PubMed Central

    Dutta, Amal K; Okada, Yasunobu; Sabirov, Ravshan Z

    2002-01-01

    Mouse mammary C127 cells responded to hypotonic stimulation with activation of the volume-dependent ATP-conductive large conductance (VDACL) anion channel and massive release of ATP. Arachidonic acid downregulated both VDACL currents and swelling-induced ATP release in the physiological concentration range with Kd of 4– 6 μm. The former effect observed in the whole-cell or excised patch mode was more prominent than the latter effect observed in intact cells. The arachidonate effects were direct and not mediated by downstream metabolic products, as evidenced by their insensitivity to inhibitors of arachidonate-metabolizing oxygenases, and by the observation that they were mimicked by cis-unsaturated fatty acids, which are not substrates for oxygenases. A membrane-impermeable analogue, arachidonyl coenzyme A was effective only from the cytosolic side of membrane patches suggesting that the binding site is localized intracellularly. Non-charged arachidonate analogues as well as trans-unsaturated and saturated fatty acids had no effect on VDACL currents and ATP release, indicating the importance of arachidonate's negative charge and specific hydrocarbon chain conformation in the inhibitory effect. VDACL anion channels were inhibited by arachidonic acid in two different ways: channel shutdown (Kd of 4– 5 μm) and reduced unitary conductance (Kd of 13–14 μm) without affecting voltage dependence of open probability. ATP4--conducting inward currents measured in the presence of 100 mm ATP in the bath were reversibly inhibited by arachidonic acid. Thus, we conclude that swelling-induced ATP release and its putative pathway, the VDACL anion channel, are under a negative control by intracellular arachidonic acid signalling in mammary C127 cells. PMID:12154180

  3. Activity and anion inhibition studies of the α-carbonic anhydrase from Thiomicrospira crunogena XCL-2 Gammaproteobacterium.

    PubMed

    Mahon, Brian P; Díaz-Torres, Natalia A; Pinard, Melissa A; Tu, Chingkuang; Silverman, David N; Scott, Kathleen M; McKenna, Robert

    2015-11-01

    Thiomicrospira crunogena XCL-2 expresses an α-carbonic anhydrase (TcruCA). Sequence alignments reveal that TcruCA displays a high sequence identity (>30%) relative to other α-CAs. This includes three conserved histidines that coordinate the active site zinc, a histidine proton shuttling residue, and opposing hydrophilic and hydrophobic sides that line the active site. The catalytic efficiency of TcruCA is considered moderate relative to other α-CAs (k(cat)/K(M)=1.1×10(7) M(-1) s(-1)), being a factor of ten less efficient than the most active α-CAs. TcruCA is also inhibited by anions with Cl(-), Br(-), and I(-), all showing Ki values in the millimolar range (53-361 mM). Hydrogen sulfide (HS(-)) revealed the highest affinity for TcruCA with a Ki of 1.1 μM. It is predicted that inhibition of TcruCA by HS(-) (an anion commonly found in the environment where Thiomicrospira crunogena is located) is a way for Thiomicrospira crunogena to regulate its carbon-concentrating mechanism (CCM) and thus the organism's metabolic functions. Results from this study provide preliminary insights into the role of TcruCA in the general metabolism of Thiomicrospira crunogena.

  4. Capturing and concentrating adenovirus using magnetic anionic nanobeads

    PubMed Central

    Sakudo, Akikazu; Baba, Koichi; Ikuta, Kazuyoshi

    2016-01-01

    We recently demonstrated how various enveloped viruses can be efficiently concentrated using magnetic beads coated with an anionic polymer, poly(methyl vinyl ether-maleic anhydrate). However, the exact mechanism of interaction between the virus particles and anionic beads remains unclear. To further investigate whether these magnetic anionic beads specifically bind to the viral envelope, we examined their potential interaction with a nonenveloped virus (adenovirus). The beads were incubated with either adenovirus-infected cell culture medium or nasal aspirates from adenovirus-infected individuals and then separated from the supernatant by applying a magnetic field. After thoroughly washing the beads, adsorption of adenovirus was confirmed by a variety of techniques, including immunochromatography, polymerase chain reaction, Western blotting, and cell culture infection assays. These detection methods positively identified the hexon and penton capsid proteins of adenovirus along with the viral genome on the magnetic beads. Furthermore, various types of adenovirus including Types 5, 6, 11, 19, and 41 were captured using the magnetic bead procedure. Our bead capture method was also found to increase the sensitivity of viral detection. Adenovirus below the detectable limit for immunochromatography was efficiently concentrated using the magnetic bead procedure, allowing the virus to be successfully detected using this methodology. Moreover, these findings clearly demonstrate that a viral envelope is not required for binding to the anionic magnetic beads. Taken together, our results show that this capture procedure increases the sensitivity of detection of adenovirus and would, therefore, be a valuable tool for analyzing both clinical and experimental samples. PMID:27274228

  5. The Determination of Anionic Surfactants in Natural and Waste Waters.

    ERIC Educational Resources Information Center

    Crisp, P. T.; And Others

    1983-01-01

    Background information, procedures, and results of an experiment suitable for measuring subpart per million concentrations of anionic surfactants in natural waters and waste effluents are provided. The experiment required only a spectrophotometer or filter photometer and has been successfully performed by students in an undergraduate environmental…

  6. Prescription Fire and Anion Retention in Tahoe Forest Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Prescribed burning is a possible option to reduce fire potential in the Lake Tahoe Basin (California and Nevada). However, subsequent nutrient loading to the lake is a major concern. The effect of residual ash on anion leaching, primarily O-PO4 and SO42-, was studied in both the field and laboratory...

  7. Physicochemical treatments of anionic surfactants wastewater: Effect on aerobic biodegradability.

    PubMed

    Aloui, Fathi; Kchaou, Sonia; Sayadi, Sami

    2009-05-15

    The effect of different physicochemical treatments on the aerobic biodegradability of an industrial wastewater resulting from a cosmetic industry has been investigated. This industrial wastewater contains 11423 and 3148mgL(-1) of chemical oxygen demand (COD) and anionic surfactants, respectively. The concentration of COD and anionic surfactants were followed throughout the diverse physicochemical treatments and biodegradation experiments. Different pretreatments of this industrial wastewater using chemical flocculation process with lime and aluminium sulphate (alum), and also advanced oxidation process (electro-coagulation (Fe and Al) and electro-Fenton) led to important COD and anionic surfactants removals. The best results were obtained using electro-Fenton process, exceeding 98 and 80% of anionic surfactants and COD removals, respectively. The biological treatment by an isolated strain Citrobacter braakii of the surfactant wastewater, as well as the pretreated wastewater by the various physicochemical processes used in this study showed that the best results were obtained with electro-Fenton pretreated wastewater. The characterization of the treated surfactant wastewater by the integrated process (electro-coagulation or electro-Fenton)-biological showed that it respects Tunisian discharge standards.

  8. Tetrathiafulvalene diindolylquinoxaline: a dual signaling anion receptor with phosphate selectivity†

    PubMed Central

    Bejger, Christopher; Park, Jung Su; Silver, Eric S.; Sessler, Jonathan L.

    2011-01-01

    Incorporation of tetrathiafulvalene into the backbone of a known neutral phosphate receptor, diindolylquinoxaline, yields a dual optical-electrochemical chemosensor for dihydrogen phosphate that functions in dichloromethane. This system shows selectivity for dihydrogen phosphate over other small anions and can be used to detect the presence of this analyte via fluorescence quenching or cyclic voltammetry. PMID:20856940

  9. Cation and anion transport through hydrophilic pores in lipid bilayers

    NASA Astrophysics Data System (ADS)

    Kandasamy, Senthil K.; Larson, Ronald G.

    2006-08-01

    To understand the origin of transmembrane potentials, formation of transient pores, and the movement of anions and cations across lipid membranes, we have performed systematic atomistic molecular dynamics simulations of palmitoyl-oleoyl-phosphatidylcholine (POPC) lipids. A double bilayer setup was employed and different transmembrane potentials were generated by varying the anion (Cl-) and cation (Na+) concentrations in the two water compartments. A transmembrane potential of ˜350mV was thereby generated per bilayer for a unit charge imbalance. For transmembrane potential differences of up to ˜1.4V, the bilayers were stable, over the time scale of the simulations (10-50ns). At larger imposed potential differences, one of the two bilayers breaks down through formation of a water pore, leading to both anion and cation translocations through the pore. The anions typically have a short residence time inside the pore, while the cations show a wider range of residence times depending on whether they bind to a lipid molecule or not. Over the time scale of the simulations, we do not observe the discharge of the entire potential difference, nor do we observe pore closing, although we observe that the size of the pore decreases as more ions translocate. We also observed a rare lipid flip-flop, in which a lipid molecule translocated from one bilayer leaflet to the opposite leaflet, assisted by the water pore.

  10. The anionic biosurfactant rhamnolipid does not denature industrial enzymes.

    PubMed

    Madsen, Jens K; Pihl, Rasmus; Møller, Anders H; Madsen, Anne T; Otzen, Daniel E; Andersen, Kell K

    2015-01-01

    Biosurfactants (BS) are surface-active molecules produced by microorganisms. Their combination of useful properties and sustainable production make them promising industrial alternatives to petrochemical and oleochemical surfactants. Here we compare the impact of the anionic BS rhamnolipid (RL) and the conventional/synthetic anionic surfactant sodium dodecyl sulfate (SDS) on the structure and stability of three different commercially used enzymes, namely the cellulase Carezyme® (CZ), the phospholipase Lecitase Ultra® (LT) and the α-amylase Stainzyme® (SZ). Our data reveal a fundamental difference in their mode of interaction. SDS shows great diversity of interaction toward the different enzymes. It efficiently unfolds both LT and CZ, but LT is unfolded by SDS through formation of SDS clusters on the enzyme well below the cmc, while CZ is only unfolded by bulk micelles and on average binds significantly less SDS than LT. SDS binds with even lower stoichiometry to SZ and leads to an increase in thermal stability. In contrast, RL does not affect the tertiary or secondary structure of any enzyme at room temperature, has little impact on thermal stability and only binds detectably (but at low stoichiometries) to SZ. Furthermore, all enzymes maintain activity at both monomeric and micellar concentrations of RL. We conclude that RL, despite its anionic charge, is a surfactant that does not compromise the structural integrity of industrially relevant enzymes. This makes RL a promising alternative to current synthetic anionic surfactants in a wide range of commercial applications.

  11. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    NASA Astrophysics Data System (ADS)

    Rodacka, Aleksandra; Serafin, Eligiusz; Puchala, Mieczyslaw

    2010-09-01

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as rad OH and ONOO -. In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  12. PHASE BEHAVIOR OF WATER/PERCHLOROETHYLENE/ANIONIC SURFACTANT SYSTEMS

    EPA Science Inventory

    Winsor Type I (o/w), Type II (w/o), and Type III (middle phase) microemulsions have been generated for water and perchloroethylene (PCE) in combination with anionic surfactants and the appropriate electrolyte concentration. The surfactant formulation was a combination of sodium d...

  13. Molecular Anions in Protostars, Prestellar Cores and Dark Clouds

    NASA Technical Reports Server (NTRS)

    Cordiner, Martin; Charnley, Steven; Buckle, Jane; Wash, Catherine; Millar, Tom

    2011-01-01

    From our recent survey work using the Green Bank Telescope, microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H have been detected in six new sources. Using HC3N = 10(exp -9) emission maps, we targeted the most carbon-chain-rich sources for our anion survey, which included the low-mass Class 0 protostar L1251A-IRS3, the prestellar cores L1389-SMM1 and L1512, and the interstellar clouds Ll172A, TMC-1C and L1495B. Derived [C6H(-)]/[C6H] anion-to-neutral ratios are approximately 1-10. The greatest C6H(-) column densities are found in the quiescent clouds TMC-1C and L1495B, but the anion-to-neutral ratios are greatest in the prestellar cores and protostars. These results are interpreted in terms of the physical and chemical properties of the sources, and the implications for molecular cloud chemistry are discussed.

  14. Comment on "Local impermeant anions establish the neuronal chloride concentration".

    PubMed

    Voipio, Juha; Boron, Walter F; Jones, Stephen W; Hopfer, Ulrich; Payne, John A; Kaila, Kai

    2014-09-05

    Glykys et al. (Reports, 7 February 2014, p. 670) conclude that, rather than ion transporters, "local impermeant anions establish the neuronal chloride concentration" and thereby determine "the magnitude and direction of GABAAR currents at individual synapses." If this were possible, perpetual ion-motion machines could be constructed. The authors' conclusions conflict with basic thermodynamic principles.

  15. Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

    NASA Technical Reports Server (NTRS)

    Nadarajah, Arunan

    1996-01-01

    Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

  16. Photocatalytic Anion Oxidation and Applications in Organic Synthesis.

    PubMed

    Hering, Thea; Meyer, Andreas Uwe; König, Burkhard

    2016-08-19

    Ions and radicals of the same kind differ by one electron only. The oxidation of many stable inorganic anions yields their corresponding highly reactive radicals, and visible light excitable photocatalysts can provide the required oxidation potential for this transformation. Air oxygen serves as the terminal oxidant, or cheap sacrificial oxidants are used, providing a very practical approach for generating reactive inorganic radicals for organic synthesis. We discuss in this perspective several recently reported examples: Nitrate radicals are obtained by one-electron photooxidation of nitrate anions and are very reactive toward organic molecules. The photooxidation of sulfinate salts yields the much more stable sulfone radicals, which smoothly add to double bonds. A two-electron oxidation of chloride anions to electrophilic chlorine species reacting with arenes in aromatic substitutions extends the method beyond radical reactions. The chloride anion oxidation proceeds via photocatalytically generated peracidic acid as the oxidation reagent. Although the number of reported examples of photocatalytically generated inorganic radical intermediates for organic synthesis is still small, future extension of the concept to other inorganic ions as radical precursors is a clear perspective.

  17. The anionic biosurfactant rhamnolipid does not denature industrial enzymes

    PubMed Central

    Madsen, Jens K.; Pihl, Rasmus; Møller, Anders H.; Madsen, Anne T.; Otzen, Daniel E.; Andersen, Kell K.

    2015-01-01

    Biosurfactants (BS) are surface-active molecules produced by microorganisms. Their combination of useful properties and sustainable production make them promising industrial alternatives to petrochemical and oleochemical surfactants. Here we compare the impact of the anionic BS rhamnolipid (RL) and the conventional/synthetic anionic surfactant sodium dodecyl sulfate (SDS) on the structure and stability of three different commercially used enzymes, namely the cellulase Carezyme® (CZ), the phospholipase Lecitase Ultra® (LT) and the α-amylase Stainzyme® (SZ). Our data reveal a fundamental difference in their mode of interaction. SDS shows great diversity of interaction toward the different enzymes. It efficiently unfolds both LT and CZ, but LT is unfolded by SDS through formation of SDS clusters on the enzyme well below the cmc, while CZ is only unfolded by bulk micelles and on average binds significantly less SDS than LT. SDS binds with even lower stoichiometry to SZ and leads to an increase in thermal stability. In contrast, RL does not affect the tertiary or secondary structure of any enzyme at room temperature, has little impact on thermal stability and only binds detectably (but at low stoichiometries) to SZ. Furthermore, all enzymes maintain activity at both monomeric and micellar concentrations of RL. We conclude that RL, despite its anionic charge, is a surfactant that does not compromise the structural integrity of industrially relevant enzymes. This makes RL a promising alternative to current synthetic anionic surfactants in a wide range of commercial applications. PMID:25941516

  18. Metabolic engineering in methanotrophic bacteria

    SciTech Connect

    Kalyuzhnaya, MG; Puri, AW; Lidstrom, ME

    2015-05-01

    Methane, as natural gas or biogas, is the least expensive source of carbon for (bio)chemical synthesis. Scalable biological upgrading of this simple alkane to chemicals and fuels can bring new sustainable solutions to a number of industries with large environmental footprints, such as natural gas/petroleum production, landfills, wastewater treatment, and livestock. Microbial biocatalysis with methane as a feedstock has been pursued off and on for almost a half century, with little enduring success. Today, biological engineering and systems biology provide new opportunities for metabolic system modulation and give new optimism to the concept of a methane-based bio-industry. Here we present an overview of the most recent advances pertaining to metabolic engineering of microbial methane utilization. Some ideas concerning metabolic improvements for production of acetyl-CoA and pyruvate, two main precursors for bioconversion, are presented. We also discuss main gaps in the current knowledge of aerobic methane utilization, which must be solved in order to release the full potential of methane-based biosystems. (C) 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  19. Anionic metabolite biosynthesis enhanced by potassium under dark, anaerobic conditions in cyanobacteria

    PubMed Central

    Ueda, Sakiko; Kawamura, Yuhki; Iijima, Hiroko; Nakajima, Mitsuharu; Shirai, Tomokazu; Okamoto, Mami; Kondo, Akihiko; Hirai, Masami Yokota; Osanai, Takashi

    2016-01-01

    Potassium (K+) is an essential macronutrient for all living organisms including cyanobacteria. Cyanobacteria are a group of bacteria performing oxygenic photosynthesis, widely studied in basic and applied sciences. The primary metabolism of the unicellular cyanobacterium Synechocystis sp. PCC 6803 is altered by environmental conditions, and it excretes organic acids and hydrogen under dark, anaerobic conditions. Here we demonstrated that K+ widely changes the primary carbon metabolism of this cyanobacterium. Succinate and lactate excretion from the cells incubated under dark, anaerobic conditions was enhanced in the presence of K+, while hydrogen production was repressed. The addition of K+ and the genetic manipulation of acetate kinase AckA and an RNA polymerase sigma factor SigE additively increased succinate and lactate production to 141.0 and 217.6 mg/L, which are 11 and 46 times, compared to the wild-type strain without K+, respectively. Intracellular levels of 2-oxoglutarate, succinate, fumarate, and malate increased by K+ under dark, anaerobic conditions. This study provides the evidence of the considerable effect of K+ on the biosynthesis of anionic metabolites in a unicellular cyanobacterium. PMID:27576448

  20. Fermi-level pinning and intrinsic surface states in cleaved GaP

    NASA Astrophysics Data System (ADS)

    Chiaradia, P.; Fanfoni, M.; Nataletti, P.; de Padova, P.; Brillson, L. J.; Slade, M. L.; Viturro, R. E.; Kilday, D.; Margaritondo, G.

    1989-03-01

    We have performed photoelectron spectroscopy of the clean GaP(110) surface, obtained by cleaving n-type specimens. The results show that Fermi-level stabilization occurs in a wide range of positions. In some cases nearly flat bands were obtained. The surface Fermi-level position in n-type GaP(110) is then due to extrinsic surface states, probably cleavage defects, as in the case of p-type samples. The density of these extrinsic states depends upon the quality of the cleave. Previously the Fermi-level pinning in n-type GaP(110) surfaces instead was attributed to (empty) intrinsic surface states located at 1.6+/-0.1 eV above the valence band. GaP(110) was considered an exception among III-V compounds, since in general atomic relaxation removes intrinsic surface states from the fundamental gap. The present results set a lower bound for the energetic position of the empty surface states slightly below the bottom of the conduction band. Therefore GaP(110) exhibits a gap practically free from intrinsic surface states, like the other III-V compounds so far investigated. We have also performed a spectroscopic study of the empty (intrinsic) surface states on the same surface by measuring the absorption edge of the P 2p core level. The result shows that the wave functions of the empty dangling-bond states, mainly cationic in origin, have a sizable localization on the anion site as well.

  1. [Metabolic syndrome].

    PubMed

    Takata, Hiroshi; Fujimoto, Shimpei

    2013-02-01

    Metabolic syndrome (Mets) is a combination of disorders including abdominal obesity, impaired glucose tolerance, dyslipidemia and hypertension, which increases risk for cardiovascular disease (CVD) and type 2 diabetes when occurring together. In Japan, diagnosis criteria of Mets consists of an increased waist circumference and 2 or more of CVD risk factors. Annual health checkups and health guidance using Mets criteria were established in 2008 for the prevention of life-style related diseases in Japan. In this issue, history and diagnostic criteria of Mets and concerns for Mets concept were described.

  2. Band gaps in bubble phononic crystals

    NASA Astrophysics Data System (ADS)

    Leroy, V.; Bretagne, A.; Lanoy, M.; Tourin, A.

    2016-12-01

    We investigate the interaction between Bragg and hybridization effects on the band gap properties of bubble phononic crystals. These latter consist of air cavities periodically arranged in an elastomer matrix and are fabricated using soft-lithography techniques. Their transmission properties are affected by Bragg effects due to the periodicity of the structure as well as hybridization between the propagating mode of the embedding medium and bubble resonance. The hybridization gap survives disorder while the Bragg gap requires a periodic distribution of bubbles. The distance between two bubble layers can be tuned to make the two gaps overlap or to create a transmission peak in the hybridization gap.

  3. Bimodal loop-gap resonator

    NASA Astrophysics Data System (ADS)

    Piasecki, W.; Froncisz, W.; Hyde, James S.

    1996-05-01

    A bimodal loop-gap resonator for use in electron paramagnetic resonance (EPR) spectroscopy at S band is described. It consists of two identical one-loop-one-gap resonators in coaxial juxtaposition. In one mode, the currents in the two loops are parallel and in the other antiparallel. By introducing additional capacitors between the loops, the frequencies of the two modes can be made to coincide. Details are given concerning variable coupling to each mode, tuning of the resonant frequency of one mode to that of the other, and adjustment of the isolation between modes. An equivalent circuit is given and network analysis carried out both experimentally and theoretically. EPR applications are described including (a) probing of the field distributions with DPPH, (b) continuous wave (cw) EPR with a spin-label line sample, (c) cw electron-electron double resonance (ELDOR), (d) modulation of saturation, and (e) saturation-recovery (SR) EPR. Bloch induction experiments can be performed when the sample extends half way through the structure, but microwave signals induced by Mx and My components of magnetization cancel when it extends completely through. This latter situation is particularly favorable for SR, modulation of saturation, and ELDOR experiments, which depend on observing Mz indirectly using a second weak observing microwave source.

  4. Localization of anionic phospholipids in Escherichia coli cells.

    PubMed

    Oliver, Piercen M; Crooks, John A; Leidl, Mathias; Yoon, Earl J; Saghatelian, Alan; Weibel, Douglas B

    2014-10-01

    Cardiolipin (CL) is an anionic phospholipid with a characteristically large curvature and is of growing interest for two primary reasons: (i) it binds to and regulates many peripheral membrane proteins in bacteria and mitochondria, and (ii) it is distributed asymmetrically in rod-shaped cells and is concentrated at the poles and division septum. Despite the growing number of studies of CL, its function in bacteria remains unknown. 10-N-Nonyl acridine orange (NAO) is widely used to image CL in bacteria and mitochondria, as its interaction with CL is reported to produce a characteristic red-shifted fluorescence emission. Using a suite of biophysical techniques, we quantitatively studied the interaction of NAO with anionic phospholipids under physiologically relevant conditions. We found that NAO is promiscuous in its binding and has photophysical properties that are largely insensitive to the structure of diverse anionic phospholipids to which it binds. Being unable to rely solely on NAO to characterize the localization of CL in Escherichia coli cells, we instead used quantitative fluorescence microscopy, mass spectrometry, and mutants deficient in specific classes of anionic phospholipids. We found CL and phosphatidylglycerol (PG) concentrated in the polar regions of E. coli cell membranes; depletion of CL by genetic approaches increased the concentration of PG at the poles. Previous studies suggested that some CL-binding proteins also have a high affinity for PG and display a pattern of cellular localization that is not influenced by depletion of CL. Framed within the context of these previous experiments, our results suggest that PG may play an essential role in bacterial physiology by maintaining the anionic character of polar membranes.

  5. NMR parameters in gapped graphene systems

    NASA Astrophysics Data System (ADS)

    Crisan, Mircea; Grosu, Ioan; Ţifrea, Ionel

    2016-06-01

    We calculate the nuclear spin-lattice relaxation time and the Knight shift for the case of gapped graphene systems. Our calculations consider both the massive and massless gap scenarios. Both the spin-lattice relaxation time and the Knight shift depend on temperature, chemical potential, and the value of the electronic energy gap. In particular, at the Dirac point, the electronic energy gap has stronger effects on the system nuclear magnetic resonance parameters in the case of the massless gap scenario. Differently, at large values of the chemical potential, both gap scenarios behave in a similar way and the gapped graphene system approaches a Fermi gas from the nuclear magnetic resonance parameters point of view. Our results are important for nuclear magnetic resonance measurements that target the 13C active nuclei in graphene samples.

  6. Identifiability of diffusion and retention parameters of anionic tracers from the diffusion and retention (DR) experiment

    NASA Astrophysics Data System (ADS)

    Yi, Shuping; Samper, Javier; Naves, Acacia; Soler, Josep M.

    2012-06-01

    SummaryIn situ diffusion experiments in low-permeability rocks are performed to study radionuclide diffusion and sorption and investigate scale effects. They are carried out in a packed-off interval of a borehole having a circulation system in which tracers are injected and allowed to diffuse into the rock. Tracer concentrations are monitored at the tracer interval during the experiment (dilution data) and measured at the end of the experiment in rock cores (overcoring data). The interpretation of in situ diffusion experiments in clay formations is challenging due to the influence of the filter, the gap between the filter and the borehole wall and the borehole disturbed zone (BDZ). The impact of the filter, the gap and the BDZ on the estimates of the accessible porosity and the effective diffusion, De, of the rock in the presence of random noise has been evaluated for the anionic tracers with synthetic experiments having the geometry and parameters of the in situ diffusion and retention (DR) experiment performed on Opalinus clay. The component of De of the clay parallel to the bedding can be estimated properly from dilution data when the standard deviation of the noise of the data is smaller than 0.05, but the component of De normal to the bedding cannot be estimated from dilution data. On the other hand, both components of De can be estimated properly from noisy overcoring data. Although the parameters of the BDZ and the undisturbed clay cannot be estimated simultaneously from noisy dilution data, they can be estimated from noisy overcoring data when the standard deviation of the noise is smaller than 0.05. Parameter estimation errors are large when the assumption about the BDZ is incorrect. The uncertainties in the De of the filter and in the volume of the circulation system have a noticeable impact on the estimates of the diffusion and porosity of the clay derived from dilution data. On the other hand, acceptable parameter estimates are obtained from overcoring

  7. Simultaneous separation of inorganic anions and cations by using anion-exchange and cation-exchange columns connected in tandem in ion chromatography.

    PubMed

    Karim, Khairil Juhanni Binti Abd; Jin, Ji-Ye; Takeuchi, Toyohide

    2003-05-02

    Inorganic anions and cations in environmental waters were determined by ion chromatography. Stationary and mobile phases were examined for the simultaneous separation of both anions and cations. Cations detection by UV detection requires a mobile phase with a UV absorbing additive, which indirectly visualizes cations as negative peaks. Simultaneous separation of anions and cations were achieved when using an eluent that consists of inorganic acid with weak basic amino acid as additives. It was convenient to separate both anions and cations by coupling anion-exchange and cation-exchange columns in tandem. The order of the separation columns connected affected the elution profiles. When the eluent comprises of multiple anions and a single cation, the anion-exchange column should be connected in the upper stream, whereas when the eluent comprises multiple cations and a single anion, the cation-exchange column should be connected in the upper stream. Use of switching valves also allowed simultaneous separation of anions and cations in a single chromatographic run. In the present work, operating conditions were optimized for the simultaneous separation of anions and cations.

  8. Metabolic Networks

    NASA Astrophysics Data System (ADS)

    Palumbo, Maria Concetta; Farina, Lorenzo; Colosimo, Alfredo; Giuliani, Alessandro

    The use of the term `network' is more and more widespread in all fields of biology. It evokes a systemic approach to biological problems able to overcome the evident limitations of the strict reductionism of the past twenty years. The expectations produced by taking into considerations not only the single elements but even the intermingled `web' of links connecting different parts of biological entities, are huge. Nevertheless, we believe that the lack of consciousness that networks, beside their biological `likelihood', are modeling tools and not real entities, could be detrimental to the exploitation of the full potential of this paradigm. Like any modeling tool the network paradigm has a range of application going from situations in which it is particularly fit to situations in which its application can be largely misleading. In this chapter we deal with an aspect of biological entities that is particularly fit for the network approach: the intermediate metabolism. This fit derives both from the existence of a privileged formalization in which the relative role of nodes (metabolites) and arches (enzymes) is immediately suggested by the system architecture. Here we will discuss some applications of both graph theory based analysis and multidimensional statistics method to metabolic network studies with the emphasis on the derivation of biologically meaningful information.

  9. Simultaneous separation and detection of anions and thiophilic cations using capillary-size anion exchange chromatography with suppressed conductivity detection.

    PubMed

    Sötz, Veronika Anna; Kochmann, Sven

    2015-05-01

    In this fundamental study, the simultaneous separation and detection of anions and thiophilic cations in anion exchange chromatography with suppressed conductivity detection is investigated. Mercury(II) and cadmium(II) served as model analytes. Separation and detection was performed by introducing 2-mercaptoethanesulfonate, which forms complexes with both mercury and cadmium with a strong metal-sulfur bond, into the KOH eluent. Additional to the separation on the column, these complexes were able to pass the suppressor. Subsequently, they could be detected as negative peaks. A simple model for the separation mechanism was developed based on these results. Furthermore, the effect of the eluent concentration on the retention factors of both cation complexes and standard anions was examined and quantified. It revealed that the concentration of 2-mercaptoethanesulfonate has more influence on the cations than the KOH concentration. Also, 2.0 mM of 2-mercaptoethanesulfonate had about the same effect on the anion separation as 60 mM KOH. Finally, selectivity and detection limits were investigated. The detection limits were 4.9 μM for mercury and 2.2 μM for cadmium.

  10. Highly effective yet simple transmembrane anion transporters based upon ortho-phenylenediamine bis-ureas.

    PubMed

    Karagiannidis, Louise E; Haynes, Cally J E; Holder, Katie J; Kirby, Isabelle L; Moore, Stephen J; Wells, Neil J; Gale, Philip A

    2014-10-18

    Simple, highly fluorinated receptors are shown to function as highly effective transmembrane anion antiporters with the most active transporters rivalling the transport efficacy of natural anion transporter prodigiosin for bicarbonate.

  11. A dual-emissive ionic liquid based on an anionic platinum(ii) complex.

    PubMed

    Ogawa, Tomohiro; Yoshida, Masaki; Ohara, Hiroki; Kobayashi, Atsushi; Kato, Masako

    2015-09-07

    An ionic liquid fabricated from an anionic cyclometalated platinum(ii) complex and an imidazolium cation exhibits dual emission from the monomeric and aggregated forms of the platinum complex anions, leading to temperature-dependent color changes of luminescence.

  12. Dietary inorganic nitrate: From villain to hero in metabolic disease?

    PubMed

    McNally, Ben; Griffin, Julian L; Roberts, Lee D

    2016-01-01

    Historically, inorganic nitrate was believed to be an inert by-product of nitric oxide (NO) metabolism that was readily excreted by the body. Studies utilising doses of nitrate far in excess of dietary and physiological sources reported potentially toxic and carcinogenic effects of the anion. However, nitrate is a significant component of our diets, with the majority of the anion coming from green leafy vegetables, which have been consistently shown to offer protection against obesity, type 2 diabetes and metabolic diseases. The discovery of a metabolic pathway in mammals, in which nitrate is reduced to NO, via nitrite, has warranted a re-examination of the physiological role of this small molecule. Obesity, type 2 diabetes and the metabolic syndrome are associated with a decrease in NO bioavailability. Recent research suggests that the nitrate-nitrite-NO pathway may be harnessed as a therapeutic to supplement circulating NO concentrations, with both anti-obesity and anti-diabetic effects, as well as improving vascular function. In this review, we examine the key studies that have led to the re-evaluation of the physiological function of inorganic nitrate, from toxic and carcinogenic metabolite, to a potentially important and beneficial agent in the treatment of metabolic disease.

  13. Dietary inorganic nitrate: From villain to hero in metabolic disease?

    PubMed Central

    McNally, Ben; Griffin, Julian L.

    2015-01-01

    Historically, inorganic nitrate was believed to be an inert by‐product of nitric oxide (NO) metabolism that was readily excreted by the body. Studies utilising doses of nitrate far in excess of dietary and physiological sources reported potentially toxic and carcinogenic effects of the anion. However, nitrate is a significant component of our diets, with the majority of the anion coming from green leafy vegetables, which have been consistently shown to offer protection against obesity, type 2 diabetes and metabolic diseases. The discovery of a metabolic pathway in mammals, in which nitrate is reduced to NO, via nitrite, has warranted a re‐examination of the physiological role of this small molecule. Obesity, type 2 diabetes and the metabolic syndrome are associated with a decrease in NO bioavailability. Recent research suggests that the nitrate‐nitrite‐NO pathway may be harnessed as a therapeutic to supplement circulating NO concentrations, with both anti‐obesity and anti‐diabetic effects, as well as improving vascular function. In this review, we examine the key studies that have led to the re‐evaluation of the physiological function of inorganic nitrate, from toxic and carcinogenic metabolite, to a potentially important and beneficial agent in the treatment of metabolic disease. PMID:26227946

  14. Photonic band gap structure simulator

    DOEpatents

    Chen, Chiping; Shapiro, Michael A.; Smirnova, Evgenya I.; Temkin, Richard J.; Sirigiri, Jagadishwar R.

    2006-10-03

    A system and method for designing photonic band gap structures. The system and method provide a user with the capability to produce a model of a two-dimensional array of conductors corresponding to a unit cell. The model involves a linear equation. Boundary conditions representative of conditions at the boundary of the unit cell are applied to a solution of the Helmholtz equation defined for the unit cell. The linear equation can be approximated by a Hermitian matrix. An eigenvalue of the Helmholtz equation is calculated. One computation approach involves calculating finite differences. The model can include a symmetry element, such as a center of inversion, a rotation axis, and a mirror plane. A graphical user interface is provided for the user's convenience. A display is provided to display to a user the calculated eigenvalue, corresponding to a photonic energy level in the Brilloin zone of the unit cell.

  15. Updated Starshade Technology Gap List

    NASA Astrophysics Data System (ADS)

    Crill, Brendan P.; Siegler, Nicholas

    2017-01-01

    NASA's Exoplanet Exploration Program (ExEP) guides the development of technology that enables the direct imaging and characterization of exo-Earths in the habitable zone of their stars, for future space observatories. Here we present the Starshade portion of the 2017 ExEP Enabling Technology Gap List, an annual update to ExEP's list of of technology to be advanced in the next 1-5 years. A Starshade is an external occulter on an independent spacecraft, allowing a space telescope to achieve exo-Earth imaging contrast requirements by blocking starlight before it enters the telescope. Building and operating a Starshade requires new technology: the occulter is a structure tens of meters in diameter that must be positioned precisely at a distance of tens of thousands of kilometers from the telescope. We review the current state-of-the-art performance and the performance level that must be achieved for a Starshade.

  16. Contact transfer of anions from hands as a function of the use of hand lotions

    NASA Technical Reports Server (NTRS)

    Welker, R. W.; Schulman, M.

    2001-01-01

    Contact transfer of anions from human hands can result in contamination of materials, increasing their rate of corrosion. Two types of hand lotion were applied to the hands: one was specially formulated for cleanroom use and the other was a popular commercial lotion. The effect on contact transfer of anions was measured versus anion transfer from washed hands without lotions.

  17. Narrow gap electronegative capacitive discharges

    SciTech Connect

    Kawamura, E.; Lieberman, M. A.; Lichtenberg, A. J.

    2013-10-15

    Narrow gap electronegative (EN) capacitive discharges are widely used in industry and have unique features not found in conventional discharges. In this paper, plasma parameters are determined over a range of decreasing gap length L from values for which an electropositive (EP) edge exists (2-region case) to smaller L-values for which the EN region connects directly to the sheath (1-region case). Parametric studies are performed at applied voltage V{sub rf}=500 V for pressures of 10, 25, 50, and 100 mTorr, and additionally at 50 mTorr for 1000 and 2000 V. Numerical results are given for a parallel plate oxygen discharge using a planar 1D3v (1 spatial dimension, 3 velocity components) particle-in-cell (PIC) code. New interesting phenomena are found for the case in which an EP edge does not exist. This 1-region case has not previously been investigated in detail, either numerically or analytically. In particular, attachment in the sheaths is important, and the central electron density n{sub e0} is depressed below the density n{sub esh} at the sheath edge. The sheath oscillations also extend into the EN core, creating an edge region lying within the sheath and not characterized by the standard diffusion in an EN plasma. An analytical model is developed using minimal inputs from the PIC results, and compared to the PIC results for a base case at V{sub rf}=500 V and 50 mTorr, showing good agreement. Selected comparisons are made at the other voltages and pressures. A self-consistent model is also developed and compared to the PIC results, giving reasonable agreement.

  18. Production of bulk chemicals via novel metabolic pathways in microorganisms.

    PubMed

    Shin, Jae Ho; Kim, Hyun Uk; Kim, Dong In; Lee, Sang Yup

    2013-11-01

    Metabolic engineering has been playing important roles in developing high performance microorganisms capable of producing various chemicals and materials from renewable biomass in a sustainable manner. Synthetic and systems biology are also contributing significantly to the creation of novel pathways and the whole cell-wide optimization of metabolic performance, respectively. In order to expand the spectrum of chemicals that can be produced biotechnologically, it is necessary to broaden the metabolic capacities of microorganisms. Expanding the metabolic pathways for biosynthesizing the target chemicals requires not only the enumeration of a series of known enzymes, but also the identification of biochemical gaps whose corresponding enzymes might not actually exist in nature; this issue is the focus of this paper. First, pathway prediction tools, effectively combining reactions that lead to the production of a target chemical, are analyzed in terms of logics representing chemical information, and designing and ranking the proposed metabolic pathways. Then, several approaches for potentially filling in the gaps of the novel metabolic pathway are suggested along with relevant examples, including the use of promiscuous enzymes that flexibly utilize different substrates, design of novel enzymes for non-natural reactions, and exploration of hypothetical proteins. Finally, strain optimization by systems metabolic engineering in the context of novel metabolic pathways constructed is briefly described. It is hoped that this review paper will provide logical ways of efficiently utilizing 'big' biological data to design and develop novel metabolic pathways for the production of various bulk chemicals that are currently produced from fossil resources.

  19. Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

    PubMed

    Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2017-02-15

    Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4 N(+) )2 [M(III) (HFl-O(-) )(Pc(.3-) )](.-) (Br(-) )⋅1.5 C6 H4 Cl2 [M=Al (1), Ga (2); HFl-O(-) =fluoren-9-olato(-) anion; Pc=phthalocyanine] and (Bu4 N(+) ) [In(III) Br(Pc(.3-) )](.-) ⋅0.875 C6 H4 Cl2 ⋅0.125 C6 H14 (3). The salts were found to contain Pc(.3-) radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc(.3-) in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O(-) anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C-O bonds [1.402(3) and 1.391(11) Å in 1 and 2, respectively] in the HFl-O(-) anions are longer than the same bond in the fluorenone ketyl (1.27-1.31 Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79 μB at 300 K, respectively, owing to the presence of unpaired S=1/2 spins on Pc(.3-) . These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30 K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/kB =-0.9 and -1.1 K, respectively, and in the π-stacking {[In(III) Br(Pc(.3-) )](.-) }2 dimers of 3 with an exchange interaction of J/kB =-10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc(.3-) . It was found that increasing the size of the central metal atom strongly broadened these EPR signals.

  20. Designing a Quantitative Structure-Activity Relationship for the Intrinsic Metabolic Clearance of Environmentally Relevant Chemicals

    EPA Science Inventory

    Toxicokinetic models serve a vital role in risk assessment by bridging the gap between chemical exposure and potentially toxic endpoints. While intrinsic metabolic clearance rates have a strong impact on toxicokinetics, limited data is available for environmentally relevant chemi...

  1. Astroglial Metabolic Networks Sustain Hippocampal Synaptic Transmission

    NASA Astrophysics Data System (ADS)

    Rouach, Nathalie; Koulakoff, Annette; Abudara, Veronica; Willecke, Klaus; Giaume, Christian

    2008-12-01

    Astrocytes provide metabolic substrates to neurons in an activity-dependent manner. However, the molecular mechanisms involved in this function, as well as its role in synaptic transmission, remain unclear. Here, we show that the gap-junction subunit proteins connexin 43 and 30 allow intercellular trafficking of glucose and its metabolites through astroglial networks. This trafficking is regulated by glutamatergic synaptic activity mediated by AMPA receptors. In the absence of extracellular glucose, the delivery of glucose or lactate to astrocytes sustains glutamatergic synaptic transmission and epileptiform activity only when they are connected by gap junctions. These results indicate that astroglial gap junctions provide an activity-dependent intercellular pathway for the delivery of energetic metabolites from blood vessels to distal neurons.

  2. Physics of metabolic organization.

    PubMed

    Jusup, Marko; Sousa, Tânia; Domingos, Tiago; Labinac, Velimir; Marn, Nina; Wang, Zhen; Klanjšček, Tin

    2017-03-01

    We review the most comprehensive metabolic theory of life existing to date. A special focus is given to the thermodynamic roots of this theory and to implications that the laws of physics-such as the conservation of mass and energy-have on all life. Both the theoretical foundations and biological applications are covered. Hitherto, the foundations were more accessible to physicists or mathematicians, and the applications to biologists, causing a dichotomy in what always should have been a single body of work. To bridge the gap between the two aspects of the same theory, we (i) adhere to the theoretical formalism, (ii) try to minimize the amount of information that a reader needs to process, but also (iii) invoke examples from biology to motivate the introduction of new concepts and to justify the assumptions made, and (iv) show how the careful formalism of the general theory enables modular, self-consistent extensions that capture important features of the species and the problem in question. Perhaps the most difficult among the introduced concepts, the utilization (or mobilization) energy flow, is given particular attention in the form of an original and considerably simplified derivation. Specific examples illustrate a range of possible applications-from energy budgets of individual organisms, to population dynamics, to ecotoxicology.

  3. Physics of metabolic organization

    NASA Astrophysics Data System (ADS)

    Jusup, Marko; Sousa, Tânia; Domingos, Tiago; Labinac, Velimir; Marn, Nina; Wang, Zhen; Klanjšček, Tin

    2017-03-01

    We review the most comprehensive metabolic theory of life existing to date. A special focus is given to the thermodynamic roots of this theory and to implications that the laws of physics-such as the conservation of mass and energy-have on all life. Both the theoretical foundations and biological applications are covered. Hitherto, the foundations were more accessible to physicists or mathematicians, and the applications to biologists, causing a dichotomy in what always should have been a single body of work. To bridge the gap between the two aspects of the same theory, we (i) adhere to the theoretical formalism, (ii) try to minimize the amount of information that a reader needs to process, but also (iii) invoke examples from biology to motivate the introduction of new concepts and to justify the assumptions made, and (iv) show how the careful formalism of the general theory enables modular, self-consistent extensions that capture important features of the species and the problem in question. Perhaps the most difficult among the introduced concepts, the utilization (or mobilization) energy flow, is given particular attention in the form of an original and considerably simplified derivation. Specific examples illustrate a range of possible applications-from energy budgets of individual organisms, to population dynamics, to ecotoxicology.

  4. [Gap edge effect of Castanopsis kawakamii community].

    PubMed

    Liu, Jinfu; Hong, Wei; Li, Junqing; Lin, Rongfu

    2003-09-01

    This paper reported the characters of gap edge effect of Castanopsis kawakamii community in Sanming, Fujian Province. The species diversity, ecological dominance, and edge effect strength of 38 forest gaps with different development stages in different stands of Castanopsis kawakamii community were measured, and Shannon-Wiener index, Simpson index, and index of edge effect strength were calculated. The results showed that the index of the gap edge effect of Castanopsis kawakamii community was about 0.7-1.3 (according to the species diversity index) and 0.3-1.8 (according to the ecological dominance index). The gap edge effect had the trend of increasing the species diversity of forest communities. The index of gap effect was affected by the size and development stage of the gap and the related forest type. The study provided a theoretical basis for the maintenance of species diversity and the forest management in Castanopsis kawakamii community.

  5. National GAP Conference 2007-Discussion Groups Report

    USGS Publications Warehouse

    Ratz, Joan M.; Lamb, Berton Lee

    2010-01-01

    We led two discussion groups during the 2007 National GAP Conference. These discussion groups provided information to help develop a survey of National Gap Analysis Program (GAP) data users. One group discussed technical issues, and the second group discussed the use of GAP data for decisionmaking. Themes emerging from the technical issues group included concerns about data quality, need for information on how to use data, and passive data distribution. The decisionmaking discussion included a wide range of topics including the need to understand presentation of information, the need to connect with and understand users of data, the revision of GAP's mission, and the adaptability of products and data. The decisionmaking group also raised concerns regarding technical issues. One conclusion is that a deep commitment to ongoing information transfer and support is a key component of success for the GAP program.

  6. Macrocyclic bis(ureas) as ligands for anion complexation

    PubMed Central

    Kretschmer, Claudia; Dittmann, Gertrud

    2014-01-01

    Summary Two macrocyclic bis(ureas) 1 and 2, both based on diphenylurea, have been synthesized. Compound 1 represents the smaller ring with two ethynylene groups as linkers and 2 the larger ring with two butadiynylene groups. On thermal treatment to 130 °C molecule 1 splits up into two dihydroindoloquinolinone (3) molecules. Both compounds 1 and 2 form adducts with polar molecules such as dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and act as complexing agents towards a series of anions (Cl−, Br−, I−, NO3 −, HSO4 −). The crystal structures of 3, 2·2DMSO, 2·2DMF, and of the complex NEt4[Br·2] have been determined. Quantitative investigations of the complexation equilibria were performed via 1H NMR titrations. While 1 is a rather weak complexing agent, the large ring of 2 binds anions with association constants up to log K = 7.93 for chloride ions. PMID:25161744

  7. Anion-switchable supramolecular gels for controlling pharmaceutical crystal growth

    NASA Astrophysics Data System (ADS)

    Foster, Jonathan A.; Piepenbrock, Marc-Oliver M.; Lloyd, Gareth O.; Clarke, Nigel; Howard, Judith A. K.; Steed, Jonathan W.

    2010-12-01

    We describe the use of low-molecular-weight supramolecular gels as media for the growth of molecular crystals. Growth of a range of crystals of organic compounds, including pharmaceuticals, was achieved in bis(urea) gels. Low-molecular-weight supramolecular gelators allow access to an unlimited range of solvent systems, in contrast to conventional aqueous gels such as gelatin and agarose. A detailed study of carbamazepine crystal growth in four different bis(urea) gelators, including a metallogelator, is reported. The crystallization of a range of other drug substances, namely sparfloxacin, piroxicam, theophylline, caffeine, ibuprofen, acetaminophen (paracetamol), sulindac and indomethacin, was also achieved in supramolecular gel media without co-crystal formation. In many cases, crystals can be conveniently recovered from the gels by using supramolecular anion-triggered gel dissolution; however, crystals of substances that themselves bind to anions are dissolved by them. Overall, supramolecular gel-phase crystallization offers an extremely versatile new tool in pharmaceutical polymorph screening.

  8. The role of catalyst precursor anions in coal gasification

    SciTech Connect

    Abotsi, G.M.K.

    1992-01-01

    The aims of the proposed project are to enrich our understanding of the roles of various aqueous soluble catalyst precursor anions on the surface electrical properties of coal and to ascertain the influence of the surface charge on the adsorption, dispersion, and activities of calcium and potassium. These goals will be achieved by impregnating a lignite and its demineralized derivative with calcium or potassium catalyst precursors containing acetate (CH{sub 3}COO{minus}), chloride (Cl{minus}), nitrate (NO{sub 3}{minus}), sulfate (SO{sub 4}{sup 2{minus}}), and carbonate (CO{sub 3}{sup 2{minus}}) anions. Catalyst loading will be conducted under well-controlled conditions of solution pH and ionic strength.

  9. Anionic lipids and the maintenance of membrane electrostatics in eukaryotes

    PubMed Central

    Platre, Matthieu Pierre

    2017-01-01

    ABSTRACT A wide range of signaling processes occurs at the cell surface through the reversible association of proteins from the cytosol to the plasma membrane. Some low abundant lipids are enriched at the membrane of specific compartments and thereby contribute to the identity of cell organelles by acting as biochemical landmarks. Lipids also influence membrane biophysical properties, which emerge as an important feature in specifying cellular territories. Such parameters are crucial for signal transduction and include lipid packing, membrane curvature and electrostatics. In particular, membrane electrostatics specifies the identity of the plasma membrane inner leaflet. Membrane surface charges are carried by anionic phospholipids, however the exact nature of the lipid(s) that powers the plasma membrane electrostatic field varies among eukaryotes and has been hotly debated during the last decade. Herein, we discuss the role of anionic lipids in setting up plasma membrane electrostatics and we compare similarities and differences that were found in different eukaryotic cells. PMID:28102755

  10. Dissolution of cellulose in room temperature ionic liquids: anion dependence.

    PubMed

    Payal, Rajdeep Singh; Bejagam, Karteek K; Mondal, Anirban; Balasubramanian, Sundaram

    2015-01-29

    The dissolution of cellulosic biomass in room temperature ionic liquids (RTILs) is studied through free energy calculations of its monomer, viz., cellobiose, within a molecular dynamics simulation approach. The solvation free energy (SFE) of cellobiose in ionic liquids containing any of seven different anions has been calculated. The ranking of these liquids based on SFE compares well with experimental data on the solubility of cellulose. The dissolution is shown to be enthalpically dominated, which is correlated with the strength of intermolecular hydrogen bonding between cellobiose and the anions of the IL. Large entropic changes upon solvation in [CF3SO3](-) and [OAc](-) based ionic liquids have been explained in terms of the solvent-aided conformational flexibility of cellobiose.

  11. Determination of sulphide by anion-exchange with lead iodate.

    PubMed

    Verma, K K; Gupta, D; Sanghi, S K; Jain, A

    1988-11-01

    A quick anion-exchange reaction, suitable for the determination of sulphide, has been found to occur on stirring a suspension of lead iodate (solubility product, K(s0) = 1.2 x 10(-13)) with sulphide solution at pH 5-8. After removal of the precipitates of lead iodate and lead sulphide (K(s0) = 3.4 x 10(-28)), the iodate released can be determined by its reaction with acidified iodide to give tri-iodide which is either titrated with thiosulphate or measured spectrophotometrically as its blue complex with starch. Chloride, bromide, iodide, fluoride, oxalate, sulphate, thiocyanate and phosphate do not interfere. Thiosulphate, sulphite, nitrite and thiols do not give an anion-exchange reaction but do interfere in the redox reaction of iodate with acidified iodide. However, this is avoided if they are first oxidized with bromine (the liberated iodate remains unaffected before iodometry.

  12. Epithelial Anion Transport as Modulator of Chemokine Signaling

    PubMed Central

    Schnúr, Andrea; Hegyi, Péter; Rousseau, Simon; Lukacs, Gergely L.; Veit, Guido

    2016-01-01

    The pivotal role of epithelial cells is to secrete and absorb ions and water in order to allow the formation of a luminal fluid compartment that is fundamental for the epithelial function as a barrier against environmental factors. Importantly, epithelial cells also take part in the innate immune system. As a first line of defense they detect pathogens and react by secreting and responding to chemokines and cytokines, thus aggravating immune responses or resolving inflammatory states. Loss of epithelial anion transport is well documented in a variety of diseases including cystic fibrosis, chronic obstructive pulmonary disease, asthma, pancreatitis, and cholestatic liver disease. Here we review the effect of aberrant anion secretion with focus on the release of inflammatory mediators by epithelial cells and discuss putative mechanisms linking these transport defects to the augmented epithelial release of chemokines and cytokines. These mechanisms may contribute to the excessive and persistent inflammation in many respiratory and gastrointestinal diseases. PMID:27382190

  13. Highly Water Resistant Anion Exchange Membrane for Fuel Cells.

    PubMed

    Yang, Zhengjin; Hou, Jianqiu; Wang, Xinyu; Wu, Liang; Xu, Tongwen

    2015-07-01

    For anion exchange membranes (AEMs), achieving efficient hydroxide conductivity without excessive hydrophilicity presents a challenge. Hence, new strategies for constructing mechanically strengthened and hydroxide conductive (especially at controlled humidity) membranes are critical for developing better AEMs. Macromolecular modification involving ylide chemistry (Wittig reaction) for the fabrication of novel AEMs with an interpenetrating polymer network structure is reported. The macromolecular modification is cost effective, facile, and based on a one-pot synthesis. AEM water uptake is reduced to 3.6 wt% and a high hydroxide conductivity (69.7 mS cm(-1) , 90 °C) is achieved simultaneously. More importantly, the membrane exhibits similar tensile strength (>35 MPa) and comparable flexibility in both dry and wet states. These AEMs could find further applications within anion exchange membrane fuel cells with low humidity or photoelectric assemblies.

  14. Photoelectron Angular Distribution and Molecular Structure in Multiply Charged Anions

    SciTech Connect

    Xing, Xiaopeng; Wang, Xue B.; Wang, Lai S.

    2009-02-12

    Photoelectrons emitted from multiply charged anions (MCAs) carry information of the intramolecular Coulomb repulsion (ICR), which is dependent on molecular structures. Using photoelectron imaging, we observed the effects of ICR on photoelectron angular distributions (PAD) of the three isomers of benzene dicarboxylate dianions C6H4(CO2)22– (o-, m- and p-BDC2–). Photoelectrons were observed to peak along the laser polarization due to the ICR, but the anisotropy was the largest for p-BDC2–, followed by the m- and o-isomer. The observed anisotropy is related to the direction of the ICR or the detailed molecular structures, suggesting that photoelectron imaging may allow structural information to be obtained for complex multiply charged anions.

  15. Gap between active and passive solar heating

    SciTech Connect

    Balcomb, J.D.

    1985-01-01

    The gap between active and passive solar could hardly be wider. The reasons for this are discussed and advantages to narrowing the gap are analyzed. Ten years of experience in both active and passive systems are reviewed, including costs, frequent problems, performance prediction, performance modeling, monitoring, and cooling concerns. Trends are analyzed, both for solar space heating and for service water heating. A tendency for the active and passive technologies to be converging is observed. Several recommendations for narrowing the gap are presented.

  16. The Hydroacoustics of Beveled Steps and Gaps

    DTIC Science & Technology

    2015-11-01

    to measure and predict the sound radiation from steps and gaps on large pales excited by turbulent boundary layers. Results are given showing the...the last few years there have been some enlightening experimental and numerical studies on the sound radiated by turbulent flow over steps and gaps...used to predict the sound radiated from steps and gaps at full scale. The purpose of this study was to develop these scaling laws by combining the

  17. Four-wave-mixing gap solitons

    SciTech Connect

    Zhang Yanpeng; Wang Zhiguo; Zheng Huaibin; Yuan Chenzhi; Li Changbiao; Lu Keqing; Xiao Min

    2010-11-15

    We report an experimental demonstration of generating gap soliton trains in a four-wave-mixing (FWM) signal. Such spatial FWM surfacelike gap soliton trains are induced in a periodically modulated self-defocusing atomic medium by the cross-phase modulation, which can be reshaped under different experimental conditions, such as different atomic densities, nonlinear dispersions, and dressing fields. Controlling spatial gap solitons can have important applications in image memory, processing, and communication.

  18. Removal of Pesticides from Water by Anionic Clays

    NASA Astrophysics Data System (ADS)

    Lakraimi, M.; Legrouri, A.; Barroug, A.; de Roy, A.; Besse, J.-P.

    1999-03-01

    The exchange of chloride ions by ions from the pesticide family 2.4-dichlorophe- noxyacetate (2.4D) in ?Zn-Al-Cl? anionic clay was investigated by X-ray diffraction and infrared spectroscopy. The effects of 2.4D concentration in solution and temperature on the ion exchange were studied. The best sample in terms of crystallinity, was obtained at 100°C with a 2.4D concentration corresponding to the solubility limit of the ion in water. This sample was further characterised by chemical analyses and scanning electron microscopy. The anion intercalation was effected without degradation of the pesticide anion. L'échange des ions chlorure par les ions d'une molécule appartenant à la famille des pesticides 2,4-dichlorophénoxyacétate (2,4D) dans l'argile anionique [Zn-Al-Cl] a été étudiée par diffraction des rayons X et spectroscopie infrarouge. Les influences de la concentration en 2,4D de la solution d'échange et de la température ont été étudiées afin d'optimiser les conditions de l'échange. La meilleure cristallinité a été obtenue à 100°C dans une solution 0.004 M en 2,4D. Une phase préparée dans ces conditions a été caractérisée par analyse chimique et microscopie électronique à balayage. L'échange a été réalisée sans dégradation de l'anion pesticide.

  19. Salts of alkali metal anions and process of preparing same

    DOEpatents

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  20. Anion Exchange Membranes: Current Status and Moving Forward

    SciTech Connect

    Hickner, MA; Herring, AM; Coughlin, EB

    2013-10-29

    This short review is meant to provide the reader with highlights in anion exchange membrane research, describe current needs in the field, and point out promising directions for future work. Anion exchange membranes (AEMs) provide one possible route to low platinum or platinum-free fuel cells with the potential for facile oxidation of complex fuels beyond hydrogen and methanol. AEMs and related stable cationic polymers also have applications in energy storage and other electrochemical technologies such as water electrolyzers and redox flow batteries. While anion exchange membranes have been known for a long time in water treatment applications, materials for electrochemical technology with robust mechanical properties in thin film format have only recently become more widely available. High hydroxide and bicarbonate anion conductivity have been demonstrated in a range of AEM formats, but intrinsic stability of the polymers and demonstration of long device lifetime remain major roadblocks. Novel approaches to stable materials have focused on new types of cations that employ delocalization and steric shielding of the positive center to mitigate nucleophilic attack by hydroxide. A number of promising polymer backbones and membrane architectures have been identified, but limited device testing and a lack of understanding of the degradation mechanisms in operating devices is slowing progress on engineered systems with alkaline fuel cell technology. Our objective is to spur more research in this area to develop fuel cell systems that approach the costs of inexpensive batteries for large-scale applications. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1727-1735, 2013

  1. A method for production of new anion exchangers

    NASA Astrophysics Data System (ADS)

    Behrendt, G.; Hunger, H. D.

    1991-12-01

    The invention relates to a method for the production of new anion exchangers that can be used in molecular biology, genetic engineering, biotechnology, and phytopathology. According to the invention, halogen-containing polyurethanes are reacted with one or more tertiary amines. By the method, polyurethane shapes with positive surface charges are produced from preformed shapes, with preservation of the form and properties thereof. The products have thermally stable bonds with biomolecules together with high binding capacity.

  2. A Reinvestigation of the Reactions of Enolate Anions with Cyclotriphosphazenes.

    DTIC Science & Technology

    1981-09-09

    PERFORMING ORG. REPORT NUMBER 7. AUTNOR(e) - . CONTRACT OR GRANT NUMESER(.) Christopher W. Allen, Kolikkara Ramachandran N001477C-0605 Randall P. Bright and...REACTIONS OF ENOLATE ANIONS WITH CYCLOTRIPHOSPHAZENES Christopher W. Allen, Kolikkara Ramachandran , Randall P. Bright and Jonathan C. Shaw Department...four days. The solvent was re- moved and the residue extracted with hexane. Following filtration and removal of hexane, 10.2 g of a pale yellow liquid

  3. Development of anion-selective membranes. [for energy storage

    NASA Technical Reports Server (NTRS)

    Lacey, R. E.; Cowsar, D. R.

    1975-01-01

    Methods were studied of preparing anion-exchange membranes that would have low resistance, high selectivity, and physical and chemical stability when used in acidic media in a redox energy storage system. Of the twelve systems selected for study, only the system that was based on crosslinked poly-4-vinylpyridinium chloride produced physically strong membranes when equilibrated in l M HCl. The resistivity of the best membrane was 12 ohm-cm, and the transference number for chloride ions was 0.81.

  4. Interactions between anionic and neutral bromine and rare gas atoms

    SciTech Connect

    Buchachenko, Alexei A.; Grinev, Timur A.; Wright, Timothy G.; Viehland, Larry A.

    2008-02-14

    High-quality, ab initio potential energy functions are obtained for the interaction of bromine atoms and anions with atoms of the six rare gases (Rg) from He to Rn. The potentials of the nonrelativistic {sup 2}{sigma}{sup +} and {sup 2}{pi} electronic states arising from the ground-state Br({sup 2}P)-Rg interactions are computed over a wide range of internuclear separations using a spin-restricted version of the coupled cluster method with single and double excitations and noniterative correction to triple excitations [RCCSD(T)] with an extrapolation to the complete basis set limit, from basis sets of d-aug-cc-pVQZ and d-aug-cc-pV5Z quality. These are compared with potentials derived previously from experimental measurements and ab initio calculations. The same approach is used also to refine the potentials of the Br{sup -}-Rg anions obtained previously [Buchachenko et al., J. Chem. Phys. 125, 064305 (2006)]. Spin-orbit coupling in the neutral species is included both ab initio and via an atomic approximation; deviations between two approaches that are large enough to affect the results significantly are observed only in the Br-Xe and Br-Rn systems. The resulting relativistic potentials are used to compute anion zero electron kinetic energy photoelectron spectra, differential scattering cross sections, and the transport coefficients of trace amounts of both anionic and neutral bromine in the rare gases. Comparison with available experimental data for all systems considered proves a very high precision of the present potentials.

  5. Mechanical Characterization of Anion Exchange Membranes Under Controlled Environmental Conditions

    DTIC Science & Technology

    2015-05-11

    membranes (AEM) have the potential to dramatically lower the cost of fuel cells by utilizing non-noble catalysts and a variety of fuel sources. Although...the cost of fuel cells by utilizing non-noble catalysts and a variety of fuel sources. Although chemical degradation typically dominates membrane...anion exchange membranes (AEM) have the potential to dramatically lower the cost of fuel cells by utilizing non-noble catalysts and a variety of

  6. Predicting Carbonate Ion Transport in Alkaline Anion Exchange Materials

    DTIC Science & Technology

    2012-01-01

    Schematic of the permeation cell experiment used to measure transient CO2 flux across the polymer electrolyte membrane. Experimental result vs. model trend...Microstructure on Charge Transfer, Mass Transfer, and Electrochemical Reactions in Solid Oxide Fuel Cells ; Part 2. Ion and Water Transport in Alkaline Anion...through the use of the Fuel Cell Technologies Test Station such as the relative humidity and flow rate of the feed gases, the cell temperature, and the

  7. Polarizabilities of the alkali anions: Li- to Fr-.

    PubMed

    Lupinetti, Concetta; Thakkar, Ajit J

    2006-11-21

    Static dipole polarizabilities are calculated for the ground states of the alkali anions from Li- to Fr-. The polarizabilities include scalar relativistic effects at the second-order Douglas-Kroll level and were computed using the finite-field, coupled-cluster CCSD(T) method with large, carefully optimized basis sets. The relativistic polarizabilities increase with Z, reach a maximum at Cs-, and then decrease again unlike their nonrelativistic counterparts which increase monotonically with Z.

  8. Anion receptor compounds for non-aqueous electrolytes

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    2000-09-19

    A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  9. Anion Recognition as a Supramolecular Switch of Cell Internalization

    PubMed Central

    Couceiro, José R.; Nitschke, Jonathan R.; Vázquez, M. Eugenio; Mascareñas, José L.

    2017-01-01

    The cell internalization of designed oligoarginine peptides equipped with six glutamic acid residues and an anionic pyranine at the N-terminus is triggered upon addition of a supramolecular host. This host binds specifically to the pyranine moiety, enabling the complex to traverse the cell membrane. Interestingly, none of the components, neither the host nor the guest, are able to cross the cell membrane on their own. PMID:27984855

  10. Carbohydrate Metabolism Disorders

    MedlinePlus

    Metabolism is the process your body uses to make energy from the food you eat. Food is ... disorder, something goes wrong with this process. Carbohydrate metabolism disorders are a group of metabolic disorders. Normally ...

  11. Blueberries and Metabolic Syndrome

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Metabolic Syndrome is a cluster of metabolic disorders that increase the risk of cardiovascular diseases. Type 2 diabetes, elevated blood pressure, and atherogenic dyslipidemia are among the metabolic alterations that predispose the individual to several adverse cardiovascular complications. The hea...

  12. Gap Assessment (FY 13 Update)

    DOE Data Explorer

    Getman, Dan

    2013-09-30

    To help guide its future data collection efforts, The DOE GTO funded a data gap analysis in FY2012 to identify high potential hydrothermal areas where critical data are needed. This analysis was updated in FY2013 and the resulting datasets are represented by this metadata. The original process was published in FY 2012 and is available here: https://pangea.stanford.edu/ERE/db/GeoConf/papers/SGW/2013/Esposito.pdf Though there are many types of data that can be used for hydrothermal exploration, five types of exploration data were targeted for this analysis. These data types were selected for their regional reconnaissance potential, and include many of the primary exploration techniques currently used by the geothermal industry. The data types include: 1. well data 2. geologic maps 3. fault maps 4. geochemistry data 5. geophysical data To determine data coverage, metadata for exploration data (including data type, data status, and coverage information) were collected and catalogued from nodes on the National Geothermal Data System (NGDS). It is the intention of this analysis that the data be updated from this source in a semi-automated fashion as new datasets are added to the NGDS nodes. In addition to this upload, an online tool was developed to allow all geothermal data providers to access this assessment and to directly add metadata themselves and view the results of the analysis via maps of data coverage in Geothermal Prospector (http://maps.nrel.gov/gt_prospector). A grid of the contiguous U.S. was created with 88,000 10-km by 10-km grid cells, and each cell was populated with the status of data availability corresponding to the five data types. Using these five data coverage maps and the USGS Resource Potential Map, sites were identified for future data collection efforts. These sites signify both that the USGS has indicated high favorability of occurrence of geothermal resources and that data gaps exist. The uploaded data are contained in two data files for

  13. Phosphate Removal by Anion Binding on Functionalized Nanoporous Sorbents

    PubMed Central

    Chouyyok, Wilaiwan; Wiacek, Robert J.; Pattamakomsan, Kanda; Sangvanich, Thanapon; Grudzien, Rafal M.; Fryxell, Glen E.; Yantasee, Wassana

    2010-01-01

    Phosphate was captured from aqueous solutions by cationic metal-EDA complexes anchored inside mesoporous silica MCM-41 supports (Cu(II)-EDA-SAMMS and Fe(III)-EDA-SAMMS). Fe-EDA-SAMMS was more effective at capturing phosphate than the Cu-EDA-SAMMS and was further studied for matrix effects (e.g., pH, ionic strength, and competing anions) and sorption performance (e.g., capacity and rate). The adsorption of phosphate was highly pH dependent; it increased with increasing pH from 1.0 to 6.5, and decreased above pH 6.5. The adsorption was affected by high ionic strength (0.1 M of NaCl). In the presence of 1000-fold molar excess of chloride and nitrate anions, phosphate removal by Fe-EDA-SAMMS was not affected. Slight, moderate and large impacts were seen with bicarbonate, sulfate and citrate anions, respectively. The phosphate adsorption data on Fe-EDA-SAMMS agreed well with the Langmuir model with the estimated maximum capacity of 43.3 mg/g. The material displayed rapid sorption rate (99% of phosphate removal within 1 min) and lowering the phosphate content to ~ 10 µg/L of phosphorus, which is lower than the EPA’s established freshwater contaminant level for phosphorous (20 µg/L). PMID:20345133

  14. Coumarin benzothiazole derivatives as chemosensors for cyanide anions.

    PubMed

    Wang, Kangnan; Liu, Zhiqiang; Guan, Ruifang; Cao, Duxia; Chen, Hongyu; Shan, Yanyan; Wu, Qianqian; Xu, Yongxiao

    2015-06-05

    Four coumarin benzothiazole derivatives, N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (1), (Z)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide (2), 7-(diethylamino)-N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (3) and (Z)-7-(diethylamino)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide) (4), have been synthesized. Their crystal structures, photophysical properties in acetonitrile and recognition properties for cyanide anions have been investigated. All the compounds are generally planar, especially compound 1 exhibits perfect planarity with dihedral angle between benzothiazolyl group and coumarin group being only 3.63°. Coumarin benzothiazole compounds 1 and 3 can recognize cyanide anions by Michael addition reaction and compound 3 exhibits color change from yellow to colorless and green fluorescence was quenched completely, which can be observed by naked eye. Coumarin benzothiazolyliden compound 4 can recognize cyanide anions with fluorescence turn-on response based on the copper complex ensemble displacement mechanism.

  15. Selected boron, aluminum, and gallium trihalide and trihydride anions

    NASA Astrophysics Data System (ADS)

    Brzeski, Jakub; Czapla, Marcin; Skurski, Piotr; Simons, Jack

    2017-01-01

    Ab initio methods with flexible orbital basis sets are used to examine the electron binding strengths of tri-fluorides, tri-chlorides, and tri-hydrides of B, Al, and Ga. The adiabatic electron affinities are found to increase with increasing atomic number of the central atom. For any given central atom M (M = B, Al, Ga), the adiabatic and vertical electronic stability for MCl3 is larger than that of the corresponding MF3. The tri-hydrides have quite different electron binding strengths than the corresponding tri-halides. BH3 has a very small EA (ca. 0.02 eV) and its anion is planar whereas the tri-halide anions and AlH3- and GaH3- are non-planar. AlH3 and GaH3 have considerably smaller EAs (ca. 0.3 eV) than the Al and Ga tri-halides (0.9-1.8 eV). In all, these anions provide species whose electron binding strengths span a considerable range (0.3-1.8 eV).

  16. Anion and divalent cation activation of phosphoglycolate phosphatase from leaves.

    PubMed

    Husic, H D; Tolbert, N E

    1984-02-15

    Phosphoglycolate (P-glycolate) phosphatase was purified 223-fold from spinach leaves by (NH4)2SO4 fractionation, DEAE-cellulose chromatography, and Sephadex G-200 chromatography. The partially purified enzyme had a broad pH optimum between 5.6 and 8.0 and was specific for the hydrolysis of P-glycolate with a Km (P-glycolate) of 26 microM. The enzyme was activated by divalent cations including Mg2+, Co2+, Mn2+, and Zn2+, and by anions including Cl-, Br-, NO-3, and HCOO-. Neither anions nor divalent cations activated the enzyme without the other. The P-glycolate phosphatase activities from tobacco leaves or the green algae, Chlamydomonas reinhardtii, also required Mg2+ and were activated by chloride. In addition, the enzyme was allosterically inhibited by ribose 5-phosphate. The activation of P-glycolate phosphatase by both anions and divalent cations and the inhibition by ribose 5-phosphate may be involved in the in vivo regulation of P-glycolate phosphatase activity.

  17. Capillary electrophoresis screening of poisonous anions extracted from biological samples.

    PubMed

    Gillette, Robert; Doyle, Janet M; Miller, Mark L; Montgomery, Madeline A; Mushrush, George W

    2006-02-02

    A method was developed for screening human biological samples for poisonous anions using capillary electrophoresis (CE) employing indirect UV detection. The run buffer consisted of 2.25 mM pyromellitic acid, 1.6 mM triethanolamine, 0.75 mM hexamethonium hydroxide and 6.5mM NaOH at pH 7.7. Biological samples were pretreated using solid phase extraction. The method was applied to the analysis of human blood, plasma, urine, and intestinal contents. Twenty-nine different anions were detectable at aqueous concentrations of 1 part per million (ppm) with a typical analysis time less than 20 min. Intraday migration time R.S.D. and peak area R.S.D. for blood samples were less than 1.1% and 6.3%, respectively. Interday migration time R.S.D. for plasma samples ranged from 7.5% to 10.4%. The new method produced efficient separations of various target anions extracted from complex biological matrices.

  18. Cassini observations of carbon-based anions in Titan's ionosphere

    NASA Astrophysics Data System (ADS)

    Desai, Ravindra; Lewis, Gethyn; Waite, J. Hunter; Kataria, Dhiren; Wellbrock, Anne; Jones, Geraint; Coates, Andrew

    2016-07-01

    Cassini observations of Titan's ionosphere revealed an atmosphere rich in positively and negatively charged ions and organic molecules. The detection of large quantities of negatively charged ions was particularly surprising and adds Titan to the growing list of locations where anion chemistry has been observed to play an important role. In this study we present updated analysis on these negatively charged ions through an enhanced understanding of the Cassini CAPS Electron Spectrometer (CAPS-ELS) instrument response. The ionisation of Titan's dominant atmospheric constituent, N2, by the HeII Solar line, results in an observable photoelectron population at 24.1eV which we use to correct for differential spacecraft charging. Correcting for further energy-angle signatures within this dataset, we use an updated fitting procedure to show how the ELS mass spectrum, previously grouped into broad mass ranges, can be resolved into specific peaks at multiples of carbon-based anion species up to over 100amu/q. These peaks are shown to be ubiquitous within Titan's upper atmosphere and reminiscent of carbon-based anions identified in dense molecular clouds beyond our Solar System. It is thus shown how the moon Titan in the Outer Solar System can be used as an analogue to study these even more remote and exotic astrophysical environments.

  19. Anion exchanger and chloride channel in cat carotid body chemotransduction.

    PubMed

    Iturriaga, R; Mokashi, A; Lahiri, S

    1998-05-28

    In order to test the hypothesis that carotid body (CB) chemoreception depends on the functions of anion channels and HCO3-/Cl- exchangers, we studied the effects of the anion channel blocker anthracene-9-carboxylic acid (9-ANC), the carbonic anhydrase inhibitor methazolamide, and the HCO3-/Cl- exchanger blocker 4,4 diisothiocyanatostilbene-2-2'disulfonic acid (DIDS) on the chemosensory discharges of cat CB, perfused-superfused in vitro at 36.5 +/- 0.5 degrees C, with a modified Tyrode solution. The chemosensory responses to hypoxia (PO2 approximately 50 Torr), hypercapnia (PCO2 approximately 60 Torr, pH = 7.10), nicotine (2-4 nmol) and NaCN (20-40 nmol) were recorded. 9-ANC (2 microM) and DIDS (10 microM) decreased the chemosensory baseline activity, and eliminated the initial peak responses to hypercapnia and hypoxia and increased the time to achieve it. Methazolamide (0.13 mM) did not alter the effect of 9-ANC. The steady state responses to hypoxia and hypercapnia were not diminished after 9-ANC but DIDS lowered the responses. Responses to NaCN effects were all diminished but those to nicotine were not affected. The results suggest that the functions of anion channels and HCO3-/Cl- exchangers are important for the resting dischargers and for the fast responses to hypoxia and hypercapnia.

  20. ANION EXCHANGE METHOD FOR SEPARATION OF METAL VALUES

    DOEpatents

    Hyde, E.K.; Raby, B.A.

    1959-02-10

    A method is described for selectively separating radium, bismuth, poloniums and lead values from a metallic mixture of thc same. The mixture is dissolved in aqueous hydrochloric acid and the acidity is adjusted to between 1 to 2M in hydrochloric acid to form the anionic polychloro complexes of polonium and bismuth. The solution is contacted with a first anion exchange resin such as strong base quaternary ammonia type to selectively absorb the polonium and bismuth leaving the radium and lead in the effluent. The effluent, after treatment in hydrochloric acid to increase the hydrochloric acid concentration to 6M is contacted with a second anion exchange iesin of the same type as the above to selectively adsorb the lead leaving the radium in the effluent. Radium is separately recovered from the effluent from the second exchange column. Lead is stripped from the loaded resin of the second column by treatment with 3M hydrochloric acid solution. The loaded resin of the first column is washed with 8M hydrochloric acid solution to recover bismuth and then treated with strong nitric acid solution to recover polonium.