Sample records for h2o positive end-expiratory

  1. Lung recruitability is better estimated according to the Berlin definition of acute respiratory distress syndrome at standard 5 cm H2O rather than higher positive end-expiratory pressure: a retrospective cohort study.

    PubMed

    Caironi, Pietro; Carlesso, Eleonora; Cressoni, Massimo; Chiumello, Davide; Moerer, Onner; Chiurazzi, Chiara; Brioni, Matteo; Bottino, Nicola; Lazzerini, Marco; Bugedo, Guillermo; Quintel, Michael; Ranieri, V Marco; Gattinoni, Luciano

    2015-04-01

    The Berlin definition of acute respiratory distress syndrome has introduced three classes of severity according to PaO2/FIO2 thresholds. The level of positive end-expiratory pressure applied may greatly affect PaO2/FIO2, thereby masking acute respiratory distress syndrome severity, which should reflect the underlying lung injury (lung edema and recruitability). We hypothesized that the assessment of acute respiratory distress syndrome severity at standardized low positive end-expiratory pressure may improve the association between the underlying lung injury, as detected by CT, and PaO2/FIO2-derived severity. Retrospective analysis. Four university hospitals (Italy, Germany, and Chile). One hundred forty-eight patients with acute lung injury or acute respiratory distress syndrome according to the American-European Consensus Conference criteria. Patients underwent a three-step ventilator protocol (at clinical, 5 cm H2O, or 15 cm H2O positive end-expiratory pressure). Whole-lung CT scans were obtained at 5 and 45 cm H2O airway pressure. Nine patients did not fulfill acute respiratory distress syndrome criteria of the novel Berlin definition. Patients were then classified according to PaO2/FIO2 assessed at clinical, 5 cm H2O, or 15 cm H2O positive end-expiratory pressure. At clinical positive end-expiratory pressure (11±3 cm H2O), patients with severe acute respiratory distress syndrome had a greater lung tissue weight and recruitability than patients with mild or moderate acute respiratory distress syndrome (p<0.001). At 5 cm H2O, 54% of patients with mild acute respiratory distress syndrome at clinical positive end-expiratory pressure were reclassified to either moderate or severe acute respiratory distress syndrome. In these patients, lung recruitability and clinical positive end-expiratory pressure were higher than in patients who remained in the mild subgroup (p<0.05). When patients were classified at 5 cm H2O, but not at clinical or 15 cm H2O, lung

  2. Physiologic Evaluation of Ventilation Perfusion Mismatch and Respiratory Mechanics at Different Positive End-expiratory Pressure in Patients Undergoing Protective One-lung Ventilation.

    PubMed

    Spadaro, Savino; Grasso, Salvatore; Karbing, Dan Stieper; Fogagnolo, Alberto; Contoli, Marco; Bollini, Giacomo; Ragazzi, Riccardo; Cinnella, Gilda; Verri, Marco; Cavallesco, Narciso Giorgio; Rees, Stephen Edward; Volta, Carlo Alberto

    2018-03-01

    Arterial oxygenation is often impaired during one-lung ventilation, due to both pulmonary shunt and atelectasis. The use of low tidal volume (VT) (5 ml/kg predicted body weight) in the context of a lung-protective approach exacerbates atelectasis. This study sought to determine the combined physiologic effects of positive end-expiratory pressure and low VT during one-lung ventilation. Data from 41 patients studied during general anesthesia for thoracic surgery were collected and analyzed. Shunt fraction, high V/Q and respiratory mechanics were measured at positive end-expiratory pressure 0 cm H2O during bilateral lung ventilation and one-lung ventilation and, subsequently, during one-lung ventilation at 5 or 10 cm H2O of positive end-expiratory pressure. Shunt fraction and high V/Q were measured using variation of inspired oxygen fraction and measurement of respiratory gas concentration and arterial blood gas. The level of positive end-expiratory pressure was applied in random order and maintained for 15 min before measurements. During one-lung ventilation, increasing positive end-expiratory pressure from 0 cm H2O to 5 cm H2O and 10 cm H2O resulted in a shunt fraction decrease of 5% (0 to 11) and 11% (5 to 16), respectively (P < 0.001). The PaO2/FIO2 ratio increased significantly only at a positive end-expiratory pressure of 10 cm H2O (P < 0.001). Driving pressure decreased from 16 ± 3 cm H2O at a positive end-expiratory pressure of 0 cm H2O to 12 ± 3 cm H2O at a positive end-expiratory pressure of 10 cm H2O (P < 0.001). The high V/Q ratio did not change. During low VT one-lung ventilation, high positive end-expiratory pressure levels improve pulmonary function without increasing high V/Q and reduce driving pressure.

  3. Effect of positive end-expiratory pressure on blood loss during retropubic and robot-assisted laparoscopic radical prostatectomy.

    PubMed

    Ehieli, Eric I; Howard, Lauren E; Monk, Terri G; Ferrandino, Michael N; Polascik, Thomas J; Walther, Philip J; Freedland, Stephen J

    2016-08-01

    To study the effect of end-expiratory pressure used during anesthesia on blood loss during radical prostatectomy. We evaluated 247 patients who underwent either radical retropubic prostatectomy or robot-assisted laparoscopic prostatectomy at a single institution from 2008 to 2013 by one of four surgeons. Patient characteristics were compared using t-tests, rank sum or χ(2) -tests as appropriate. The association between positive end-expiratory pressure and estimated blood loss was tested using linear regression. Patients were classified into high (≥4 cmH2 O) and low (≤1 cmH2 O) positive-end expiratory pressure groups. Estimated blood loss in radical retropubic prostatectomy was higher in the high positive end-expiratory pressure group (1000 mL vs 800 mL, P = 0.042). Estimated blood loss in robot-assisted laparoscopic prostatectomy was lower in the high positive end-expiratory pressure group (150 mL vs 250 mL, P = 0.015). After adjusting for other factors known to influence blood loss, a 5-cmH2 O increase in positive end-expiratory pressure was associated with a 34.9% increase in estimated blood loss (P = 0.030) for radical retropubic prostatectomy, and a 33.0% decrease for robot-assisted laparoscopic prostatectomy (P = 0.038). In radical retropubic prostatectomy, high positive end-expiratory pressure was associated with higher estimated blood loss, and the benefits of positive end-expiratory pressure should be weighed against the risk of increased estimated blood loss. In robot-assisted laparoscopic prostatectomy, high positive end-expiratory pressure was associated with lower estimated blood loss, and might have more than just pulmonary benefits. © 2016 The Japanese Urological Association.

  4. Spontaneous Effort During Mechanical Ventilation: Maximal Injury With Less Positive End-Expiratory Pressure.

    PubMed

    Yoshida, Takeshi; Roldan, Rollin; Beraldo, Marcelo A; Torsani, Vinicius; Gomes, Susimeire; De Santis, Roberta R; Costa, Eduardo L V; Tucci, Mauro R; Lima, Raul G; Kavanagh, Brian P; Amato, Marcelo B P

    2016-08-01

    We recently described how spontaneous effort during mechanical ventilation can cause "pendelluft," that is, displacement of gas from nondependent (more recruited) lung to dependent (less recruited) lung during early inspiration. Such transfer depends on the coexistence of more recruited (source) liquid-like lung regions together with less recruited (target) solid-like lung regions. Pendelluft may improve gas exchange, but because of tidal recruitment, it may also contribute to injury. We hypothesize that higher positive end-expiratory pressure levels decrease the propensity to pendelluft and that with lower positive end-expiratory pressure levels, pendelluft is associated with improved gas exchange but increased tidal recruitment. Crossover design. University animal research laboratory. Anesthetized landrace pigs. Surfactant depletion was achieved by saline lavage in anesthetized pigs, and ventilator-induced lung injury was produced by ventilation with high tidal volume and low positive end-expiratory pressure. Ventilation was continued in each of four conditions: positive end-expiratory pressure (low or optimized positive end-expiratory pressure after recruitment) and spontaneous breathing (present or absent). Tidal recruitment was assessed using dynamic CT and regional ventilation/perfusion using electric impedance tomography. Esophageal pressure was measured using an esophageal balloon manometer. Among the four conditions, spontaneous breathing at low positive end-expiratory pressure not only caused the largest degree of pendelluft, which was associated with improved ventilation/perfusion matching and oxygenation, but also generated the greatest tidal recruitment. At low positive end-expiratory pressure, paralysis worsened oxygenation but reduced tidal recruitment. Optimized positive end-expiratory pressure decreased the magnitude of spontaneous efforts (measured by esophageal pressure) despite using less sedation, from -5.6 ± 1.3 to -2.0 ± 0.7 cm H2

  5. Effects of positive end-expiratory pressure on brain tissue oxygen pressure of severe traumatic brain injury patients with acute respiratory distress syndrome: A pilot study.

    PubMed

    Nemer, Sérgio Nogueira; Caldeira, Jefferson B; Santos, Ricardo G; Guimarães, Bruno L; Garcia, João Márcio; Prado, Darwin; Silva, Ricardo T; Azeredo, Leandro M; Faria, Eduardo R; Souza, Paulo Cesar P

    2015-12-01

    To verify whether high positive end-expiratory pressure levels can increase brain tissue oxygen pressure, and also their effects on pulse oxygen saturation, intracranial pressure, and cerebral perfusion pressure. Twenty traumatic brain injury patients with acute respiratory distress syndrome were submitted to positive end-expiratory pressure levels of 5, 10, and 15 cm H2O progressively. The 3 positive end-expiratory pressure levels were used during 20 minutes for each one, whereas brain tissue oxygen pressure, oxygen saturation, intracranial pressure, and cerebral perfusion pressure were recorded. Brain tissue oxygen pressure and oxygen saturation increased significantly with increasing positive end-expiratory pressure from 5 to 10 and from 10 to 15 cm H2O (P=.0001 and P=.0001 respectively). Intracranial pressure and cerebral perfusion pressure did not differ significantly with increasing positive end-expiratory pressure from 5 to 10 and from 10 to 15 cm H2O (P=.16 and P=.79 respectively). High positive end-expiratory pressure levels increased brain tissue oxygen pressure and oxygen saturation, without increase in intracranial pressure or decrease in cerebral perfusion pressure. High positive end-expiratory pressure levels can be used in severe traumatic brain injury patients with acute respiratory distress syndrome as a safe alternative to improve brain oxygenation. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Effects of recruitment maneuver and positive end-expiratory pressure on respiratory mechanics and transpulmonary pressure during laparoscopic surgery.

    PubMed

    Cinnella, Gilda; Grasso, Salvatore; Spadaro, Savino; Rauseo, Michela; Mirabella, Lucia; Salatto, Potito; De Capraris, Antonella; Nappi, Luigi; Greco, Pantaleo; Dambrosio, Michele

    2013-01-01

    The authors tested the hypothesis that during laparoscopic surgery, Trendelenburg position and pneumoperitoneum may worsen chest wall elastance, concomitantly decreasing transpulmonary pressure, and that a protective ventilator strategy applied after pneumoperitoneum induction, by increasing transpulmonary pressure, would result in alveolar recruitment and improvement in respiratory mechanics and gas exchange. In 29 consecutive patients, a recruiting maneuver followed by positive end-expiratory pressure 5 cm H(2)O maintained until the end of surgery was applied after pneumoperitoneum induction. Respiratory mechanics, gas exchange, blood pressure, and cardiac index were measured before (T(BSL)) and after pneumoperitoneum with zero positive end-expiratory pressure (T(preOLS)), after recruitment with positive end-expiratory pressure (T(postOLS)), and after peritoneum desufflation with positive end-expiratory pressure (T(end)). Esophageal pressure was used for partitioning respiratory mechanics between lung and chest wall (data are mean ± SD): on T(preOLS), chest wall elastance (E(cw)) and elastance of the lung (E(L)) increased (8.2 ± 0.9 vs. 6.2 ± 1.2 cm H(2)O/L, respectively, on T(BSL); P = 0.00016; and 11.69 ± 1.68 vs. 9.61 ± 1.52 cm H(2)O/L on T(BSL); P = 0.0007). On T(postOLS), both chest wall elastance and E(L) decreased (5.2 ± 1.2 and 8.62 ± 1.03 cm H(2)O/L, respectively; P = 0.00015 vs. T(preOLS)), and Pao(2)/inspiratory oxygen fraction improved (491 ± 107 vs. 425 ± 97 on T(preOLS); P = 0.008) remaining stable thereafter. Recruited volume (the difference in lung volume for the same static airway pressure) was 194 ± 80 ml. Pplat(RS) remained stable while inspiratory transpulmonary pressure increased (11.65 + 1.37 cm H(2)O vs. 9.21 + 2.03 on T(preOLS); P = 0.007). All respiratory mechanics parameters remained stable after abdominal desufflation. Hemodynamic parameters remained stable throughout the study. In patients submitted to laparoscopic surgery in

  7. Effects of inhaled fenoterol and positive end-expiratory pressure on the respiratory mechanics of patients with chronic obstructive pulmonary disease.

    PubMed

    Guérin, Claude; Durand, Pierre-Guy; Pereira, Cécile; Richard, Jean-Christophe; Poupelin, Jean-Charles; Lemasson, Stéphane; Badet, Michel; Philit, François; Vecellio, Laurent; Chantrel, Gilles

    2005-09-01

    During acute ventilatory failure in patients with chronic obstructive pulmonary disease (COPD), applying external positive end-expiratory pressure (PEEPe) will reopen small airways and, thus, may enhance peripheral deposition as well as the physiological effects of inhaled beta-2 agonists. To investigate the efficacy of inhaled fenoterol applied by zero end-expiratory pressure (ZEEPe) or PEEPe. Ten patients with COPD who were intubated and mechanically ventilated received fenoterol (10 mg/4 mL) via the ventilator using a jet nebulizer for 30 min on ZEEPe and PEEPe set at 80% of the total PEEP in a random order. The total resistance of the respiratory system (rapid airway occlusion technique), change in end-expiratory lung volume and expiratory flow limitation were assessed before and 5 min, 15 min, 30 min, 60 min and 240 min after fenoterol inhalation. Before inhalation and 60 min after inhalation, the total PEEP, the change in end-expiratory lung volume and the total resistance of the respiratory system were 8+/-3 cmH2O and 6+/-3 cmH2O, 0.61+/-0.34 L and 0.43+/-0.32 L, and 26+/-7 cmH2O/L/s and 23+/-6 cmH2O/L/s, respectively, with ZEEPe, and 9+/-3 cmH2O and 8+/-3 cmH2O (P<0.05 versus ZEEPe), 0.62+/-0.34 L and 0.62+/-0.37 L (P<0.05 versus ZEEPe), and 26+/-9 H2O/L/s and 25+/-9 H2O/L/s, respectively, with PEEPe. Three patients became not flow-limited under the combination of PEEPe and fenoterol. In patients with COPD, fenoterol combined with PEEPe has opposing effects on respiratory mechanics. First, it does not significantly reduce lung hyperinflation or inspiratory resistances. Second, it allows expiratory flow limitation reversal in some patients. These findings result from the net effect on end-expiratory lung volume of each intervention. This implies that if fenoterol is used in combination with PEEPe, the level of PEEPe should be reassessed during the time course of the drug to prevent any further lung hyperinflation.

  8. 21 CFR 868.5965 - Positive end expiratory pressure breathing attachment.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... in a patient's lungs above atmospheric pressure at the end of exhalation. (b) Classification. Class... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Positive end expiratory pressure breathing... Positive end expiratory pressure breathing attachment. (a) Identification. A positive end expiratory...

  9. Safety and effectiveness of alveolar recruitment maneuvers and positive end-expiratory pressure during general anesthesia for cesarean section: a prospective, randomized trial.

    PubMed

    Aretha, D; Fligou, F; Kiekkas, P; Messini, C; Panteli, E; Zintzaras, E; Karanikolas, M

    2017-05-01

    During cesarean section, the supine position reduces functional residual capacity and worsens lung compliance. We tested the hypothesis that alveolar recruitment maneuvers and positive end-expiratory pressure improve lung compliance in women undergoing general anesthesia for cesarean section. Ninety women undergoing cesarean section were randomly assigned to one of two groups in a prospective, double-blind trial. In the alveolar recruitment maneuver group, pressure-control ventilation was used and inspiratory time was increased to 50% after delivery; positive end-expiratory pressure was increased to 20cmH 2 O and peak airway inspiratory pressure gradually increased to 45-50cmH 2 O. Volume-control ventilation was then used with low tidal volumes (6mL/kg) and positive end-expiratory pressure was reduced stepwise to 8cmH 2 O. In the control group, alveolar recruitment maneuvers were not used. Data were collected before and 3, 10 and 20min after the alveolar recruitment maneuver, before extubation and postoperatively at 10 and 20min. Dynamic compliance, peak airway inspiratory pressure, PaO 2 and PaO 2 /FiO 2 were significantly different in the alveolar recruitment maneuver group compared to controls at all time points during surgery except at baseline. Oxygen saturation was significantly greater in the alveolar recruitment maneuver group at 10 and 20min and before extubation. Dynamic compliance was 29.7-42.5% higher and peak airway inspiratory pressure 3.6-10.2% lower in the alveolar recruitment maneuver group compared to controls. The PaO 2 , PaO 2 /FiO 2 and oxygen saturation were higher (9.4-12%, 10.3-11.9% and 0.4-1.3%, respectively) in the alveolar recruitment maneuver group. Postoperatively, PaO 2 and oxygen saturation were significantly higher in the alveolar recruitment maneuver group compared to controls (PaO 2 9.2% at 10min and 8.4% at 20min, oxygen saturation 0.8% at 10min and 1.1% at 20min). There were no significant differences in hemodynamic stability or

  10. Intratidal recruitment/derecruitment persists at low and moderate positive end-expiratory pressure in paediatric patients.

    PubMed

    Wirth, Steffen; Artner, Lisa; Broß, Tobias; Lozano-Zahonero, Sara; Spaeth, Johannes; Schumann, Stefan

    2016-12-01

    In paediatric patients positive end-expiratory pressure (PEEP) is traditionally set lower than in adults. We investigated whether moderately higher PEEP improves respiratory mechanics and regional ventilation. Therefore, 40 children were mechanically ventilated with PEEP 2 and 5cmH 2 O. Volume-dependent compliance profiles were analysed as a measure of intratidal recruitment/derecruitment. Regional ventilation was assessed using electrical impedance tomography. Mean compliance was 17.9±9.9mLcmH 2 O -1 (PEEP 2cmH 2 O), and 19.0±10.9mLcmH 2 O -1 (PEEP 5 cmH 2 O, p<0.001). Strong intratidal recruitment/derecruitment occurred in 40% of children at PEEP 2 cmH 2 O, and 36% at PEEP 5 cmH 2 O. Children showing strong recruitment/derecruitment were 33 (PEEP 2 cmH 2 0) and 20 (PEEP 5 cmH 2 0) months younger than children showing moderate recruitment/derecruitment. A higher PEEP improved peripheral ventilation. In conclusion, mechanically ventilated paediatric patients undergo intratidal recruitment/derecruitment which occurs more prominently in younger than in older children. A PEEP of 5cmH 2 O does not fully prevent intratidal recruitment/derecruitment but homogenizes regional ventilation in comparison to 2cmH 2 O. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Setting individualized positive end-expiratory pressure level with a positive end-expiratory pressure decrement trial after a recruitment maneuver improves oxygenation and lung mechanics during one-lung ventilation.

    PubMed

    Ferrando, Carlos; Mugarra, Ana; Gutierrez, Andrea; Carbonell, Jose Antonio; García, Marisa; Soro, Marina; Tusman, Gerardo; Belda, Francisco Javier

    2014-03-01

    We investigated whether individualized positive end-expiratory pressure (PEEP) improves oxygenation, ventilation, and lung mechanics during one-lung ventilation compared with standardized PEEP. Thirty patients undergoing thoracic surgery were randomly allocated to the study or control group. Both groups received an alveolar recruitment maneuver at the beginning and end of one-lung ventilation. After the alveolar recruitment maneuver, the control group had their lungs ventilated with a 5 cm·H2O PEEP, while the study group had their lungs ventilated with an individualized PEEP level determined by a PEEP decrement trial. Arterial blood samples, lung mechanics, and volumetric capnography were recorded at multiple timepoints throughout the procedure. The individualized PEEP values in study group were higher than the standardized PEEP values (10 ± 2 vs 5 cm·H2O; P < 0.001). In both groups, arterial oxygenation decreased when bilateral-lung ventilation was switched to one-lung ventilation and increased after the alveolar recruitment maneuver. During one-lung ventilation, oxygenation was maintained in the study group but decreased in the control group. After one-lung ventilation, arterial oxygenation was significantly higher in the study group (306 vs 231 mm·Hg, P = 0.007). Static compliance decreased in both groups when bilateral-lung ventilation was switched to one-lung ventilation. Static compliance increased significantly only in the study group (P < 0.001) after the alveolar recruitment maneuver and optimal PEEP adjustment. The alveolar recruitment maneuver did not decrease cardiac index in any patient. During one-lung ventilation, the improvements in oxygenation and lung mechanics after an alveolar recruitment maneuver were better preserved by ventilation by using individualized PEEP with a PEEP decrement trial than with a standardized 5 cm·H2O of PEEP.

  12. [POSITIVE END-EXPIRATORY PRESSURE (PEEP) INFLUENCES ON INTRACRANIAL PRESSURE, SYSTEMIC HEMODYNAMICS AND PULMONARY GAS EXCHANGE IN PATIENTS WITH INTRACRANIAl HEMORRHAGE IN CRITICAL STATE].

    PubMed

    Solodov, A A; Petrikov, S S; Krylov, V V

    2016-01-01

    Positive end-expiratory pressure is one of the main parameters of respiratory support influencing the gas exchange. However, despite the number ofpositive effects, PEEP can compromise venous outflow from the cranial cavity, increased intracranial pressure, decreased venous return and cardiac output and, consequently, reduced blood pressure and cerebral perfusion. The article presents the results of a survey of 39 patients with intracranial hemorrhage in critical state, undergoing respiratory support with different levels of positive end-expiratory pressure. Increasing of PEEP to 15 cm H2O had no adverse effect on mean arterial pressure, heart rate and cerebral perfusion pressure and led only to an clinical insignificant increase (maximum on 2.4 +/- 5.1 mmHg) in intracranial pressure. The greatest hemodynamic changes were observed with increasing PEEP up to 20 cm H2O in patients with preserved compliance ofthe respiratory system. The instability of cerebral perfusion and intracranial pressure associated with a decrease in cardiac output and preload and the exhaustion of compensatory mechanism of peripheral vascular resistance. High levels of PEEP despite the trend towards Cstat reduction will not lead to an increase in the content of extravascular lung water Thus a gradual increase of PEEP to 15 cm H2O can be safe and effective method of improving pulmonary gas exchange in patients with intracranial hemorrhage in critical state.

  13. Respiratory System Mechanics During Low Versus High Positive End-Expiratory Pressure in Open Abdominal Surgery: A Substudy of PROVHILO Randomized Controlled Trial.

    PubMed

    D'Antini, Davide; Huhle, Robert; Herrmann, Jacob; Sulemanji, Demet S; Oto, Jun; Raimondo, Pasquale; Mirabella, Lucia; Hemmes, Sabrine N T; Schultz, Marcus J; Pelosi, Paolo; Kaczka, David W; Vidal Melo, Marcos Francisco; Gama de Abreu, Marcelo; Cinnella, Gilda

    2018-01-01

    In the 2014 PROtective Ventilation using HIgh versus LOw positive end-expiratory pressure (PROVHILO) trial, intraoperative low tidal volume ventilation with high positive end-expiratory pressure (PEEP = 12 cm H2O) and lung recruitment maneuvers did not decrease postoperative pulmonary complications when compared to low PEEP (0-2 cm H2O) approach without recruitment breaths. However, effects of intraoperative PEEP on lung compliance remain poorly understood. We hypothesized that higher PEEP leads to a dominance of intratidal overdistension, whereas lower PEEP results in intratidal recruitment/derecruitment (R/D). To test our hypothesis, we used the volume-dependent elastance index %E2, a respiratory parameter that allows for noninvasive and radiation-free assessment of dominant overdistension and intratidal R/D. We compared the incidence of intratidal R/D, linear expansion, and overdistension by means of %E2 in a subset of the PROVHILO cohort. In 36 patients from 2 participating centers of the PROVHILO trial, we calculated respiratory system elastance (E), resistance (R), and %E2, a surrogate parameter for intratidal overdistension (%E2 > 30%) and R/D (%E2 < 0%). To test the main hypothesis, we compared the incidence of intratidal overdistension (primary end point) and R/D in higher and lower PEEP groups, as measured by %E2. E was increased in the lower compared to higher PEEP group (18.6 [16…22] vs 13.4 [11.0…17.0] cm H2O·L; P < .01). %E2 was reduced in the lower PEEP group compared to higher PEEP (-15.4 [-28.0…6.5] vs 6.2 [-0.8…14.0] %; P < .05). Intratidal R/D was increased in the lower PEEP group (61% vs 22%; P = .037). The incidence of intratidal overdistension did not differ significantly between groups (6%). During mechanical ventilation with protective tidal volumes in patients undergoing open abdominal surgery, lung recruitment followed by PEEP of 12 cm H2O decreased the incidence of intratidal R/D and did not worsen overdistension, when compared

  14. Non-invasive positive-pressure ventilation with positive end-expiratory pressure counteracts inward air leaks during preoxygenation: a randomised crossover controlled study in healthy volunteers.

    PubMed

    Hanouz, J-L; Le Gall, F; Gérard, J-L; Terzi, N; Normand, H

    2018-04-01

    During preoxygenation, the lack of tight fit between the mask and the patient's face results in inward air leak preventing effective preoxygenation. We hypothesized that non-invasive positive-pressure ventilation and positive end-expiratory pressure (PEEP) could counteract inward air leak. Healthy volunteers were randomly assigned to preoxygenated through spontaneous breathing without leak (SB), spontaneous breathing with a calibrated air leak (T-shaped piece between the mouth and the breathing system; SB-leak), or non-invasive positive inspiratory pressure ventilation (inspiratory support +6 cm H 2 O; PEEP +5 cm H 2 O) with calibrated leak (PPV-leak). The volunteers breathed through a mouthpiece connected to an anaesthesia ventilator. The expired oxygen fraction (FeO 2 ) and air-leak flow (ml s -1 ) were measured. The primary end point was the proportion of volunteers with FeO 2 >90% at 3 min. The secondary end points were FeO 2 at 3 min, time to reach FeO 2 of 90%, and the inspiratory air-leak flow. Twenty healthy volunteers were included. The proportion of volunteers with FeO 2 >90% at 3 min was 0% in the SB-leak group, 95% in the SB group, and 100% in the PPV-leak group (P<0.001). At 3 min, the mean [standard deviation (sd)] FeO 2 was 89 (1)%, 76 (1)%, and 90 (0)% in the SB, SB-leak, and PPV-leak groups, respectively (P<0.001). The mean (sd) inward air leak was 59 (12) ml s -1 in the SB-leak group, but 0 (0) ml s -1 in the PPV-leak group (P<0.001). Preoxygenation through non-invasive positive-pressure ventilation and PEEP provided effective preoxygenation despite an inward air leak. NCT03087825. Copyright © 2017 British Journal of Anaesthesia. Published by Elsevier Ltd. All rights reserved.

  15. Effects of positive end-expiratory pressure and recruitment maneuvers in a ventilator-induced injury mouse model

    PubMed Central

    Franzi, Lisa M.; Linderholm, Angela L.; Last, Jerold A.; Adams, Jason Y.; Harper, Richart W.

    2017-01-01

    Background Positive-pressure mechanical ventilation is an essential therapeutic intervention, yet it causes the clinical syndrome known as ventilator-induced lung injury. Various lung protective mechanical ventilation strategies have attempted to reduce or prevent ventilator-induced lung injury but few modalities have proven effective. A model that isolates the contribution of mechanical ventilation on the development of acute lung injury is needed to better understand biologic mechanisms that lead to ventilator-induced lung injury. Objectives To evaluate the effects of positive end-expiratory pressure and recruitment maneuvers in reducing lung injury in a ventilator-induced lung injury murine model in short- and longer-term ventilation. Methods 5–12 week-old female BALB/c mice (n = 85) were anesthetized, placed on mechanical ventilation for either 2 hrs or 4 hrs with either low tidal volume (8 ml/kg) or high tidal volume (15 ml/kg) with or without positive end-expiratory pressure and recruitment maneuvers. Results Alteration of the alveolar-capillary barrier was noted at 2 hrs of high tidal volume ventilation. Standardized histology scores, influx of bronchoalveolar lavage albumin, proinflammatory cytokines, and absolute neutrophils were significantly higher in the high-tidal volume ventilation group at 4 hours of ventilation. Application of positive end-expiratory pressure resulted in significantly decreased standardized histology scores and bronchoalveolar absolute neutrophil counts at low- and high-tidal volume ventilation, respectively. Recruitment maneuvers were essential to maintain pulmonary compliance at both 2 and 4 hrs of ventilation. Conclusions Signs of ventilator-induced lung injury are evident soon after high tidal volume ventilation (as early as 2 hours) and lung injury worsens with longer-term ventilation (4 hrs). Application of positive end-expiratory pressure and recruitment maneuvers are protective against worsening VILI across all time points

  16. Hyperinflation and intrinsic positive end-expiratory pressure: less room to breathe.

    PubMed

    Krieger, Bruce P

    2009-01-01

    Clinically, the symptoms and limited exercise capabilities of patients with chronic obstructive pulmonary disease (COPD) correlate better with changes in lung volumes than with airflow measurements. The realization of the clinical importance of hyperinflation has been overshadowed for decades by the use of forced expiratory volume during 1 s (FEV(1)) and the ratio of the FEV(1) to the forced expiratory vital capacity (FEV(1)/FVC) to categorize the severity and progression of COPD. Hyperinflation is defined as an elevation in the end-expiratory lung volume or functional residual capacity. When severe hyperinflation encroaches upon inspiratory capacity and limits vital capacity, it results in elevated intrinsic positive end-expiratory pressure (PEEPi) that places the diaphragm at a mechanical disadvantage and increases the work of breathing. Severe hyperinflation is the major physiologic cause of the resulting hypercarbic respiratory failure and patients' inability to transition (i.e. wean) from mechanical ventilatory support to spontaneous breathing. This paper reviews the basic physiologic principles of hyperinflation and its clinical manifestations as demonstrated by PEEPi. Also reviewed are the adverse effects of hyperinflation and PEEPi in critically ill patients with COPD, and methods for minimizing or counterbalancing these effects. Copyright 2009 S. Karger AG, Basel.

  17. Application of dead space fraction to titrate optimal positive end-expiratory pressure in an ARDS swine model.

    PubMed

    Bian, Weishuai; Chen, Wei; Chao, Yangong; Wang, Lan; Li, Liming; Guan, Jian; Zang, Xuefeng; Zhen, Jie; Sheng, Bo; Zhu, Xi

    2017-04-01

    This study aimed to apply the dead space fraction [ratio of dead space to tidal volume (VD/VT)] to titrate the optimal positive end-expiratory pressure (PEEP) in a swine model of acute respiratory distress syndrome (ARDS). Twelve swine models of ARDS were constructed. A lung recruitment maneuver was then conducted and the PEEP was set at 20 cm H 2 O. The PEEP was reduced by 2 cm H 2 O every 10 min until 0 cm H 2 O was reached, and VD/VT was measured after each decrement step. VD/VT was measured using single-breath analysis of CO 2 , and calculated from arterial CO 2 partial pressure (PaCO 2 ) and mixed expired CO 2 (PeCO 2 ) using the following formula: VD/VT = (PaCO 2 - PeCO 2 )/PaCO 2 . The optimal PEEP was identified by the lowest VD/VT method. Respiration and hemodynamic parameters were recorded during the periods of pre-injury and injury, and at 4 and 2 cm H 2 O below and above the optimal PEEP (Po). The optimal PEEP in this study was found to be 13.25±1.36 cm H 2 O. During the Po period, VD/VT decreased to a lower value (0.44±0.08) compared with that during the injury period (0.68±0.10) (P<0.05), while the intrapulmonary shunt fraction reached its lowest value. In addition, a significant change of dynamic tidal respiratory compliance and oxygenation index was induced by PEEP titration. These results indicate that minimal VD/VT can be used for PEEP titration in ARDS.

  18. The Effect of Positive End-Expiratory Pressure on Intracranial Pressure and Cerebral Hemodynamics.

    PubMed

    Boone, Myles D; Jinadasa, Sayuri P; Mueller, Ariel; Shaefi, Shahzad; Kasper, Ekkehard M; Hanafy, Khalid A; O'Gara, Brian P; Talmor, Daniel S

    2017-04-01

    Lung protective ventilation has not been evaluated in patients with brain injury. It is unclear whether applying positive end-expiratory pressure (PEEP) adversely affects intracranial pressure (ICP) and cerebral perfusion pressure (CPP). We aimed to evaluate the effect of PEEP on ICP and CPP in a large population of patients with acute brain injury and varying categories of acute lung injury, defined by PaO 2 /FiO 2 . Retrospective data were collected from 341 patients with severe acute brain injury admitted to the ICU between 2008 and 2015. These patients experienced a total of 28,644 paired PEEP and ICP observations. Demographic, hemodynamic, physiologic, and ventilator data at the time of the paired PEEP and ICP observations were recorded. In the adjusted analysis, a statistically significant relationship between PEEP and ICP and PEEP and CPP was found only among observations occurring during periods of severe lung injury. For every centimeter H 2 O increase in PEEP, there was a 0.31 mmHg increase in ICP (p = 0.04; 95 % CI [0.07, 0.54]) and a 0.85 mmHg decrease in CPP (p = 0.02; 95 % CI [-1.48, -0.22]). Our results suggest that PEEP can be applied safely in patients with acute brain injury as it does not have a clinically significant effect on ICP or CPP. Further prospective studies are required to assess the safety of applying a lung protective ventilation strategy in brain-injured patients with lung injury.

  19. Effects of positive end-expiratory pressure on arthroscopic shoulder surgery under general anesthesia.

    PubMed

    Ersoy, Ayşın; Çakırgöz, Mensure; Ervatan, Zekeriya; Kıran, Özlem; Türkmen, Aygen; Esenyel, Cem Zeki

    2016-01-01

    Our study is a prospective, randomized study on patients undergoing arthroscopic shoulder surgery in the beach-chair position to evaluate the effects of positive end-expiratory pressure (PEEP) on hemodynamic stability, providing a bloodless surgical field and surgical satisfaction. Fifty patients were divided into two groups. Group I (n=25) had zero end-expiratory pressure (ZEEP) administered under general anesthesia, and group II (n=25) had +5 PEEP administered. During surgery, intraarticular hemorrhage and surgical satisfaction were evaluated on a scale of 0-10. During surgery, at the 5th, 30th, 60th, and 90th minutes and at the end of surgery, heart rate, mean arterial pressure (MAP), and positive inspiratory pressure were recorded. At the end of the surgery, the amount of bleeding and duration of the operation were recorded. In group I, the duration of operation and amount of bleeding were found to be significantly greater than those in group II (p<0.05). The surgical satisfaction score and clarity of the surgical field were found to be significantly lower in group I than in group II (p<0.05). MAP values in group I were significantly lower than those in group II. The SPO² values in group I were significantly lower than those in group II. Adding PEEP to the ventilation parameters of arthroscopic shoulder surgery in the beach-chair position reduces the amount of hemorrhage in the surgical field and thus increases surgical satisfaction without requiring the creation of controlled hypotension.

  20. Compliance-guided versus FiO2-driven positive-end expiratory pressure in patients with moderate or severe acute respiratory distress syndrome according to the Berlin definition.

    PubMed

    Pintado, M-C; de Pablo, R; Trascasa, M; Milicua, J-M; Sánchez-García, M

    To study the effect of setting positive end-expiratory pressure (PEEP) in an individualized manner (based on highest static compliance) compared to setting PEEP according to FiO 2 upon mortality at 28 and 90 days, in patients with different severity acute respiratory distress syndrome (ARDS). A Spanish medical-surgical ICU. A post hoc analysis of a randomized controlled pilot study. Patients with ARDS. Ventilation with low tidal volumes and pressure limitation at 30cmH 2 O, randomized in two groups according to the method used to set PEEP: FiO 2 -guided PEEP group according to FiO 2 applied and compliance-guided group according to the highest compliance. Demographic data, risk factors and severity of ARDS, APACHE II and SOFA scores, daily Lung Injury Score, ventilatory measurements, ICU and hospital stay, organ failure and mortality at day 28 and 90 after inclusion. A total of 159 patients with ARDS were evaluated, but just 70 patients were included. Severe ARDS patients showed more organ dysfunction-free days at 28 days (12.83±10.70 versus 3.09±7.23; p=0.04) and at 90 days (6.73±22.31 vs. 54.17±42.14, p=0.03), and a trend toward lower 90-days mortality (33.3% vs. 90.9%, p=0.02), when PEEP was applied according to the best static compliance. Patients with moderate ARDS did not show these effects. In patients with severe ARDS, individualized PEEP selection based on the best static compliance was associated to lower mortality at 90 days, with an increase in organ dysfunction-free days at 28 and 90 days. Copyright © 2016 Elsevier España, S.L.U. y SEMICYUC. All rights reserved.

  1. Effects of Prone Position and Positive End-Expiratory Pressure on Noninvasive Estimators of ICP: A Pilot Study.

    PubMed

    Robba, Chiara; Bragazzi, Nicola Luigi; Bertuccio, Alessandro; Cardim, Danilo; Donnelly, Joseph; Sekhon, Mypinder; Lavinio, Andrea; Duane, Derek; Burnstein, Rowan; Matta, Basil; Bacigaluppi, Susanna; Lattuada, Marco; Czosnyka, Marek

    2017-07-01

    Prone positioning and positive end-expiratory pressure can improve pulmonary gas exchange and respiratory mechanics. However, they may be associated with the development of intracranial hypertension. Intracranial pressure (ICP) can be noninvasively estimated from the sonographic measurement of the optic nerve sheath diameter (ONSD) and from the transcranial Doppler analysis of the pulsatility (ICPPI) and the diastolic component (ICPFVd) of the velocity waveform. The effect of the prone positioning and positive end-expiratory pressure on ONSD, ICPFVd, and ICPPI was assessed in a prospective study of 30 patients undergoing spine surgery. One-way repeated measures analysis of variance, fixed-effect multivariate regression models, and receiver operating characteristic analyses were used to analyze numerical data. The mean values of ONSD, ICPFVd, and ICPPI significantly increased after change from supine to prone position. Receiver operating characteristic analyses demonstrated that, among the noninvasive methods, the mean ONSD measure had the greatest area under the curve signifying it is the most effective in distinguishing a hypothetical change in ICP between supine and prone positioning (0.86±0.034 [0.79 to 0.92]). A cutoff of 0.43 cm was found to be a best separator of ONSD value between supine and prone with a specificity of 75.0 and a sensitivity of 86.7. Noninvasive ICP estimation may be useful in patients at risk of developing intracranial hypertension who require prone positioning.

  2. Effect of betamethasone, surfactant, and positive end-expiratory pressures on lung aeration at birth in preterm rabbits.

    PubMed

    Crawshaw, Jessica R; Hooper, Stuart B; Te Pas, Arjan B; Allison, Beth A; Wallace, Megan J; Kerr, Lauren T; Lewis, Robert A; Morley, Colin J; Leong, Andrew F; Kitchen, Marcus J

    2016-09-01

    Antenatal glucocorticoids, exogenous surfactant, and positive end-expiratory pressure (PEEP) ventilation are commonly provided to preterm infants to enhance respiratory function after birth. It is unclear how these treatments interact to improve the transition to air-breathing at birth. We investigated the relative contribution of antenatal betamethasone, prophylactic surfactant, and PEEP (3 cmH 2 O) on functional residual capacity (FRC) and dynamic lung compliance (C DL ) in preterm (28 day GA) rabbit kittens at birth. Kittens were delivered by cesarean section and mechanically ventilated. FRC was calculated from X-ray images, and C DL was measured using plethysmography. Without betamethasone, PEEP increased FRC recruitment and C DL Surfactant did not further increase FRC, but significantly increased C DL Betamethasone abolished the benefit of PEEP on FRC, but surfactant counteracted this effect of betamethasone. These findings indicate that low PEEP levels are insufficient to establish FRC at birth following betamethasone treatment. However, surfactant reversed the effect of betamethasone and when combined, these two treatments enhanced FRC recruitment irrespective of PEEP level. Copyright © 2016 the American Physiological Society.

  3. Ventilation with positive end-expiratory pressure reduces extravascular lung water and increases lymphatic flow in hydrostatic pulmonary edema.

    PubMed

    Fernández Mondéjar, E; Vazquez Mata, G; Cárdenas, A; Mansilla, A; Cantalejo, F; Rivera, R

    1996-09-01

    To analyze the effect of different levels of positive end-expiratory pressure (PEEP) on extravascular lung water and on lymphatic drainage through the thoracic duct during hydrostatic pulmonary edema. Randomized, controlled, experimental study. Research laboratory of a tertiary care hospital. Eighteen beagle dogs weighing between 10 and 19 kg. Dogs were anesthetized and cannulated via a thoracic duct. Hydrostatic pulmonary edema was provoked by inflating the balloon of a Foley catheter in the left atrium. Different amounts of PEEP were applied. Extravascular lung water was determined by the double indicator dilution method (indocyanine green in glucoside solution at 0 degree C), and lymphatic drainage was measured every 30 mins. After a baseline measurement, the left atrial pressure was increased to 24 to 26 mm Hg, and measurements were recorded after 30, 60, 90, and 120 mins. The animals were divided into three groups. Group I (n = 6): PEEP of 20 cm H2O was instituted at 120 mins, and the other determinations were made without PEEP; group II (n = 7): PEEP of 10 cm H2O was instituted at 60 and 90 mins; group III (n = 5): PEEP of 20 cm H2O was instituted at 60 and 90 mins. Extravascular lung water increased after the increase of left atrial pressure in all three groups. After 90 mins, the extravascular lung water was significantly greater (p < .01) in group I (no PEEP application) at 21.2 +/- 5.1 mL/kg than in groups II and III (with 10 and 20 cm H2O of PEEP) at 12.8 +/- 2.01 and 14.8 +/- 4.8 mL/kg, respectively. Lymphatic drainage tended to increase over time in all three groups. Ninety minutes after the left atrial pressure increase, lymphatic drainage was significantly greater (p < .05) in group II, at 6.06 +/- 2.53 mL/kg/30 mins, than in group I, at 2.83 +/- 0.76 mL/kg/30 mins. a) The application of PEEP levels of between 10 and 20 cm H2O limits the increase of extravascular lung water in cases of hydrostatic pulmonary edema; and b) the application of 10 cm H2O

  4. Hemodynamic responses to external counterbalancing of auto-positive end-expiratory pressure in mechanically ventilated patients with chronic obstructive pulmonary disease.

    PubMed

    Baigorri, F; de Monte, A; Blanch, L; Fernández, R; Vallés, J; Mestre, J; Saura, P; Artigas, A

    1994-11-01

    To study the effect of positive end-expiratory pressure (PEEP) on right ventricular hemodynamics and ejection fraction in patients with chronic obstructive pulmonary disease and positive alveolar pressure throughout expiration by dynamic hyperinflation (auto-PEEP). Open, prospective, controlled trial. General intensive care unit of a community hospital. Ten patients sedated and paralyzed with an acute exacerbation of chronic obstructive pulmonary disease undergoing mechanical ventilation. Insertion of a pulmonary artery catheter modified with a rapid response thermistor and a radial arterial catheter. PEEP was then increased from 0 (PEEP 0) to auto-PEEP level (PEEP = auto-PEEP) and 5 cm H2O above that (PEEP = auto-PEEP +5). At each level of PEEP, airway pressures, flow and volume, hemodynamic variables (including right ventricular ejection fraction by thermodilution technique), and blood gas analyses were recorded. The mean auto-PEEP was 6.6 +/- 2.8 cm H2O and the total PEEP reached was 12.2 +/- 2.4 cm H2O. The degree of lung inflation induced by PEEP averaged 145 +/- 87 mL with PEEP = auto-PEEP and 495 +/- 133 mL with PEEP = auto-PEEP + 5. The PEEP = auto-PEEP caused a right ventricular end-diastolic pressure increase, but there was no other significant hemodynamic change. With PEEP = auto-PEEP + 5, there was a significant increase in intravascular pressures; this amount of PEEP reduced cardiac output (from 4.40 +/- 1.38 L/min at PEEP 0 to 4.13 +/- 1.48 L/min; p < .05). The cardiac output reduction induced by PEEP = auto-PEEP + 5 was > 10% in only five cases and this group of patients had significantly lower right ventricular volumes than the group with less cardiac output variation (right ventricular end-diastolic volume: 64 +/- 9 vs. 96 +/- 26 mL/m2; right ventricular end-systolic volume: 38 +/- 6 vs. 65 +/- 21 mL/m2; p < .05) without significant difference in the other variables that were measured. Neither right ventricular ejection fraction nor right ventricle

  5. Effects of positive end-expiratory pressure on intracranial pressure in mechanically ventilated dogs under hyperbaric oxygenation.

    PubMed

    Sun, Qing; Wu, Di; Yu, Tao; Yang, Ying; Wei, Li; Lv, Fuxiang; Gao, Guangkai

    2014-01-01

    Mechanical ventilation with positive end-expiratory pressure (PEEP) has been advocated as an essential life support for critical patients. However, its side effect, which is demonstrated by an elevation of intracranial pressure (ICP) under normobaric (NBO2) conditions, is potentially detrimental to patients. Hyperbaric oxygen (HBO2) therapy, on the other hand, is frequently applied for the same group of patients, and its efficacy is shown by maintaining a higher PaO2 and a reduced ICP. Our study investigated the effect of HBO2 and NBO2 on ICP with or without PEEP ventilation on healthy dogs by comparing cerebrospinal fluid pressure (CSFP) and concluded that the elevation of PEEP resulted in a significant increase of ICP (CSFP) under both conditions (p < 0.05). HBO2 leads to a lower ICP increase compared to the NBO2 group. Under the same level of PEEP, the joint use of PEEP and HBO2 is safe and highly practical in clinical medicine.

  6. Comparison of static end-expiratory and effective lung volumes for gas exchange in healthy and surfactant-depleted lungs.

    PubMed

    Albu, Gergely; Wallin, Mats; Hallbäck, Magnus; Emtell, Per; Wolf, Andrew; Lönnqvist, Per-Arne; Göthberg, Sylvia; Peták, Ferenc; Habre, Walid

    2013-07-01

    Effective lung volume (ELV) for gas exchange is a new measure that could be used as a real-time guide during controlled mechanical ventilation. The authors established the relationships of ELV to static end-expiratory lung volume (EELV) with varying levels of positive end-expiratory pressure (PEEP) in healthy and surfactant-depleted rabbit lungs. Nine rabbits were anesthetized and ventilated with a modified volume-controlled mode where periods of five consecutive alterations in inspiratory/expiratory ratio (1:2-1.5:1) were imposed to measure ELV from the corresponding carbon dioxide elimination traces. EELV and the lung clearance index were concomitantly determined by helium wash-out technique. Airway and tissue mechanics were assessed by using low-frequency forced oscillations. Measurements were collected at PEEP 0, 3, 6, and 9 cm H2O levels under control condition and after surfactant depletion by whole-lung lavage. ELV was greater than EELV at all PEEP levels before lavage, whereas there was no evidence for a difference in the lung volume indices after surfactant depletion at PEEP 6 or 9 cm H2O. Increasing PEEP level caused significant parallel increases in both ELV and EELV levels, decreases in ventilation heterogeneity, and improvement in airway and tissue mechanics under control condition and after surfactant depletion. ELV and EELV exhibited strong and statistically significant correlations before (r=0.84) and after lavage (r=0.87). The parallel changes in ELV and EELV with PEEP in healthy and surfactant-depleted lungs support the clinical value of ELV measurement as a bedside tool to estimate dynamic changes in EELV in children and infants.

  7. Positive end expiratory pressure in acute hypoxemic respiratory failure due to community acquired pneumonia: do we need a personalized approach?

    PubMed Central

    Paolini, Valentina; Faverio, Paola; Aliberti, Stefano; Messinesi, Grazia; Foti, Giuseppe; Sibila, Oriol; Monzani, Anna; Stainer, Anna; Pesci, Alberto

    2018-01-01

    Background Acute respiratory failure (ARF) is a life-threatening complication in patients with community acquired pneumonia (CAP). The use of non-invasive ventilation is controversial. With this prospective, observational study we aimed to describe a protocol to assess whether a patient with moderate-to-severe hypoxemic ARF secondary to CAP benefits, in clinical and laboratoristic terms, from the application of a positive end expiratory pressure (PEEP) + oxygen vs oxygen alone. Methods Patients who benefit from PEEP application (PEEP-responders) were defined as those with partial pressure of arterial oxygen to the fraction of inspired oxygen (PaO2/FiO2) increase >20% and/or reduction of respiratory distress during PEEP + oxygen therapy compared to oxygen therapy alone. Clinical characteristics and outcomes were compared between PEEP-responders and PEEP-non responders. Results Out of 41 patients, 27 (66%) benefit from PEEP application (PEEP-responders), the best response was obtained with a PEEP of 10 cmH2O in 13 patients, 7.5 cmH2O in eight and 5 cmH2O in six. PEEP-responders were less likely to present comorbidities compared to PEEP-non responders. No differences between groups were found in regards to endotracheal intubation criteria fullfillment, intensive care unit admission and in-hospital mortality, while PEEP-responders had a shorter length of hospital stay. Discussion The application of a protocol to evaluate PEEP responsiveness might be useful in patients with moderate-to-severe hypoxemic ARF due to CAP in order to personalize and maximize the effectiveness of therapy, and prevent the inappropriate PEEP use. PEEP responsiveness does not seem to be associated with better outcomes, with the exception of a shorter length of hospital stay. PMID:29404202

  8. Effect of PEEP and Tidal Volume on Ventilation Distribution and End-Expiratory Lung Volume: A Prospective Experimental Animal and Pilot Clinical Study

    PubMed Central

    Becher, Tobias; Schädler, Dirk; Pulletz, Sven; Freitag-Wolf, Sandra; Weiler, Norbert; Frerichs, Inéz

    2013-01-01

    Introduction Lung-protective ventilation aims at using low tidal volumes (VT) at optimum positive end-expiratory pressures (PEEP). Optimum PEEP should recruit atelectatic lung regions and avoid tidal recruitment and end-inspiratory overinflation. We examined the effect of VT and PEEP on ventilation distribution, regional respiratory system compliance (CRS), and end-expiratory lung volume (EELV) in an animal model of acute lung injury (ALI) and patients with ARDS by using electrical impedance tomography (EIT) with the aim to assess tidal recruitment and overinflation. Methods EIT examinations were performed in 10 anaesthetized pigs with normal lungs ventilated at 5 and 10 ml/kg body weight VT and 5 cmH2O PEEP. After ALI induction, 10 ml/kg VT and 10 cmH2O PEEP were applied. Afterwards, PEEP was set according to the pressure-volume curve. Animals were randomized to either low or high VT ventilation changed after 30 minutes in a crossover design. Ventilation distribution, regional CRS and changes in EELV were analyzed. The same measures were determined in five ARDS patients examined during low and high VT ventilation (6 and 10 (8) ml/kg) at three PEEP levels. Results In healthy animals, high compared to low VT increased CRS and ventilation in dependent lung regions implying tidal recruitment. ALI reduced CRS and EELV in all regions without changing ventilation distribution. Pressure-volume curve-derived PEEP of 21±4 cmH2O (mean±SD) resulted in comparable increase in CRS in dependent and decrease in non-dependent regions at both VT. This implied that tidal recruitment was avoided but end-inspiratory overinflation was present irrespective of VT. In patients, regional CRS differences between low and high VT revealed high degree of tidal recruitment and low overinflation at 3±1 cmH2O PEEP. Tidal recruitment decreased at 10±1 cmH2O and was further reduced at 15±2 cmH2O PEEP. Conclusions Tidal recruitment and end-inspiratory overinflation can be assessed by EIT

  9. End-expiratory lung volume and ventilation distribution with different continuous positive airway pressure systems in volunteers.

    PubMed

    Andersson, B; Lundin, S; Lindgren, S; Stenqvist, O; Odenstedt Hergès, H

    2011-02-01

    Continuous positive airway pressure (CPAP) has been shown to improve oxygenation and a number of different CPAP systems are available. The aim of this study was to assess lung volume and ventilation distribution using three different CPAP techniques. A high-flow CPAP system (HF-CPAP), an ejector-driven system (E-CPAP) and CPAP using a Servo 300 ventilator (V-CPAP) were randomly applied at 0, 5 and 10 cmH₂O in 14 volunteers. End-expiratory lung volume (EELV) was measured by N₂ dilution at baseline; changes in EELV and tidal volume distribution were assessed by electric impedance tomography. Higher end-expiratory and mean airway pressures were found using the E-CPAP vs. the HF-CPAP and the V-CPAP system (P<0.01). EELV increased markedly from baseline, 0 cmH₂O, with increased CPAP levels: 1110±380, 1620±520 and 1130±350 ml for HF-, E- and V-CPAP, respectively, at 10 cmH₂O. A larger fraction of the increase in EELV occurred for all systems in ventral compared with dorsal regions (P<0.01). In contrast, tidal ventilation was increasingly directed toward dorsal regions with increasing CPAP levels (P<0.01). The increase in EELV as well as the tidal volume redistribution were more pronounced with the E-CPAP system as compared with both the HF-CPAP and the V-CPAP systems (P<0.05) at 10 cmH₂O. EELV increased more in ventral regions with increasing CPAP levels, independent of systems, leading to a redistribution of tidal ventilation toward dorsal regions. Different CPAP systems resulted in different airway pressure profiles, which may result in different lung volume expansion and tidal volume distribution. © 2010 The Authors. Journal compilation © 2010 The Acta Anaesthesiologica Scandinavica Foundation.

  10. Effects of positive end-expiratory pressure titration and recruitment maneuver on lung inflammation and hyperinflation in experimental acid aspiration-induced lung injury.

    PubMed

    Ambrosio, Aline M; Luo, Rubin; Fantoni, Denise T; Gutierres, Claudia; Lu, Qin; Gu, Wen-Jie; Otsuki, Denise A; Malbouisson, Luiz M S; Auler, Jose O C; Rouby, Jean-Jacques

    2012-12-01

    In acute lung injury positive end-expiratory pressure (PEEP) and recruitment maneuver are proposed to optimize arterial oxygenation. The aim of the study was to evaluate the impact of such a strategy on lung histological inflammation and hyperinflation in pigs with acid aspiration-induced lung injury. Forty-seven pigs were randomly allocated in seven groups: (1) controls spontaneously breathing; (2) without lung injury, PEEP 5 cm H2O; (3) without lung injury, PEEP titration; (4) without lung injury, PEEP titration + recruitment maneuver; (5) with lung injury, PEEP 5 cm H2O; (6) with lung injury, PEEP titration; and (7) with lung injury, PEEP titration + recruitment maneuver. Acute lung injury was induced by intratracheal instillation of hydrochloric acid. PEEP titration was performed by incremental and decremental PEEP from 5 to 20 cm H2O for optimizing arterial oxygenation. Three recruitment maneuvers (pressure of 40 cm H2O maintained for 20 s) were applied to the assigned groups at each PEEP level. Proportion of lung inflammation, hemorrhage, edema, and alveolar wall disruption were recorded on each histological field. Mean alveolar area was measured in the aerated lung regions. Acid aspiration increased mean alveolar area and produced alveolar wall disruption, lung edema, alveolar hemorrhage, and lung inflammation. PEEP titration significantly improved arterial oxygenation but simultaneously increased lung inflammation in juxta-diaphragmatic lung regions. Recruitment maneuver during PEEP titration did not induce additional increase in lung inflammation and alveolar hyperinflation. In a porcine model of acid aspiration-induced lung injury, PEEP titration aimed at optimizing arterial oxygenation, substantially increased lung inflammation. Recruitment maneuvers further improved arterial oxygenation without additional effects on inflammation and hyperinflation.

  11. Positive end-expiratory pressure during resuscitation at birth in very-low birth weight infants: A randomized-controlled pilot trial.

    PubMed

    Kitsommart, Ratchada; Nakornchai, Kittaya; Yangthara, Buranee; Jiraprasertwong, Ratchada; Paes, Bosco

    2017-12-09

    There is limited evidence of the effect of positive end-expiratory pressure (PEEP) during resuscitation soon after birth. Premature neonates may experience respiratory distress from surfactant insufficiency and providing PEEP after the very first breath, may improve outcomes following appropriate resuscitation. The objective of this study was to evaluate the short term respiratory outcomes after positive pressure ventilation (PPV) with PEEP in preterm infants at birth. A prospective randomized-controlled, pilot trial was conducted. Premature neonates ≤ 32 weeks gestational age or birth weight < 1500 g were recruited. Subjects were allocated to either PEEP of 5 cm H 2 O (PEEP-5) or no PEEP (PEEP-0) if PPV was administered. Pre-ductal, peripheral capillary oxygen saturation (SpO 2 ) and fraction of inspired oxygen concentration (FiO 2 ) were monitored at 1, 3, 5, 10, 15, and 20 min after birth. FiO 2 was adjusted to achieve targeted SpO 2 using the 2010 neonatal resuscitation protocol guidelines. 56% (14/25; PEEP-0) and 50% (13/26; PEEP-5) infants received PPV. Mean gestational age was 30 (PEEP-0) vs 31 (PEEP-5) weeks. The mean [SD] birthweight (g) of PEEP-0 was significantly lower than PEEP-5 (1050.4 [262.7] vs 1218.8 [236.8], p = 0.02). Pre-ductal SpO 2, FiO 2 delivered at each time point, and rates of pneumothorax, surfactant administration and oxygen dependency at 36 weeks postmenstrual age or death was similar. Due to the small sample size and potential bias accrued through random allocation of higher birthweight infants to the PEEP-5 group, the results did not confirm differences in outcomes between the groups, despite evidence favoring postnatal ventilation with PEEP. A further randomized, controlled clinical trial with a larger sample size is warranted to determine the utility and safety of PEEP during the resuscitation of premature infants immediately after birth. Copyright © 2017. Published by Elsevier B.V.

  12. Positive End-Expiratory Pressure and Variable Ventilation in Lung-Healthy Rats under General Anesthesia

    PubMed Central

    Camilo, Luciana M.; Ávila, Mariana B.; Cruz, Luis Felipe S.; Ribeiro, Gabriel C. M.; Spieth, Peter M.; Reske, Andreas A.; Amato, Marcelo; Giannella-Neto, Antonio; Zin, Walter A.; Carvalho, Alysson R.

    2014-01-01

    Objectives Variable ventilation (VV) seems to improve respiratory function in acute lung injury and may be combined with positive end-expiratory pressure (PEEP) in order to protect the lungs even in healthy subjects. We hypothesized that VV in combination with moderate levels of PEEP reduce the deterioration of pulmonary function related to general anesthesia. Hence, we aimed at evaluating the alveolar stability and lung protection of the combination of VV at different PEEP levels. Design Randomized experimental study. Setting Animal research facility. Subjects Forty-nine male Wistar rats (200–270 g). Interventions Animals were ventilated during 2 hours with protective low tidal volume (VT) in volume control ventilation (VCV) or VV and PEEP adjusted at the level of minimum respiratory system elastance (Ers), obtained during a decremental PEEP trial subsequent to a recruitment maneuver, and 2 cmH2O above or below of this level. Measurements and Main Results Ers, gas exchange and hemodynamic variables were measured. Cytokines were determined in lung homogenate and plasma samples and left lung was used for histologic analysis and diffuse alveolar damage scoring. A progressive time-dependent increase in Ers was observed independent on ventilatory mode or PEEP level. Despite of that, the rate of increase of Ers and lung tissue IL-1 beta concentration were significantly lower in VV than in VCV at the level of the PEEP of minimum Ers. A significant increase in lung tissue cytokines (IL-6, IL-1 beta, CINC-1 and TNF-alpha) as well as a ventral to dorsal and cranial to caudal reduction in aeration was observed in all ventilated rats with no significant differences among groups. Conclusions VV combined with PEEP adjusted at the level of the PEEP of minimal Ers seemed to better prevent anesthesia-induced atelectasis and might improve lung protection throughout general anesthesia. PMID:25383882

  13. Effects of positive end-expiratory pressure and 30% inspired oxygen on pulmonary mechanics and atelectasis in cats undergoing non-bronchoscopic bronchoalveolar lavage.

    PubMed

    Bernhard, Christa; Masseau, Isabelle; Dodam, John; Outi, Hilton; Krumme, Stacy; Bishop, Kaitlin; Graham, Amber; Reinero, Carol

    2017-06-01

    Objectives The objective of this study was to determine if modification of inspired oxygen concentration or positive end-expiratory pressure (PEEP) would alter bronchoalveolar lavage (BAL)-induced changes in pulmonary mechanics or atelectasis, as measured using ventilator-acquired pulmonary mechanics and thoracic CT. Methods Six experimentally asthmatic cats underwent anesthesia and non-bronchoscopic BAL, each under four randomized treatment conditions: 100% oxygen, zero PEEP; 30% oxygen, zero PEEP; 100% oxygen, PEEP 2 cmH 2 O; and 30% oxygen, PEEP 2 cmH 2 O. Pulse oximetry was used to estimate oxygen saturation (SpO 2 ). Ventilator-acquired pulmonary mechanics and thoracic CT scans were collected prior to BAL and at 1, 5 and 15 mins post-BAL. Results While receiving 100% oxygen, no cat had SpO 2 <91%. Some cats receiving 30% oxygen had decreased saturation immediately post-BAL (mean ± SD 70.8 ± 31%), but 6/8 of these had SpO 2 >90% by 1 min later. There was a significant increase in airway resistance and a decrease in lung compliance following BAL, but there was no significant difference between treatment groups. Cats receiving no PEEP and 30% oxygen conserved better aeration of the lung parenchyma in BAL-sampled areas than those receiving no PEEP and 100% oxygen. Conclusions and relevance Alterations in pulmonary mechanics or atelectasis may not be reflected by SpO 2 following BAL. The use of 30% inspired oxygen concentration failed to show any significant improvement in pulmonary mechanics but did diminish atelectasis. In some cats, it was also associated with desaturation of hemoglobin. The use of PEEP in this study did not show any effect on our outcome parameters. Further studies using higher PEEP (5-10 cmH 2 O) and intermediate inspired oxygen concentration (40-60%) are warranted to determine if they would confer clinical benefit in cats undergoing diagnostic BAL.

  14. High altitude pulmonary edema and exercise at 4,400 meters on Mount McKinley. Effect of expiratory positive airway pressure.

    PubMed

    Schoene, R B; Roach, R C; Hackett, P H; Harrison, G; Mills, W J

    1985-03-01

    Breathing against positive expiratory pressure has been used to improve gas exchange in many forms of pulmonary edema, and forced expiration against resistance during exercise has been advocated for climbing at high altitude as a method to optimize performance. To evaluate the effect of expiratory positive airway pressure (EPAP) on climbers with high altitude pulmonary edema (HAPE) and on exercise at high altitude, we studied four climbers with HAPE at rest and 13 healthy climbers during exercise on a bicycle ergometer at 4400 m. We measured minute ventilation (VI, L/min), arterial oxygen saturation (SaO2 percent), end-tidal carbon dioxide (PACO2, mm Hg), respiratory rate (RR), and heart rate (HR) during the last minute of a five minute interval at rest in the climbers with HAPE, and at rest, 300, and 600 kpm/minute workloads on a bicycle ergometer in the healthy subjects. The HAPE subjects demonstrated an increased SaO2 percent, no change in HR or VI, and a decrease in RR on EPAP as compared to control. In normal subjects, SaO2 percent, VI, and heart rate were significantly higher on EPAP 10 cm H2O than 0 cm H2O control (p less than 0.01, 0.01, and 0.05, respectively). The RR and PaCO2 were not significantly different. In summary, EPAP improves gas exchange in HAPE subjects at rest. The EPAP in normal subjects at high altitude resulted in a higher SaO2 percent at the expense of a higher VI and higher HR. These results suggest that the work of breathing is higher and the stroke volume lower on EPAP. The positive pressure mask may be an effective temporizing measure for victims of HAPE who cannot immediately go to a lower altitude.

  15. [Spontaneous positive end-expiratory pressure ventilation in elderly patients with cardiogenic pulmonary edema. Assessment in an emergency admissions unit].

    PubMed

    L'Her, E; Duquesne, F; Paris, A; Mouline, J; Renault, A; Garo, B; Boles, J M

    1998-06-20

    Intubation and ventilatory assistance are often required in patients presenting severe hypoxemic respiratory distress, but may be contraindicated in elderly subjects due to an underlying condition. The aim of this study was to assess the feasibility, acceptability and contribution of early assistance with spontaneous positive end-expiratory pressure ventilation for elderly subjects admitted to an emergency unit for acute respiratory distress due to cardiogenic pulmonary edema. In our emergency admission unit, all patients with life-threatening hypoxemic respiratory distress are initially assisted with noninvasive spontaneous positive end-expiratory pressure ventilation using a standardized commercial device. We retrospectively analyzed the the files of all patients aged over 70 years who were treated with this standard protocol for cardiogenic pulmonary edema from April 1996 through September 1997. During the study period, 36 patients aged over 70 years required ventilatory assistance according to the standard protocol. Intubation was not reasonable in most of the patients (n = 30). After 1 hour of ventilation, none of the patients developed clinical signs of life-threatening distress. Blood gases demonstrated improved oxygenation (AEPO2 = +184.9 +/- 105.4 mmHg; p < 0.000001). Thirty-two patients were considered to be cured (88.9%) and were discharged; the cardiovascular condition was fatal in 4 patients (11.1%). The rapid improvement in clinical signs and blood gases as well as the final outcome suggests that early assistance with spontaneous positive end-expiratory pressure ventilation is warranted at admission for elderly patients with respiratory distress due to cardiogenic pulmonary edema. Compared with a control group of hospitalized patients cared for during the preceding year and who were not treated with the standard protocol, we also demonstrated a clear improvement in mortality (11% versus 20%).

  16. Low tidal volume and high positive end-expiratory pressure mechanical ventilation results in increased inflammation and ventilator-associated lung injury in normal lungs.

    PubMed

    Hong, Caron M; Xu, Da-Zhong; Lu, Qi; Cheng, Yunhui; Pisarenko, Vadim; Doucet, Danielle; Brown, Margaret; Aisner, Seena; Zhang, Chunxiang; Deitch, Edwin A; Delphin, Ellise

    2010-06-01

    Protective mechanical ventilation with low tidal volume (Vt) and low plateau pressure reduces mortality and decreases the length of mechanical ventilation in patients with acute respiratory distress syndrome. Mechanical ventilation that will protect normal lungs during major surgical procedures of long duration may improve postoperative outcomes. We performed an animal study comparing 3 ventilation strategies used in the operating room in normal lungs. We compared the effects on pulmonary mechanics, inflammatory mediators, and lung tissue injury. Female pigs were randomized into 3 groups. Group H-Vt/3 (n = 6) was ventilated with a Vt of 15 mL/kg predicted body weight (PBW)/positive end-expiratory pressure (PEEP) of 3 cm H(2)O, group L-Vt/3 (n = 6) with a Vt of 6 mL/kg PBW/PEEP of 3 cm H(2)O, and group L-Vt/10 (n = 6) with a Vt of 6 mL/kg PBW/PEEP of 10 cm H(2)O, for 8 hours. Hemodynamics, airway mechanics, arterial blood gases, and inflammatory markers were monitored. Bronchoalveolar lavage (BAL) was analyzed for inflammatory markers and protein concentration. The right lower lobe was assayed for mRNA of specific cytokines. The right lower lobe and right upper lobe were evaluated histologically. In contrast to groups H-Vt/3 and L-Vt/3, group L-Vt/10 exhibited a 6-fold increase in inflammatory mediators in BAL (P < 0.001). Cytokines in BAL were similar in groups H-Vt/3 and L-Vt/3. Group H-Vt/3 had a significantly lower lung injury score than groups L-Vt/3 and L-Vt/10. Comparing intraoperative strategies, ventilation with high PEEP resulted in increased production of inflammatory markers. Low PEEP resulted in lower levels of inflammatory markers. High Vt/low PEEP resulted in less histologic lung injury.

  17. OPTIMUM LEVEL OF POSITIVE END-EXPIRATORY PRESSURE IN ACUTE RESPIRATORY DISTRESS SYNDROME CAUSED BY INFLUENZA A(H1NI)PDM09: BALANCE BETWEEN MAXIMAL END-EXPIRATORY VOLUME AND MINIMAL ALVEOLAR OVERDISTENSION.

    PubMed

    Yaroshetskiym A I; Protsenko, D N; Boytsov, P V; Chentsov, V B; Nistratov, S L; Kudlyakov, O N; Solov'ev, V V; Banova, Zh I; Shkuratova, N V; Rezenov, N A; Gel'fand, B R

    2016-11-01

    to determine optimum level ofpositive end-expiratory pressure (PEEP) according to balance between maxi- mal end-expiratory lung volume (EEL V)(more than predicted) and minimal decrease in exhaled carbon dioxide volume (VCO) and then to develop the algorithm of gas exchange correction based on prognostic values of EEL K; alveolar recruitability, PA/FiO2, static compliance (C,,,) and VCO2. 27 mechanically ventilatedpatients with acute respiratory distress syndrome (ARDS) caused by influenza A (HINJ)pdm09 in Moscow Municipal Clinics ICU's from January to March 2016 were included in the trial. At the beginning of the study patients had the following characteristic: duration offlu symptoms 5 (3-10) days, p.0/FiO2 120 (70-50) mmHg. SOFA 7 (5-9), body mass index 30.1 (26.4-33.8) kg/m², static compliance of respiratory system 35 (30-40) ml/mbar: Under sedation and paralysis we measured EELV, C VCO and end-tidal carbon dioxide concentration (EtCO) (for CO₂ measurements we fixed short-term values after 2 min after PEEP level change) at PEEP 8, 11,13,15,18, 20 mbar consequently, and incase of good recruitability, at 22 and 24 mbar. After analyses of obtained data we determined PEEP value in which increase in EELV was maximal (more than predicted) and depression of VCO₂ was less than 20%, change in mean blood pressure and heart rate were both less than 20% (measured at PEEP 8 mbar). After that we set thus determined level of PEEP and didn't change it for 5 days. Comparision of predicted and measured EELV revealed two typical points of alveloar recruiment: the first at PEEP 11-15 mbar, the second at PEEP 20-22 mbar. EELV measured at PEEP 18 mbar appeared to be higher than predicted at PEEP 8 mbar by 400 ml (approx.), which was the sign of alveolar recruitment-1536 (1020-1845) ml vs 1955 (1360-2320) ml, p=0,001, Friedman test). we didn't found significant changes of VCO₂ when increased PEEP in the range from 8 to 15 mbar (p>0.05, Friedman test). PEEP increase from 15 to

  18. Clinical review: Positive end-expiratory pressure and cardiac output

    PubMed Central

    Luecke, Thomas; Pelosi, Paolo

    2005-01-01

    In patients with acute lung injury, high levels of positive end-expiratory pressure (PEEP) may be necessary to maintain or restore oxygenation, despite the fact that 'aggressive' mechanical ventilation can markedly affect cardiac function in a complex and often unpredictable fashion. As heart rate usually does not change with PEEP, the entire fall in cardiac output is a consequence of a reduction in left ventricular stroke volume (SV). PEEP-induced changes in cardiac output are analyzed, therefore, in terms of changes in SV and its determinants (preload, afterload, contractility and ventricular compliance). Mechanical ventilation with PEEP, like any other active or passive ventilatory maneuver, primarily affects cardiac function by changing lung volume and intrathoracic pressure. In order to describe the direct cardiocirculatory consequences of respiratory failure necessitating mechanical ventilation and PEEP, this review will focus on the effects of changes in lung volume, factors controlling venous return, the diastolic interactions between the ventricles and the effects of intrathoracic pressure on cardiac function, specifically left ventricular function. Finally, the hemodynamic consequences of PEEP in patients with heart failure, chronic obstructive pulmonary disease and acute respiratory distress syndrome are discussed. PMID:16356246

  19. The Supraglottic Effect of a Reduction in Expiratory Mask Pressure During Continuous Positive Airway Pressure

    PubMed Central

    Masdeu, Maria J.; Patel, Amit V.; Seelall, Vijay; Rapoport, David M.; Ayappa, Indu

    2012-01-01

    Study Objectives: Patients with obstructive sleep apnea may have difficulty exhaling against positive pressure, hence limiting their acceptance of continuous positive airway pressure (CPAP). C-Flex is designed to improve comfort by reducing pressure in the mask during expiration proportionally to expiratory airflow (3 settings correspond to increasing pressure changes). When patients use CPAP, nasal resistance determines how much higher supraglottic pressure is than mask pressure. We hypothesized that increased nasal resistance results in increased expiratory supraglottic pressure swings that could be mitigated by the effects of C-Flex on mask pressure. Design: Cohort study. Setting: Sleep center. Participants: Seventeen patients with obstructive sleep apnea/hypopnea syndrome and a mechanical model of the upper airway. Interventions: In patients on fixed CPAP, CPAP with different C-Flex levels was applied multiple times during the night. In the model, 2 different respiratory patterns and resistances were tested. Measurements and Results: Airflow, expiratory mask, and supraglottic pressures were measured on CPAP and on C-Flex. Swings in pressure during expiration were determined. On CPAP, higher nasal resistance produced greater expiratory pressure swings in the supraglottis in the patients and in the model, as expected. C-Flex 3 produced expiratory drops in mask pressure (range −0.03 to −2.49 cm H2O) but mitigated the expira-tory pressure rise in the supraglottis only during a sinusoidal respiratory pattern in the model. Conclusions: Expiratory changes in mask pressure induced by C-Flex did not uniformly transmit to the supraglottis in either patients with obstructive sleep apnea on CPAP or in a mechanical model of the upper airway with fixed resistance. Data suggest that the observed lack of expiratory drop in supraglottic pressure swings is related to dynamics of the C-Flex algorithm. Citation: Masdeu MJ; Patel AV; Seelall V; Rapoport DM; Ayappa I. The

  20. Positive end-expiratory pressure at minimal respiratory elastance represents the best compromise between mechanical stress and lung aeration in oleic acid induced lung injury.

    PubMed

    Carvalho, Alysson Roncally S; Jandre, Frederico C; Pino, Alexandre V; Bozza, Fernando A; Salluh, Jorge; Rodrigues, Rosana; Ascoli, Fabio O; Giannella-Neto, Antonio

    2007-01-01

    Protective ventilatory strategies have been applied to prevent ventilator-induced lung injury in patients with acute lung injury (ALI). However, adjustment of positive end-expiratory pressure (PEEP) to avoid alveolar de-recruitment and hyperinflation remains difficult. An alternative is to set the PEEP based on minimizing respiratory system elastance (Ers) by titrating PEEP. In the present study we evaluate the distribution of lung aeration (assessed using computed tomography scanning) and the behaviour of Ers in a porcine model of ALI, during a descending PEEP titration manoeuvre with a protective low tidal volume. PEEP titration (from 26 to 0 cmH2O, with a tidal volume of 6 to 7 ml/kg) was performed, following a recruitment manoeuvre. At each PEEP, helical computed tomography scans of juxta-diaphragmatic parts of the lower lobes were obtained during end-expiratory and end-inspiratory pauses in six piglets with ALI induced by oleic acid. The distribution of the lung compartments (hyperinflated, normally aerated, poorly aerated and non-aerated areas) was determined and the Ers was estimated on a breath-by-breath basis from the equation of motion of the respiratory system using the least-squares method. Progressive reduction in PEEP from 26 cmH2O to the PEEP at which the minimum Ers was observed improved poorly aerated areas, with a proportional reduction in hyperinflated areas. Also, the distribution of normally aerated areas remained steady over this interval, with no changes in non-aerated areas. The PEEP at which minimal Ers occurred corresponded to the greatest amount of normally aerated areas, with lesser hyperinflated, and poorly and non-aerated areas. Levels of PEEP below that at which minimal Ers was observed increased poorly and non-aerated areas, with concomitant reductions in normally inflated and hyperinflated areas. The PEEP at which minimal Ers occurred, obtained by descending PEEP titration with a protective low tidal volume, corresponded to the

  1. Ultrasonic monitoring in the assessment of pulmonary recruitment and the best positive end-expiratory pressure.

    PubMed

    Tang, Ke-Qiang; Yang, Shao-Ling; Zhang, Bin; Liu, Hong-Xiang; Ye, Dong-Ying; Zhang, Hong-Ze; Ma, Shuang

    2017-09-01

    The aim of this study was to explore the clinical value of ultrasonic monitoring in the assessment of pulmonary recruitment and the best positive end-expiratory pressure (PEEP).Between January 2015 and June 2017, 40 patients with acute respiratory distress syndrome in our hospital were randomly divided into 2 groups: ultrasound group (ULS group; n = 20) and oxygenation group (OXY group; n = 20). The PEEP incremental method was used to perform recruitment maneuvers. Ultrasound scoring and the oxygenation method were used to evaluate the pulmonary recruitment endpoint. The best PEEP was chosen by ultrasound scoring and the oxygenation method after achieving the pulmonary recruitment endpoint and sustaining it for 15 minutes.The oxygenation index, PEEP, peak airway pressure (Ppeak), mean airway pressure (Pmean), and dynamic compliance (Cdyn) in the OXY group were significantly lower than those in the ULS group (P < .05) at the pulmonary recruitment endpoint; however, there was no statistical significance in the mean arterial blood pressure (MAP) or heart rate (HR) (P > .05). The best PEEPs in the OXY and ULS groups were 13.1 ± 3.1 and 15.7 ± 4.2 cmH2O, respectively, with a significant difference between the 2 groups (t = 2.227, P = .016). Compared with the basal state, the Cdyn, oxygenation index, Pmean, and Ppeak in both groups significantly increased after pulmonary recruitment (P < .05). Furthermore, the Cdyn and oxygenation index in the ULS group were significantly higher than those in the OXY group after pulmonary recruitment (P < .05). The HR in both groups significantly increased, and the MAP significantly decreased. Two hours after recruitment, the HR and MAP returned to near basal levels without a significant difference between the 2 groups (P > .05).Lung ultrasound can be used to detect the endpoint of lung recruitment and the best PEEP, with good effects on lung compliance and oxygenation improvement.

  2. Pulmonary lesion induced by low and high positive end-expiratory pressure levels during protective ventilation in experimental acute lung injury.

    PubMed

    Pássaro, Caroline P; Silva, Pedro L; Rzezinski, Andréia F; Abrantes, Simone; Santiago, Viviane R; Nardelli, Liliane; Santos, Raquel S; Barbosa, Carolina M L; Morales, Marcelo M; Zin, Walter A; Amato, Marcelo B P; Capelozzi, Vera L; Pelosi, Paolo; Rocco, Patricia R M

    2009-03-01

    To investigate the effects of low and high levels of positive end-expiratory pressure (PEEP), without recruitment maneuvers, during lung protective ventilation in an experimental model of acute lung injury (ALI). Prospective, randomized, and controlled experimental study. University research laboratory. Wistar rats were randomly assigned to control (C) [saline (0.1 mL), intraperitoneally] and ALI [paraquat (15 mg/kg), intraperitoneally] groups. After 24 hours, each group was further randomized into four groups (six rats each) at different PEEP levels = 1.5, 3, 4.5, or 6 cm H2O and ventilated with a constant tidal volume (6 mL/kg) and open thorax. Lung mechanics [static elastance (Est, L) and viscoelastic pressure (DeltaP2, L)] and arterial blood gases were measured before (Pre) and at the end of 1-hour mechanical ventilation (Post). Pulmonary histology (light and electron microscopy) and type III procollagen (PCIII) messenger RNA (mRNA) expression were measured after 1 hour of mechanical ventilation. In ALI group, low and high PEEP levels induced a greater percentage of increase in Est, L (44% and 50%) and DeltaP2, L (56% and 36%) in Post values related to Pre. Low PEEP yielded alveolar collapse whereas high PEEP caused overdistension and atelectasis, with both levels worsening oxygenation and increasing PCIII mRNA expression. In the present nonrecruited ALI model, protective mechanical ventilation with lower and higher PEEP levels than required for better oxygenation increased Est, L and DeltaP2, L, the amount of atelectasis, and PCIII mRNA expression. PEEP selection titrated for a minimum elastance and maximum oxygenation may prevent lung injury while deviation from these settings may be harmful.

  3. Mechanical ventilation with lower tidal volumes and positive end-expiratory pressure prevents pulmonary inflammation in patients without preexisting lung injury.

    PubMed

    Wolthuis, Esther K; Choi, Goda; Dessing, Mark C; Bresser, Paul; Lutter, Rene; Dzoljic, Misa; van der Poll, Tom; Vroom, Margreeth B; Hollmann, Markus; Schultz, Marcus J

    2008-01-01

    Mechanical ventilation with high tidal volumes aggravates lung injury in patients with acute lung injury or acute respiratory distress syndrome. The authors sought to determine the effects of short-term mechanical ventilation on local inflammatory responses in patients without preexisting lung injury. Patients scheduled to undergo an elective surgical procedure (lasting > or = 5 h) were randomly assigned to mechanical ventilation with either higher tidal volumes of 12 ml/kg ideal body weight and no positive end-expiratory pressure (PEEP) or lower tidal volumes of 6 ml/kg and 10 cm H2O PEEP. After induction of anesthesia and 5 h thereafter, bronchoalveolar lavage fluid and/or blood was investigated for polymorphonuclear cell influx, changes in levels of inflammatory markers, and nucleosomes. Mechanical ventilation with lower tidal volumes and PEEP (n = 21) attenuated the increase of pulmonary levels of interleukin (IL)-8, myeloperoxidase, and elastase as seen with higher tidal volumes and no PEEP (n = 19). Only for myeloperoxidase, a difference was found between the two ventilation strategies after 5 h of mechanical ventilation (P < 0.01). Levels of tumor necrosis factor alpha, IL-1alpha, IL-1beta, IL-6, macrophage inflammatory protein 1alpha, and macrophage inflammatory protein 1beta in the bronchoalveolar lavage fluid were not affected by mechanical ventilation. Plasma levels of IL-6 and IL-8 increased with mechanical ventilation, but there were no differences between the two ventilation groups. The use of lower tidal volumes and PEEP may limit pulmonary inflammation in mechanically ventilated patients without preexisting lung injury. The specific contribution of both lower tidal volumes and PEEP on the protective effects of the lung should be further investigated.

  4. Individualized positive end-expiratory pressure application in patients with acute respiratory distress syndrome.

    PubMed

    Pintado, M C; de Pablo, R

    2014-11-01

    Current treatment of acute respiratory distress syndrome is based on ventilatory support with a lung protective strategy, avoiding the development of iatrogenic injury, including ventilator-induced lung injury. One of the mechanisms underlying such injury is atelectrauma, and positive end-expiratory pressure (PEEP) is advocated in order to avoid it. The indicated PEEP level has not been defined, and in many cases is based on the patient oxygen requirements for maintaining adequate oxygenation. However, this strategy does not consider the mechanics of the respiratory system, which varies in each patient and depends on many factors-including particularly the duration of acute respiratory distress syndrome. A review is therefore made of the different methods for adjusting PEEP, focusing on the benefits of individualized application. Copyright © 2013 Elsevier España, S.L.U. and SEMICYUC. All rights reserved.

  5. Protective intraoperative ventilation with higher versus lower levels of positive end-expiratory pressure in obese patients (PROBESE): study protocol for a randomized controlled trial.

    PubMed

    Bluth, T; Teichmann, R; Kiss, T; Bobek, I; Canet, J; Cinnella, G; De Baerdemaeker, L; Gregoretti, C; Hedenstierna, G; Hemmes, S N; Hiesmayr, M; Hollmann, M W; Jaber, S; Laffey, J G; Licker, M J; Markstaller, K; Matot, I; Müller, G; Mills, G H; Mulier, J P; Putensen, C; Rossaint, R; Schmitt, J; Senturk, M; Serpa Neto, A; Severgnini, P; Sprung, J; Vidal Melo, M F; Wrigge, H; Schultz, M J; Pelosi, P; Gama de Abreu, M

    2017-04-28

    Postoperative pulmonary complications (PPCs) increase the morbidity and mortality of surgery in obese patients. High levels of positive end-expiratory pressure (PEEP) with lung recruitment maneuvers may improve intraoperative respiratory function, but they can also compromise hemodynamics, and the effects on PPCs are uncertain. We hypothesized that intraoperative mechanical ventilation using high PEEP with periodic recruitment maneuvers, as compared with low PEEP without recruitment maneuvers, prevents PPCs in obese patients. The PRotective Ventilation with Higher versus Lower PEEP during General Anesthesia for Surgery in OBESE Patients (PROBESE) study is a multicenter, two-arm, international randomized controlled trial. In total, 2013 obese patients with body mass index ≥35 kg/m 2 scheduled for at least 2 h of surgery under general anesthesia and at intermediate to high risk for PPCs will be included. Patients are ventilated intraoperatively with a low tidal volume of 7 ml/kg (predicted body weight) and randomly assigned to PEEP of 12 cmH 2 O with lung recruitment maneuvers (high PEEP) or PEEP of 4 cmH 2 O without recruitment maneuvers (low PEEP). The occurrence of PPCs will be recorded as collapsed composite of single adverse pulmonary events and represents the primary endpoint. To our knowledge, the PROBESE trial is the first multicenter, international randomized controlled trial to compare the effects of two different levels of intraoperative PEEP during protective low tidal volume ventilation on PPCs in obese patients. The results of the PROBESE trial will support anesthesiologists in their decision to choose a certain PEEP level during general anesthesia for surgery in obese patients in an attempt to prevent PPCs. ClinicalTrials.gov identifier: NCT02148692. Registered on 23 May 2014; last updated 7 June 2016.

  6. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    PubMed Central

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  7. High Positive End-Expiratory Pressure Renders Spontaneous Effort Noninjurious.

    PubMed

    Morais, Caio C A; Koyama, Yukiko; Yoshida, Takeshi; Plens, Glauco M; Gomes, Susimeire; Lima, Cristhiano A S; Ramos, Ozires P S; Pereira, Sérgio M; Kawaguchi, Naomasa; Yamamoto, Hirofumi; Uchiyama, Akinori; Borges, João B; Vidal Melo, Marcos F; Tucci, Mauro R; Amato, Marcelo B P; Kavanagh, Brian P; Costa, Eduardo L V; Fujino, Yuji

    2018-05-15

    In acute respiratory distress syndrome (ARDS), atelectatic solid-like lung tissue impairs transmission of negative swings in pleural pressure (Ppl) that result from diaphragmatic contraction. The localization of more negative Ppl proportionally increases dependent lung stretch by drawing gas either from other lung regions (e.g., nondependent lung [pendelluft]) or from the ventilator. Lowering the level of spontaneous effort and/or converting solid-like to fluid-like lung might render spontaneous effort noninjurious. To determine whether spontaneous effort increases dependent lung injury, and whether such injury would be reduced by recruiting atelectatic solid-like lung with positive end-expiratory pressure (PEEP). Established models of severe ARDS (rabbit, pig) were used. Regional histology (rabbit), inflammation (positron emission tomography; pig), regional inspiratory Ppl (intrabronchial balloon manometry), and stretch (electrical impedance tomography; pig) were measured. Respiratory drive was evaluated in 11 patients with ARDS. Although injury during muscle paralysis was predominantly in nondependent and middle lung regions at low (vs. high) PEEP, strong inspiratory effort increased injury (indicated by positron emission tomography and histology) in dependent lung. Stronger effort (vs. muscle paralysis) caused local overstretch and greater tidal recruitment in dependent lung, where more negative Ppl was localized and greater stretch was generated. In contrast, high PEEP minimized lung injury by more uniformly distributing negative Ppl, and lowering the magnitude of spontaneous effort (i.e., deflection in esophageal pressure observed in rabbits, pigs, and patients). Strong effort increased dependent lung injury, where higher local lung stress and stretch was generated; effort-dependent lung injury was minimized by high PEEP in severe ARDS, which may offset need for paralysis.

  8. Effectiveness of positive end-expiratory pressure, decreased fraction of inspired oxygen and vital capacity recruitment maneuver in the prevention of pulmonary atelectasis in patients undergoing general anesthesia: a systematic review.

    PubMed

    Martin, Jennifer Bourgeois; Garbee, Deborah; Bonanno, Laura

    2015-09-16

    , and Blood Institute). Two independent reviewers appraised articles for methodological quality using the JBI Critical Appraisal Checklist for Randomized Control/Pseudo-randomized Trials. All studies included in this review were of high methodological quality. Data was extracted by two independent reviewers from papers using the standardized data extraction tool from the Joanna Briggs Institute Meta-Analysis of Statistics Assessment and Review Instrument. Meta-analysis was attempted using STATA 12 software; however, due to the heterogeneity of interventions and outcomes it was not possible to pool data. A narrative summary including tables have been used to report results and findings. This review included ten studies with a total of 427 participants aged from 18-78. Although a decreased inspired oxygen content (less than 60%) was shown to be effective individually at decreasing the incidence of postoperative atelectasis, this intervention in combination with a vital capacity recruitment maneuver (+40cm H20 for 15 seconds, and positive end-expiratory pressure, +10cm H2O) was shown to be statistically significant (relative risk=1.149; 95% confidence interval= 1.018, 1.297; p= 0.024). Anesthesia providers should utilize multiple interventions at their disposal to combat the formation and effects of atelectasis for their patients undergoing general anesthesia. Positive end-expiratory pressure following a vital capacity recruitment maneuver can virtually eliminate atelectasis formation even in the presence of a high inspired oxygen content. The majority of atelectasis occurs within minutes of induction and intubation; therefore, further research is needed for testing interventions during this specific time. The Joanna Briggs Institute.

  9. Levels of maximum end-expiratory carbon monoxide and certain cardiovascular parameters following hubble-bubble smoking.

    PubMed

    Shafagoj, Yanal A; Mohammed, Faisal I

    2002-08-01

    The physiological effects of cigarette smoking have been widely studied, however, little is known regarding the effects of smoking hubble-bubble. We examined the acute effects of hubble-bubble smoking on heart rate, systolic, diastolic, and mean arterial blood pressure and maximum end-expiratory carbon monoxide. This study was carried out in the student laboratory, School of Medicine, Department of Physiology, University of Jordan, Amman, Jordan, during the summer of 1999. In 18 healthy habitual hubble-bubble smokers, heart rate, blood pressure, and maximum end-expiratory carbon monoxide was measured before, during and post smoking of one hubble-bubble run (45 minutes). Compared to base line (time zero), at the end of smoking heart rate, systolic blood pressure, diastolic blood pressure, mean arterial blood pressure, and maximum end-expiratory carbon monoxide were increased 16 2.4 beats per minute, 6.7 2.5 mm Hg, 4.4 1.6 mm Hg, 5.2 1.7 mm Hg, and 14.2 1.8 ppm, (mean standard error of mean, P<.05). Acute short-term active hubble-bubble smoking elicits a modest increase in heart rate, systolic blood pressure, diastolic blood pressure, mean arterial blood pressure and maximum end-expiratory carbon monoxide in healthy hubble-bubble smokers.

  10. Effect of Very-High-Flow Nasal Therapy on Airway Pressure and End-Expiratory Lung Impedance in Healthy Volunteers.

    PubMed

    Parke, Rachael L; Bloch, Andreas; McGuinness, Shay P

    2015-10-01

    Previous research has demonstrated a positive linear correlation between flow delivered and airway pressure generated by high-flow nasal therapy. Current practice is to use flows over a range of 30-60 L/min; however, it is technically possible to apply higher flows. In this study, airway pressure measurements and electrical impedance tomography were used to assess the relationship between flows of up to 100 L/min and changes in lung physiology. Fifteen healthy volunteers were enrolled into this study. A high-flow nasal system capable of delivering a flow of 100 L/min was purpose-built using 2 Optiflow systems. Airway pressure was measured via the nasopharynx, and cumulative changes in end-expiratory lung impedance were recorded using the PulmoVista 500 system at gas flows of 30-100 L/min in increments of 10 L/min. The mean age of study participants was 31 (range 22-44) y, the mean ± SD height was 171.8 ± 7.5 cm, the mean ± SD weight was 69.7 ± 10 kg, and 47% were males. Flows ranged from 30 to 100 L/min with resulting mean ± SD airway pressures of 2.7 ± 0.7 to 11.9 ± 2.7 cm H2O. A cumulative and linear increase in end-expiratory lung impedance was observed with increasing flows, as well as a decrease in breathing frequency. Measured airway pressure and lung impedance increased linearly with increased gas flow. Observed airway pressures were in the range used clinically with face-mask noninvasive ventilation. Developments in delivery systems may result in this therapy being an acceptable alternative to face-mask noninvasive ventilation. Copyright © 2015 by Daedalus Enterprises.

  11. Value and limitations of transpulmonary pressure calculations during intra-abdominal hypertension.

    PubMed

    Cortes-Puentes, Gustavo A; Gard, Kenneth E; Adams, Alexander B; Faltesek, Katherine A; Anderson, Christopher P; Dries, David J; Marini, John J

    2013-08-01

    To clarify the effect of progressively increasing intra-abdominal pressure on esophageal pressure, transpulmonary pressure, and functional residual capacity. Controlled application of increased intra-abdominal pressure at two positive end-expiratory pressure levels (1 and 10 cm H2O) in an anesthetized porcine model of controlled ventilation. Large animal laboratory of a university-affiliated hospital. Eleven deeply anesthetized swine (weight 46.2 ± 6.2 kg). Air-regulated intra-abdominal hypertension (0-25 mm Hg). Esophageal pressure, tidal compliance, bladder pressure, and end-expiratory lung aeration by gas dilution. Functional residual capacity was significantly reduced by increasing intra-abdominal pressure at both positive end-expiratory pressure levels (p ≤ 0.0001) without corresponding changes of end-expiratory esophageal pressure. Above intra-abdominal pressure 5 mm Hg, plateau airway pressure increased linearly by ~ 50% of the applied intra-abdominal pressure value, associated with commensurate changes of esophageal pressure. With tidal volume held constant, negligible changes occurred in transpulmonary pressure due to intra-abdominal pressure. Driving pressures calculated from airway pressures alone (plateau airway pressure--positive end-expiratory pressure) did not equate to those computed from transpulmonary pressure (tidal changes in transpulmonary pressure). Increasing positive end-expiratory pressure shifted the predominantly negative end-expiratory transpulmonary pressure at positive end-expiratory pressure 1 cm H2O (mean -3.5 ± 0.4 cm H2O) into the positive range at positive end-expiratory pressure 10 cm H2O (mean 0.58 ± 1.2 cm H2O). Despite its insensitivity to changes in functional residual capacity, measuring transpulmonary pressure may be helpful in explaining how different levels of positive end-expiratory pressure influence recruitment and collapse during tidal ventilation in the presence of increased intra-abdominal pressure and in

  12. [Use of positive pressure in pre and intraoperative of bariatric surgery and its effect on the time of extubation].

    PubMed

    Baltieri, Letícia; Santos, Laisa Antonela Dos; Rasera-Junior, Irineu; Montebelo, Maria Imaculada de Lima; Pazzianotto-Forti, Eli Maria

    2015-01-01

    to investigate the influence of intraoperative and preoperative airway positive pressure in the time of extubation in patients undergoing bariatric surgery. Randomized clinical trial, in which 40 individuals with a body mass index between 40 and 55kg/m(2), age between 25 and 55 years, nonsmokers, underwent bariatric surgery type Roux-en-Y gastric bypass by laparotomy and with normal preoperative pulmonary function were randomized into the following groups: G-pre (n = 10): individuals who received treatment with noninvasive positive pressure before surgery for one hour, G-intra (n = 10): individuals who received positive end-expiratory pressure of 10cm H2O throughout the surgical procedure and G-control (n = 20): not received any pre or intraoperative intervention. Following were recorded: time between induction of anesthesia and extubation, between the end of anesthesia and extubation, duration of mechanical ventilation, and time between extubation and discharge from the Post-Anesthetic Recovery. there was no statistical difference between groups. However, when applied to the Cohen coefficient, the use of positive end-expiratory pressure of 10cm H2O during surgery showed a large effect on the time between the end of anesthesia and extubation. About this same time, the treatment performed preoperatively showed moderate effect. The use of positive end-expiratory pressure of 10cm H2O in the intraoperative and positive pressure preoperatively, influenced the time of extubation of patients undergoing bariatric surgery. Copyright © 2014 Sociedade Brasileira de Anestesiologia. Publicado por Elsevier Editora Ltda. All rights reserved.

  13. [Effect of nasal CPAP on human diaphragm position and lung volume].

    PubMed

    Yoshimura, N; Abe, T; Kusuhara, N; Tomita, T

    1994-11-01

    The cephalic margin of the zone of apposition (ZOA) was observed with ultrasonography at ambient pressure and during nasal continuous positive airway pressure (nasal CPAP) in nine awake healthy males in a supine position. In a relaxed state at ambient pressure, there was a significant (p < 0.001) linear relationship between lung volume and the movement of the cephalic margin of the ZOA over the range from maximum expiratory position (MEP) to maximum inspiratory position (MIP). With nasal CPAP, functional residual capacity increased significantly (p < 0.01) in proportion to the increase in CPAP. At 20 cmH2O CPAP, the mean increase in volume at end expiration was 36% of the vital capacity measured at ambient pressure. The cephalic margin of the ZOA moved significantly (p < 0.01) in a caudal direction as CPAP was increased. At 20 cmH2O CPAP, the cephalic margin of the ZOA at end expiratory position (EEP) had moved 55% of the difference from MIP to MEP measured at ambient pressure. The end expiratory diaphragm position during nasal CPAP was lower than the diaphragm position at ambient pressure when lung volumes were equal. These results suggest that during nasal CPAP the chest wall is distorted from its relaxed configuration, with a decrease in rib cage expansion and an increase in outward displacement of the abdominal wall.

  14. Clinical assessment of auto-positive end-expiratory pressure by diaphragmatic electrical activity during pressure support and neurally adjusted ventilatory assist.

    PubMed

    Bellani, Giacomo; Coppadoro, Andrea; Patroniti, Nicolò; Turella, Marta; Arrigoni Marocco, Stefano; Grasselli, Giacomo; Mauri, Tommaso; Pesenti, Antonio

    2014-09-01

    Auto-positive end-expiratory pressure (auto-PEEP) may substantially increase the inspiratory effort during assisted mechanical ventilation. Purpose of this study was to assess whether the electrical activity of the diaphragm (EAdi) signal can be reliably used to estimate auto-PEEP in patients undergoing pressure support ventilation and neurally adjusted ventilatory assist (NAVA) and whether NAVA was beneficial in comparison with pressure support ventilation in patients affected by auto-PEEP. In 10 patients with a clinical suspicion of auto-PEEP, the authors simultaneously recorded EAdi, airway, esophageal pressure, and flow during pressure support and NAVA, whereas external PEEP was increased from 2 to 14 cm H2O. Tracings were analyzed to measure apparent "dynamic" auto-PEEP (decrease in esophageal pressure to generate inspiratory flow), auto-EAdi (EAdi value at the onset of inspiratory flow), and IDEAdi (inspiratory delay between the onset of EAdi and the inspiratory flow). The pressure necessary to overcome auto-PEEP, auto-EAdi, and IDEAdi was significantly lower in NAVA as compared with pressure support ventilation, decreased with increase in external PEEP, although the effect of external PEEP was less pronounced in NAVA. Both auto-EAdi and IDEAdi were tightly correlated with auto-PEEP (r = 0.94 and r = 0.75, respectively). In the presence of auto-PEEP at lower external PEEP levels, NAVA was characterized by a characteristic shape of the airway pressure. In patients with auto-PEEP, NAVA, compared with pressure support ventilation, led to a decrease in the pressure necessary to overcome auto-PEEP, which could be reliably monitored by the electrical activity of the diaphragm before inspiratory flow onset (auto-EAdi).

  15. Relationship between pre-extubation positive endexpiratory pressure and oxygenation after coronary artery bypass grafting

    PubMed Central

    Lima, Reijane Oliveira; Borges, Daniel Lago; Costa, Marina de Albuquerque Gonçalves; Baldez, Thiago Eduardo Pereira; Silva, Mayara Gabrielle Barbosa e; Sousa, Felipe André Silva; Soares, Milena de Oliveira; Pinto, Jivago Gentil Moreira

    2015-01-01

    Introduction After removal of endotracheal tube and artificial ventilation, ventilatory support should be continued, offering oxygen supply to ensure an arterial oxygen saturation close to physiological. Objective The aim of this study was to investigate the effects of positive-end expiratory pressure before extubation on the oxygenation indices of patients undergoing coronary artery bypass grafting. Methods A randomized clinical trial with seventy-eight patients undergoing coronary artery bypass grafting divided into three groups and ventilated with different positive-end expiratory pressure levels prior to extubation: Group A, 5 cmH2O (n=32); Group B, 8 cmH2O (n=26); and Group C, 10 cmH2O (n=20). Oxygenation index data were obtained from arterial blood gas samples collected at 1, 3, and 6 h after extubation. Patients with chronic pulmonary disease and those who underwent off-pump, emergency, or combined surgeries were excluded. For statistical analysis, we used Shapiro-Wilk, G, Kruskal-Wallis, and analysis of variance tests and set the level of significance at P<0.05. Results Groups were homogenous with regard to demographic, clinical, and surgical variables. There were no statistically significant differences between groups in the first 6 h after extubation with regard to oxygenation indices and oxygen therapy utilization. Conclusion In this sample of patients undergoing coronary artery bypass grafting, the use of different positive-end expiratory pressure levels before extubation did not affect gas exchange or oxygen therapy utilization in the first 6 h after endotracheal tube removal. PMID:27163418

  16. Effect of external PEEP in patients under controlled mechanical ventilation with an auto-PEEP of 5 cmH2O or higher.

    PubMed

    Natalini, Giuseppe; Tuzzo, Daniele; Rosano, Antonio; Testa, Marco; Grazioli, Michele; Pennestrì, Vincenzo; Amodeo, Guido; Berruto, Francesco; Fiorillo, Marialinda; Peratoner, Alberto; Tinnirello, Andrea; Filippini, Matteo; Marsilia, Paolo F; Minelli, Cosetta; Bernardini, Achille

    2016-12-01

    In some patients with auto-positive end-expiratory pressure (auto-PEEP), application of PEEP lower than auto-PEEP maintains a constant total PEEP, therefore reducing the inspiratory threshold load without detrimental cardiovascular or respiratory effects. We refer to these patients as "complete PEEP-absorbers." Conversely, adverse effects of PEEP application could occur in patients with auto-PEEP when the total PEEP rises as a consequence. From a pathophysiological perspective, all subjects with flow limitation are expected to be "complete PEEP-absorbers," whereas PEEP should increase total PEEP in all other patients. This study aimed to empirically assess the extent to which flow limitation alone explains a "complete PEEP-absorber" behavior (i.e., absence of further hyperinflation with PEEP), and to identify other factors associated with it. One hundred patients with auto-PEEP of at least 5 cmH2O at zero end-expiratory pressure (ZEEP) during controlled mechanical ventilation were enrolled. Total PEEP (i.e., end-expiratory plateau pressure) was measured both at ZEEP and after applied PEEP equal to 80 % of auto-PEEP measured at ZEEP. All measurements were repeated three times, and the average value was used for analysis. Forty-seven percent of the patients suffered from chronic pulmonary disease and 52 % from acute pulmonary disease; 61 % showed flow limitation at ZEEP, assessed by manual compression of the abdomen. The mean total PEEP was 7 ± 2 cmH2O at ZEEP and 9 ± 2 cmH2O after the application of PEEP (p < 0.001). Thirty-three percent of the patients were "complete PEEP-absorbers." Multiple logistic regression was used to predict the behavior of "complete PEEP-absorber." The best model included a respiratory rate lower than 20 breaths/min and the presence of flow limitation. The predictive ability of the model was excellent, with an overoptimism-corrected area under the receiver operating characteristics curve of 0.89 (95 % CI 0

  17. Effects of positive end expiratory pressure administration during non-invasive ventilation in patients affected by amyotrophic lateral sclerosis: A randomized crossover study.

    PubMed

    Crescimanno, Grazia; Greco, Francesca; Arrisicato, Salvo; Morana, Noemi; Marrone, Oreste

    2016-10-01

    No studies have evaluated the impact of different settings of non-invasive ventilation (NIV) in patients affected by amyotrophic lateral sclerosis (ALS). We explored consequences of positive end-expiratory pressure (PEEP) application on effectiveness of ventilation, sleep architecture and heart rate variability (HRV) in patients with ALS naïve to ventilatory treatment. In two consecutive nights, 25 patients received in random order 0 or 4 cm H2 0 of PEEP during nocturnal NIV administration (Idea Ultra ResMed) with the same level of total positive inspiratory pressure. Polysomnographies were performed to evaluate sleep and NIV quality, as well as HRV. HRV was analyzed on 4-h periods and on 5-min segments of stable NREM sleep. We did not observe differences in gas exchanges during NIV with and without PEEP. Conversely, during PEEP application increases in leaks (41.4 ± 29.3% vs 31.0 ± 25.7%, P = 0.0007) and in autotriggerings (4.2 (IQR 1.3-10.0) vs 0.9 (IQR 0.0-3.0) events/h, P < 0.001, PEEP vs no PEEP, respectively) occurred. Besides, N3 sleep stage duration decreased (2.5% (IQR 0.0-18.0) vs 0.0% (IQR0.0-12.1), P = 0.001) and arousal/awakening index increased (16.9 ± 7.4 vs 13.4 ± 5.0 events/h, P = 0.01). Data on HRV were available in 15 patients. A higher low/high frequency ratio, either in the 4-h (3.8 ± 2.6 vs 2.9 ± 1.7, P = 0.04, PEEP vs no PEEP, respectively) or in the 5-min segments (2.6 ± 1.8 vs 1.45 ± 0.9 P = 0.01) was found during PEEP administration. In ALS patients, PEEP application during NIV was associated with worse NIV and sleep quality and with higher sympathetic activity. © 2016 Asian Pacific Society of Respirology.

  18. Deep breathing exercises with positive expiratory pressure in patients with multiple sclerosis - a randomized controlled trial.

    PubMed

    Westerdahl, Elisabeth; Wittrin, Anna; Kånåhols, Margareta; Gunnarsson, Martin; Nilsagård, Ylva

    2016-11-01

    Breathing exercises with positive expiratory pressure are often recommended to patients with advanced neurological deficits, but the potential benefit in multiple sclerosis (MS) patients with mild and moderate symptoms has not yet been investigated in randomized controlled trials. To study the effects of 2 months of home-based breathing exercises for patients with mild to moderate MS on respiratory muscle strength, lung function, and subjective breathing and health status outcomes. Forty-eight patients with MS according to the revised McDonald criteria were enrolled in a randomized controlled trial. Patients performing breathing exercises (n = 23) were compared with a control group (n = 25) performing no breathing exercises. The breathing exercises were performed with a positive expiratory pressure device (10-15 cmH 2 O) and consisted of 30 slow deep breaths performed twice a day for 2 months. Respiratory muscle strength (maximal inspiratory and expiratory pressure at the mouth), spirometry, oxygenation, thoracic excursion, subjective perceptions of breathing and self-reported health status were evaluated before and after the intervention period. Following the intervention, there was a significant difference between the breathing group and the control group regarding the relative change in lung function, favoring the breathing group (vital capacity: P < 0.043; forced vital capacity: P < 0.025). There were no other significant differences between the groups. Breathing exercises may be beneficial in patients with mild to moderate stages of MS. However, the clinical significance needs to be clarified, and it remains to be seen whether a sustainable effect in delaying the development of respiratory dysfunction in MS can be obtained. © 2015 The Authors. The Clinical Respiratory Journal published by John Wiley & Sons Ltd.

  19. Mechanisms of decreased left ventricular preload during continuous positive pressure ventilation in ARDS

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

    Dhainaut, J.F.; Devaux, J.Y.; Monsallier, J.F.

    1986-07-01

    Continuous positive pressure ventilation is associated with a reduction in left ventricular preload and cardiac output, but the mechanisms responsible are controversial. The decrease in left ventricular preload may result exclusively from a decreased systemic venous return due to increased pleural pressure, or from an additional effect such as decreased left ventricular compliance. To determine the mechanisms responsible, we studied the changes in cardiac output induced by continuous positive pressure ventilation in eight patients with the adult respiratory distress syndrome. We measured cardiac output by thermodilution, and biventricular ejection fraction by equilibrium gated blood pool scintigraphy. Biventricular end-diastolic volumes weremore » then calculated by dividing stroke volume by ejection fraction. As positive end-expiratory pressure increased from 0 to 20 cm H/sub 2/O, stroke volume and biventricular end-diastolic volumes fell about 25 percent, and biventricular ejection fraction remained unchanged. At 20 cm H/sub 2/O positive end-expiratory pressure, volume expansion for normalizing cardiac output restored biventricular end-diastolic volumes without markedly changing biventricular end-diastolic transmural pressures. The primary cause of the reduction in left ventricular preload with continuous positive pressure ventilation appears to be a fall in venous return and hence in right ventricular stroke volume, without evidence of change in left ventricular diastolic compliance.« less

  20. Combined Effects of Ventilation Mode and Positive End-Expiratory Pressure on Mechanics, Gas Exchange and the Epithelium in Mice with Acute Lung Injury

    PubMed Central

    Thammanomai, Apiradee; Hamakawa, Hiroshi; Bartolák-Suki, Erzsébet; Suki, Béla

    2013-01-01

    The accepted protocol to ventilate patients with acute lung injury is to use low tidal volume (VT) in combination with recruitment maneuvers or positive end-expiratory pressure (PEEP). However, an important aspect of mechanical ventilation has not been considered: the combined effects of PEEP and ventilation modes on the integrity of the epithelium. Additionally, it is implicitly assumed that the best PEEP-VT combination also protects the epithelium. We aimed to investigate the effects of ventilation mode and PEEP on respiratory mechanics, peak airway pressures and gas exchange as well as on lung surfactant and epithelial cell integrity in mice with acute lung injury. HCl-injured mice were ventilated at PEEPs of 3 and 6 cmH2O with conventional ventilation (CV), CV with intermittent large breaths (CVLB) to promote recruitment, and a new mode, variable ventilation, optimized for mice (VVN). Mechanics and gas exchange were measured during ventilation and surfactant protein (SP)-B, proSP-B and E-cadherin levels were determined from lavage and lung homogenate. PEEP had a significant effect on mechanics, gas exchange and the epithelium. The higher PEEP reduced lung collapse and improved mechanics and gas exchange but it also down regulated surfactant release and production and increased epithelial cell injury. While CVLB was better than CV, VVN outperformed CVLB in recruitment, reduced epithelial injury and, via a dynamic mechanotransduction, it also triggered increased release and production of surfactant. For long-term outcome, selection of optimal PEEP and ventilation mode may be based on balancing lung physiology with epithelial injury. PMID:23326543

  1. Effects of positive expiratory pressure on pulmonary clearance of aerosolized technetium-99m-labeled diethylenetriaminepentaacetic acid in healthy individuals

    PubMed Central

    de Albuquerque, Isabella Martins; Cardoso, Dannuey Machado; Masiero, Paulo Ricardo; Paiva, Dulciane Nunes; Resqueti, Vanessa Regiane; Fregonezi, Guilherme Augusto de Freitas; Menna-Barreto, Sérgio Saldanha

    2016-01-01

    ABSTRACT Objective: To evaluate the effects of positive expiratory pressure (PEP) on pulmonary epithelial membrane permeability in healthy subjects. Methods: We evaluated a cohort of 30 healthy subjects (15 males and 15 females) with a mean age of 28.3 ± 5.4 years, a mean FEV1/FVC ratio of 0.89 ± 0.14, and a mean FEV1 of 98.5 ± 13.1% of predicted. Subjects underwent technetium-99m-labeled diethylenetriaminepentaacetic acid (99mTc-DTPA) radioaerosol inhalation lung scintigraphy in two stages: during spontaneous breathing; and while breathing through a PEP mask at one of three PEP levels-10 cmH2O (n = 10), 15 cmH2O (n = 10), and 20 cmH2O (n = 10). The 99mTc-DTPA was nebulized for 3 min, and its clearance was recorded by scintigraphy over a 30-min period during spontaneous breathing and over a 30-min period during breathing through a PEP mask. Results: The pulmonary clearance of 99mTc-DTPA was significantly shorter when PEP was applied-at 10 cmH2O (p = 0.044), 15 cmH2O (p = 0.044), and 20 cmH2O (p = 0.004)-in comparison with that observed during spontaneous breathing. Conclusions: Our findings indicate that PEP, at the levels tested, is able to induce an increase in pulmonary epithelial membrane permeability and lung volume in healthy subjects. PMID:28117469

  2. Maximum static inspiratory and expiratory pressures with different lung volumes

    PubMed Central

    Lausted, Christopher G; Johnson, Arthur T; Scott, William H; Johnson, Monique M; Coyne, Karen M; Coursey, Derya C

    2006-01-01

    Background Maximum pressures developed by the respiratory muscles can indicate the health of the respiratory system, help to determine maximum respiratory flow rates, and contribute to respiratory power development. Past measurements of maximum pressures have been found to be inadequate for inclusion in some exercise models involving respiration. Methods Maximum inspiratory and expiratory airway pressures were measured over a range of lung volumes in 29 female and 19 male adults. A commercial bell spirometry system was programmed to occlude airflow at nine target lung volumes ranging from 10% to 90% of vital capacity. Results In women, maximum expiratory pressure increased with volume from 39 to 61 cmH2O and maximum inspiratory pressure decreased with volume from 66 to 28 cmH2O. In men, maximum expiratory pressure increased with volume from 63 to 97 cmH2O and maximum inspiratory pressure decreased with volume from 97 to 39 cmH2O. Equations describing pressures for both sexes are: Pe/Pmax = 0.1426 Ln( %VC) + 0.3402 R2 = 0.95 Pi/Pmax = 0.234 Ln(100 - %VC) - 0.0828 R2 = 0.96 Conclusion These results were found to be consistent with values and trends obtained by other authors. Regression equations may be suitable for respiratory mechanics models. PMID:16677384

  3. Risk stratification using SpO2/FiO2 and PEEP at initial ARDS diagnosis and after 24 h in patients with moderate or severe ARDS.

    PubMed

    Pisani, Luigi; Roozeman, Jan-Paul; Simonis, Fabienne D; Giangregorio, Antonio; van der Hoeven, Sophia M; Schouten, Laura R; Horn, Janneke; Neto, Ary Serpa; Festic, Emir; Dondorp, Arjen M; Grasso, Salvatore; Bos, Lieuwe D; Schultz, Marcus J

    2017-10-25

    We assessed the potential of risk stratification of ARDS patients using SpO 2 /FiO 2 and positive end-expiratory pressure (PEEP) at ARDS onset and after 24 h. We used data from a prospective observational study in patients admitted to a mixed medical-surgical intensive care unit of a university hospital in the Netherlands. Risk stratification was by cutoffs for SpO 2 /FiO 2 and PEEP. The primary outcome was in-hospital mortality. Patients with moderate or severe ARDS with a length of stay of > 24 h were included in this study. Patients were assigned to four predefined risk groups: group I (SpO 2 /FiO 2  ≥ 190 and PEEP < 10 cm H 2 O), group II (SpO 2 /FiO 2  ≥ 190 and PEEP ≥ 10 cm), group III (SpO 2 /FiO 2  < 190 and PEEP < 10 cm H 2 O) and group IV (SpO 2 /FiO 2  < 190 and PEEP ≥ 10 cm H 2 O). The analysis included 456 patients. SpO 2 /FiO 2 and PaO 2 /FiO 2 had a strong relationship (P < 0.001, R 2  = 0.676) that could be described in a linear regression equation (SpO 2 /FiO 2  = 42.6 + 1.0 * PaO 2 /FiO 2 ). Risk stratification at initial ARDS diagnosis resulted in groups that had no differences in in-hospital mortality. Risk stratification at 24 h resulted in groups with increasing mortality rates. The association between group assignment at 24 h and outcome was confounded by several factors, including APACHE IV scores, arterial pH and plasma lactate levels, and vasopressor therapy. In this cohort of patients with moderate or severe ARDS, SpO 2 /FiO 2 and PaO 2 /FiO 2 have a strong linear relationship. In contrast to risk stratification at initial ARDS diagnosis, risk stratification using SpO 2 /FiO 2 and PEEP after 24 h resulted in groups with worsening outcomes. Risk stratification using SpO 2 /FiO 2 and PEEP could be practical, especially in resource-limited settings.

  4. Influence of inspiratory resistive loading on expiratory muscle fatigue in healthy humans.

    PubMed

    Peters, Carli M; Welch, Joseph F; Dominelli, Paolo B; Molgat-Seon, Yannick; Romer, Lee M; McKenzie, Donald C; Sheel, A William

    2017-09-01

    What is the central question of this study? This study is the first to measure objectively both inspiratory and expiratory muscle fatigue after inspiratory resistive loading to determine whether the expiratory muscles are activated to the point of fatigue when specifically loading the inspiratory muscles. What is the main finding and its importance? The absence of abdominal muscle fatigue suggests that future studies attempting to understand the neural and circulatory consequences of diaphragm fatigue can use inspiratory resistive loading without considering the confounding effects of abdominal muscle fatigue. Expiratory resistive loading elicits inspiratory as well as expiratory muscle fatigue, suggesting parallel coactivation of the inspiratory muscles during expiration. It is unknown whether the expiratory muscles are likewise coactivated to the point of fatigue during inspiratory resistive loading (IRL). The purpose of this study was to determine whether IRL elicits expiratory as well as inspiratory muscle fatigue. Healthy male subjects (n = 9) underwent isocapnic IRL (60% maximal inspiratory pressure, 15 breaths min -1 , 0.7 inspiratory duty cycle) to task failure. Abdominal and diaphragm contractile function was assessed at baseline and at 3, 15 and 30 min post-IRL by measuring gastric twitch pressure (P ga,tw ) and transdiaphragmatic twitch pressure (P di,tw ) in response to potentiated magnetic stimulation of the thoracic and phrenic nerves, respectively. Fatigue was defined as a significant reduction from baseline in P ga,tw or P di,tw . Throughout IRL, there was a time-dependent increase in cardiac frequency and mean arterial blood pressure, suggesting activation of the respiratory muscle metaboreflex. The P di,tw was significantly lower than baseline (34.3 ± 9.6 cmH 2 O) at 3 (23.2 ± 5.7 cmH 2 O, P < 0.001), 15 (24.2 ± 5.1 cmH 2 O, P < 0.001) and 30 min post-IRL (26.3 ± 6.0 cmH 2 O, P < 0.001). The P ga,tw was not significantly

  5. Effects of inspiratory and expiratory resistance in divers' breathing apparatus.

    PubMed

    Warkander, D E; Nagasawa, G K; Lundgren, C E

    2001-01-01

    This study was performed to determine if inspiratory breathing resistance causes greater or smaller changes than expiratory resistance. Unacceptable inspiratory resistances were also determined. Five subjects exercised at 60% of their VO2max while immersed in a hyperbaric chamber. The chamber was pressurized to either 147 kPa (1.45 atm abs, 4.5 msw, 15 fsw) or 690 kPa (6.8 atm abs, 57 msw, 190 fsw). Breathing resistance was imposed on the inspiratory or expiratory side and was as high as 0.8-1.2 kPa liter(-1) x s(-1) (8-12 cm H2O x liter(-1) x s(-1)) at a flow of 2-3 liter x s(-1) at 1 atm abs., the other side being unloaded. The subjects reacted to the imposed load by prolonging the phase of breathing that was loaded. Inspiratory breathing resistance caused greater changes than expiratory resistance in end-tidal CO2, dyspnea scores, maximum voluntary ventilation, and respiratory duty cycle. Using previously published criteria for acceptable levels of dyspnea scores and the CO2 levels, we found that an inspiratory resistance inducing a volume-averaged pressure of 1.5 kPa is not acceptable. Similarly, an expiratory resistance should not induce a volume-averaged pressure exceeding 2.0 kPa

  6. HF/H2O2 treated graphite felt as the positive electrode for vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    He, Zhangxing; Jiang, Yingqiao; Meng, Wei; Jiang, Fengyun; Zhou, Huizhu; Li, Yuehua; Zhu, Jing; Wang, Ling; Dai, Lei

    2017-11-01

    In order to improve the electrochemical performance of the positive graphite felt electrode in vanadium flow redox battery, a novel method is developed to effectively modify the graphite felt by combination of etching of HF and oxidation of H2O2. After the etching of HF for the graphite felt at ambient temperature, abundant oxygen-containing functional groups were further introduced on the surface of graphite felt by hydrothermal treatment using H2O2 as oxidant. Benefiting from the surface etching and introduction of functional groups, mass transfer and electrode process can be improved significantly on the surface of graphite felt. VO2+/VO2+ redox reaction on the graphite felt modified by HF and H2O2 jointly (denote: GF-HF/H2O2) exhibits superior electrochemical kinetics in comparison with the graphite felt modified by single HF or H2O2 treatment. The cell using GF-HF/H2O2 as the positive electrode was assembled and its electrochemical properties were evaluated. The increase of energy efficiency of 4.1% for GF-HF/H2O2 at a current density of 50 mA cm-2 was obtained compared with the pristine graphite felt. The cell using GF-HF/H2O2 also demonstrated higher discharge capacity. Our study revealed that HF/H2O2 treatment is an efficient method to enhance the electrochemical performance of graphite felt, further improving the comprehensive energy storage performance of the vanadium flow redox battery.

  7. Improved lung recruitment and oxygenation during mandatory ventilation with a new expiratory ventilation assistance device: A controlled interventional trial in healthy pigs.

    PubMed

    Schmidt, Johannes; Wenzel, Christin; Mahn, Marlene; Spassov, Sashko; Cristina Schmitz, Heidi; Borgmann, Silke; Lin, Ziwei; Haberstroh, Jörg; Meckel, Stephan; Eiden, Sebastian; Wirth, Steffen; Buerkle, Hartmut; Schumann, Stefan

    2018-05-04

    In contrast to conventional mandatory ventilation, a new ventilation mode, expiratory ventilation assistance (EVA), linearises the expiratory tracheal pressure decline. We hypothesised that due to a recruiting effect, linearised expiration oxygenates better than volume controlled ventilation (VCV). We compared the EVA with VCV mode with regard to gas exchange, ventilation volumes and pressures and lung aeration in a model of peri-operative mandatory ventilation in healthy pigs. Controlled interventional trial. Animal operating facility at a university medical centre. A total of 16 German Landrace hybrid pigs. The lungs of anaesthetised pigs were ventilated with the EVA mode (n=9) or VCV (control, n=7) for 5 h with positive end-expiratory pressure of 5 cmH2O and tidal volume of 8 ml kg. The respiratory rate was adjusted for a target end-tidal CO2 of 4.7 to 6 kPa. Tracheal pressure, minute volume and arterial blood gases were recorded repeatedly. Computed thoracic tomography was performed to quantify the percentages of normally and poorly aerated lung tissue. Two animals in the EVA group were excluded due to unstable ventilation (n=1) or unstable FiO2 delivery (n=1). Mean tracheal pressure and PaO2 were higher in the EVA group compared with control (mean tracheal pressure: 11.6 ± 0.4 versus 9.0 ± 0.3 cmH2O, P < 0.001 and PaO2: 19.2 ± 0.7 versus 17.5 ± 0.4 kPa, P = 0.002) with comparable peak inspiratory tracheal pressure (18.3 ± 0.9 versus 18.0 ± 1.2 cmH2O, P > 0.99). Minute volume was lower in the EVA group compared with control (5.5 ± 0.2 versus 7.0 ± 1.0 l min, P = 0.02) with normoventilation in both groups (PaCO2 5.4 ± 0.3 versus 5.5 ± 0.3 kPa, P > 0.99). In the EVA group, the percentage of normally aerated lung tissue was higher (81.0 ± 3.6 versus 75.8 ± 3.0%, P = 0.017) and of poorly aerated lung tissue lower (9.5 ± 3.3 versus 15.7 ± 3.5%, P

  8. Functional Magnetic Stimulation of Inspiratory and Expiratory Muscles in Subjects With Tetraplegia.

    PubMed

    Zhang, Xiaoming; Plow, Ela; Ranganthan, Vinoth; Huang, Honglian; Schmitt, Melissa; Nemunaitis, Gregory; Kelly, Clay; Frost, Frederick; Lin, Vernon

    2016-07-01

    Respiratory complications are major causes of morbidity and mortality in persons with a spinal cord injury, partly because of respiratory muscle paralysis. Earlier investigation has demonstrated that functional magnetic stimulation (FMS) can be used as a noninvasive technology for activating expiratory muscles, thus producing useful expiratory functions (simulated cough) in subjects with spinal cord injury. To evaluate the effectiveness of FMS for conditioning inspiratory and expiratory muscles in persons with tetraplegia. A prospective before and after trial. FMS Laboratory, Louis Stokes Cleveland VA Medical Center, Cleveland, OH. Six persons with tetraplegia. Each subject participated in a 6-week FMS protocol for conditioning the inspiratory and expiratory muscles. A magnetic stimulator was used with the center of a magnetic coil placed at the C7-T1 and T9-T10 spinous processes, respectively. Pulmonary function tests were performed before, during, and after the protocol. Respiratory variables included maximal inspiratory pressure (MIP), inspiratory reserve volume (IRV), peak inspiratory flow (PIF), maximal expiratory pressure (MEP), expiratory reserve volume (ERV), and peak expiratory flow (PEF). After 6 weeks of conditioning, the main outcome measurements (mean ± standard error) were as follows: MIP, 89.6 ± 7.3 cm H2O; IRV, 1.90 ± 0.34 L; PIF, 302.4 ± 36.3 L/min; MEP, 67.4 ± 11.1 cm H2O; ERV, 0.40 ± 0.06 L; and PEF, 372.4 ± 31.9 L/min. These values corresponded to 117%, 107%, 136%, 109%, 130%, and 124% of pre-FMS conditioning values, respectively. Significant improvements were observed in MIP (P = .022), PIF (P = .0001), and PEF (P = .0006), respectively. When FMS was discontinued for 4 weeks, these values showed decreases from their values at the end of the conditioning protocol, which suggests that continual FMS may be necessary to maintain improved respiratory functions. FMS conditioning of the inspiratory and expiratory muscles improved

  9. Titration of Ideal Positive End-expiratory Pressure in Acute Respiratory Distress Syndrome: Comparison between Lower Inflection Point and Esophageal Pressure Method Using Volumetric Capnography.

    PubMed

    Baikunje, Nandakishore; Sehgal, Inderpaul Singh; Dhooria, Sahajal; Prasad, Kuruswamy Thurai; Agarwal, Ritesh

    2017-05-01

    The tenets of mechanical ventilation in acute respiratory distress syndrome (ARDS) include the utilization of low tidal volume and optimal application of positive end-expiratory pressure (PEEP). Optimal PEEP in ARDS is characterized by reduction in alveolar dead space along with improvement in the lung compliance and resultant betterment in oxygenation. There are various methods of setting PEEP in ARDS. Herein, we report a patient of ARDS, wherein we employed measurement of dead space using volumetric capnography to compare two different PEEP strategies, namely, the lower inflection point and transpulmonary pressure monitoring.

  10. Effect of Positive End-Expiratory Pressure on Central Venous Pressure in Patients under Mechanical Ventilation.

    PubMed

    Shojaee, Majid; Sabzghabaei, Anita; Alimohammadi, Hossein; Derakhshanfar, Hojjat; Amini, Afshin; Esmailzadeh, Bahareh

    2017-01-01

    Finding the probable governing pattern of PEEP and CVP changes is an area of interest for in-charge physicians and researchers. Therefore, the present study was designed with the aim of evaluating the relationship between the mentioned pressures. In this quasi-experimental study, patients under mechanical ventilation were evaluated with the aim of assessing the effect of PEEP change on CVP. Non-trauma patients, over 18 years of age, who were under mechanical ventilation and had stable hemodynamics, with inserted CV line were entered. After gathering demographic data, patients underwent 0, 5, and 10 cmH 2 O PEEPs and the respective CVPs of the mentioned points were recorded. The relationship of CVP and PEEP in different cut points were measured using SPSS 21.0 statistical software. 60 patients with the mean age of 73.95 ± 11.58 years were evaluated (68.3% male). The most frequent cause of ICU admission was sepsis with 45.0%. 5 cmH 2 O increase in PEEP led to 2.47 ± 1.53 mean difference in CVP level. If the PEEP baseline is 0 at the time of 5 cmH 2 O increase, it leads to a higher raise in CVP compared to when the baseline is 5 cmH 2 O (2.47 ± 1.53 vs. 1.57 ± 1.07; p = 0.039). The relationship between CVP and 5 cmH 2 O (p = 0.279), and 10 cmH 2 O (p = 0.292) PEEP changes were not dependent on the baseline level of CVP. The findings of this study revealed the direct relationship between PEEP and CVP. Approximately, a 5 cmH 2 O increase in PEEP will be associated with about 2.5 cmH 2 O raise in CVP. When applying a 5 cmH 2 O PEEP increase, if the baseline PEEP is 0, it leads to a significantly higher raise in CVP compared to when it is 5 cmH 2 O (2.5 vs. 1.6). It seems that sex, history of cardiac failure, baseline CVP level, and hypertension do not have a significant effect in this regard.

  11. Effects of vertical positioning on gas exchange and lung volumes in acute respiratory distress syndrome.

    PubMed

    Richard, Jean-Christophe M; Maggiore, Salvatore Maurizio; Mancebo, Jordi; Lemaire, François; Jonson, Bjorn; Brochard, Laurent

    2006-10-01

    Supine position may contribute to the loss of aerated lung volume in patients with acute respiratory distress syndrome (ARDS). We hypothesized that verticalization increases lung volume and improves gas exchange by reducing the pressure surrounding lung bases. Prospective observational physiological study in a medical ICU. In 16 patients with ARDS we measured arterial blood gases, pressure-volume curves of the respiratory system recorded from positive-end expiratory pressure (PEEP), and changes in lung volume in supine and vertical positions (trunk elevated at 45 degrees and legs down at 45 degrees ). Vertical positioning increased PaO(2) significantly from 94+/-33 to 142+/-49 mmHg, with an increase higher than 40% in 11 responders. The volume at 20 cmH(2)O measured on the PV curve from PEEP increased using the vertical position only in responders (233+/-146 vs. -8+/-9 1ml in nonresponders); this change was correlated to oxygenation change (rho=0.55). End-expiratory lung volume variation from supine to vertical and 1 h later back to supine, measured in 12 patients showed a significant increase during the 1-h upright period in responders (n=7) but not in nonresponders (n=5; 215+/-220 vs. 10+/-22 ml), suggesting a time-dependent recruitment. Vertical positioning is a simple technique that may improve oxygenation and lung recruitment in ARDS patients.

  12. Is there an optimal level of positive expiratory pressure (PEP) to improve walking tolerance in patients with severe COPD?

    PubMed

    Russo, Davide; Simonelli, Carla; Paneroni, Mara; Saleri, Manuela; Piroddi, Ines Maria Grazia; Cardinale, Francesco; Vitacca, Michele; Nicolini, Antonello

    2016-07-01

    The application of positive expiratory pressure (PEP) devices during exercise had been proposed in order to counteract the pulmonary hyperinflation, reduce the dyspnea and thus increase the exercise tolerance in patients with severe chronic obstructive pulmonary disease (COPD). This randomized controlled crossover trial investigated the effect of two different levels of PEP (1 cmH2O and 10 cmH2O) on distance covered at 6minute walk test (6MWT) in patients with severe COPD. Secondary outcomes were the evaluation of PEP effects on physiological and pulmonary function variables. Seventy-two severe COPD patients, referred to our hospitals as in and out patients, were recruited. A basal 6MWT without devices was performed on the first day, and then repeated with PEP 1 cmH2O (PEP1) and 10 cmH2O (PEP10), with a randomized crossover design. Slow and forced spirometries, including the inspiratory capacity measure, were repeated before and after each 6MWT. 50 patients (average age 69,92 year, mean FEV1 41,42% of predicted) concluded the trial. The 6MWT improved significantly among both PEP levels and baseline (323,8 mt at baseline vs. 337,8 PEP1 and 341,8 PEP10; p<.002 and p<.018, respectively). The difference between PEP10 and PEP1 did not reach the significance. No improvements were found in pulmonary function, symptoms and physiological variables after the 6MWT. In patients with severe COPD, the application of 1 cmH2O of PEP seems to improve the exercise tolerance as 10 cmH2O, with similar dyspnea. Further studies should investigate the effects of low levels of PEP on aerobic training programs. Copyright © 2016 SEPAR. Published by Elsevier Espana. All rights reserved.

  13. Candidate Water Vapor Lines to Locate the H2O Snowline through High-dispersion Spectroscopic Observations. III. Submillimeter H2 16O and H2 18O Lines

    NASA Astrophysics Data System (ADS)

    Notsu, Shota; Nomura, Hideko; Walsh, Catherine; Honda, Mitsuhiko; Hirota, Tomoya; Akiyama, Eiji; Millar, T. J.

    2018-03-01

    In this paper, we extend the results presented in our former papers on using ortho-{{{H}}}2{}16{{O}} line profiles to constrain the location of the H2O snowline in T Tauri and Herbig Ae disks, to include submillimeter para-{{{H}}}2{}16{{O}} and ortho- and para-{{{H}}}2{}18{{O}} lines. Since the number densities of the ortho- and para-{{{H}}}2{}18{{O}} molecules are about 560 times smaller than their 16O analogs, they trace deeper into the disk than the ortho-{{{H}}}2{}16{{O}} lines (down to z = 0, i.e., the midplane). Thus these {{{H}}}2{}18{{O}} lines are potentially better probes of the position of the H2O snowline at the disk midplane, depending on the dust optical depth. The values of the Einstein A coefficients of submillimeter candidate water lines tend to be lower (typically <10‑4 s‑1) than infrared candidate water lines. Thus in the submillimeter candidate water line cases, the local intensity from the outer optically thin region in the disk is around 104 times smaller than that in the infrared candidate water line cases. Therefore, in the submillimeter lines, especially {{{H}}}2{}18{{O}} and para-{{{H}}}2{}16{{O}} lines with relatively lower upper state energies (∼a few 100 K) can also locate the position of the H2O snowline. We also investigate the possibility of future observations with ALMA to identify the position of the water snowline. There are several candidate water lines that trace the hot water gas inside the H2O snowline in ALMA Bands 5–10.

  14. Bronchial fenestration improves expiratory flow in emphysematous human lungs.

    PubMed

    Lausberg, Henning F; Chino, Kimiaki; Patterson, G Alexander; Meyers, Bryan F; Toeniskoetter, Patricia D; Cooper, Joel D

    2003-02-01

    The crippling effects of emphysema are due in part to dynamic hyperinflation, resulting in altered respiratory mechanics, an increased work of breathing, and a pervasive sense of dyspnea. Because of the extensive collateral ventilation present in emphysematous lungs, we hypothesize that placement of stents between pulmonary parenchyma and large airways could effectively improve expiratory flow, thus reducing dynamic hyperinflation. Twelve human emphysematous lungs, removed at the time of lung transplantation, were placed in an airtight ventilation chamber with the bronchus attached to a tube traversing the chamber wall, and attached to a pneumotachometer. The chamber was evacuated to -10 cm H2O pressure for lung inflation. A forced expiratory maneuver was simulated by rapidly pressurizing the chamber to 20 cm H2O, while the expiratory volume was continuously recorded. A flexible bronchoscope was then inserted into the airway and a radiofrequency catheter (Broncus Technologies) was used to create a passage through the wall of three separate segmental bronchi into the adjacent lung parenchyma. An expandable stent, 1.5 cm in length and 3 mm in diameter, was then inserted through each passage. Expiratory volumes were then remeasured as above. In six experiments, two additional stents were then inserted and forced expiratory volumes again determined. The forced expiratory volume in 1 second (FEV1) increased from 245 +/- 107 mL at baseline to 447 +/- 199 mL after placement of three bronchopulmonary stents (p < 0.001). With two additional stents, the FEV1 increased to 666 +/- 284 mL (p < 0.001). Creation of extra-anatomic bronchopulmonary passages is a potential therapeutic option for emphysematous patients with marked hyperinflation and severe homogeneous pulmonary destruction.

  15. Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

    2013-01-01

    We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

  16. Alveolar Tidal recruitment/derecruitment and Overdistension During Four Levels of End-Expiratory Pressure with Protective Tidal Volume During Anesthesia in a Murine Lung-Healthy Model.

    PubMed

    Soares, Joao Henrique Neves; Carvalho, Alysson Roncally; Bergamini, Bruno Curty; Gress, Maria Alice Kuster; Jandre, Frederico Caetano; Zin, Walter Araujo; Giannella-Neto, Antonio

    2018-06-01

    We compared respiratory mechanics between the positive end-expiratory pressure of minimal respiratory system elastance (PEEP minErs ) and three levels of PEEP during low-tidal-volume (6 mL/kg) ventilation in rats. Twenty-four rats were anesthetized, paralyzed, and mechanically ventilated. Airway pressure (P aw ), flow (F), and volume (V) were fitted by a linear single compartment model (LSCM) P aw (t) = E rs  × V(t) + R rs  × F(t) + PEEP or a volume- and flow-dependent SCM (VFDSCM) P aw (t) = (E 1  + E 2  × V(t)) × V(t) + (K 1  + K 2  × |F(t)|) × F(t) + PEEP, where E rs and R rs are respiratory system elastance and resistance, respectively; E 1 and E 2 × V are volume-independent and volume-dependent E rs , respectively; and K 1 and K 2  × F are flow-independent and flow-dependent R rs , respectively. Animals were ventilated for 1 h at PEEP 0 cmH 2 O (ZEEP); PEEP minErs ; 2 cmH 2 O above PEEP minErs (PEEP minErs+2 ); or 4 cmH 2 O above PEEP minErs (PEEP minErs+4 ). Alveolar tidal recruitment/derecruitment and overdistension were assessed by the index %E 2  = 100 × [(E 2  × V T )/(E 1  + |E 2 | × V T )], and alveolar stability by the slope of E rs (t). %E 2 varied between 0 and 30% at PEEP minErs in most respiratory cycles. Alveolar Tidal recruitment/derecruitment (%E 2  < 0) and overdistension (%E 2  > 30) were predominant in the absence of PEEP and in PEEP levels higher than PEEP minErs , respectively. The slope of E rs (t) was different from zero in all groups besides PEEP minErs+4 . PEEP minErs presented the best compromise between alveolar tidal recruitment/derecruitment and overdistension, during 1 h of low-V T mechanical ventilation.

  17. Intraoperative protective mechanical ventilation for prevention of postoperative pulmonary complications: a comprehensive review of the role of tidal volume, positive end-expiratory pressure, and lung recruitment maneuvers.

    PubMed

    Güldner, Andreas; Kiss, Thomas; Serpa Neto, Ary; Hemmes, Sabrine N T; Canet, Jaume; Spieth, Peter M; Rocco, Patricia R M; Schultz, Marcus J; Pelosi, Paolo; Gama de Abreu, Marcelo

    2015-09-01

    Postoperative pulmonary complications are associated with increased morbidity, length of hospital stay, and mortality after major surgery. Intraoperative lung-protective mechanical ventilation has the potential to reduce the incidence of postoperative pulmonary complications. This review discusses the relevant literature on definition and methods to predict the occurrence of postoperative pulmonary complication, the pathophysiology of ventilator-induced lung injury with emphasis on the noninjured lung, and protective ventilation strategies, including the respective roles of tidal volumes, positive end-expiratory pressure, and recruitment maneuvers. The authors propose an algorithm for protective intraoperative mechanical ventilation based on evidence from recent randomized controlled trials.

  18. Oxygen kinetics and debt during recovery from expiratory flow-limited exercise in healthy humans

    PubMed Central

    Zakynthinos, S.; Georgiadou, O.; Golemati, S.; Pedotti, A.; Macklem, P. T.; Roussos, C.; Aliverti, A.

    2006-01-01

    In healthy subjects expiratory flow limitation (EFL) during exercise can lower O2 delivery to the working muscles. We hypothesized that if this affects exercise performance it should influence O2 kinetics at the end of exercise when the O2 debt is repaid. We performed an incremental exercise test on six healthy males with a Starling resistor in the expiratory line limiting expiratory flow to ∼ 1 l s−1 to determine maximal EFL exercise workload (Wmax). In two more square-wave exercise runs subjects exercised with and without EFL at Wmax for 6 min, while measuring arterial O2 saturation (% SaO2), end-tidal pressure of CO2 (PETCO2) and breath-by-breath O2 consumption \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${({\\dot{V}}\\hbox{O}_{2})}$$\\end{document} taking into account changes in O2 stored in the lungs. Over the last minute of EFL exercise, mean PETCO2 (54.7 ± 9.9 mmHg) was significantly higher (P < 0.05) compared to control (41.4 ± 3.9 mmHg). At the end of EFL exercise %SaO2 fell significantly by 4 ± 3%. When exercise stopped, EFL was removed, and we continued to measure \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\dot{V}}\\hbox{O}_{2}.}$$\\end{document} During recovery, there was an immediate step increase in \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\dot{V}}\\hbox{O}_{2},}$$\\end{document} so that repayment of EFL O2 debt started at a higher

  19. Study Looking at End Expiratory Pressure for Altitude Illness Decrease (SLEEP-AID).

    PubMed

    Lipman, Grant S; Kanaan, Nicholas C; Phillips, Caleb; Pomeranz, Dave; Cain, Patrick; Fontes, Kristin; Higbee, Becky; Meyer, Carolyn; Shaheen, Michael; Wentworth, Sean; Walsh, Diane

    2015-06-01

    Lipman, Grant S., Nicholas C. Kanaan, Caleb Phillips, Dave Pomeranz, Patrick Cain, Kristin Fontes, Becky Higbee, Carolyn Meyer, Michael Shaheen, Sean Wentworth, and Diane Walsh. Study Looking at End Expiratory Pressure for Altitude Illness Decrease (SLEEP-AID). High Alt Med Biol 16:154-161, 2015.--Acute mountain sickness (AMS) affects 25%-70% of the tens of millions of high altitude travelers annually, with hypoxia and nocturnal desaturations as major contributing factors. This is the first double blind randomized placebo controlled trial to assess expiratory positive airway pressure (EPAP) for AMS prevention and nocturnal hypoxic events. Healthy adult participants trekking in the Khumbu region of the Himalayas were randomized to a single-use EPAP nasal strip, or a visually identical sham device (placebo) prior to first night sleeping between 4371-4530 m (14,340-14,800 ft). The primary outcome was AMS incidence, measured by Lake Louise Questionnaire (LLQ), with secondary outcomes of AMS severity (by LLQ) and physiologic sleep indices measured by continuous sleep monitor. Intent-to-treat analysis included 219 participants with comparable demographic characteristics, of which 115 received EPAP and 104 placebo. There was no decrease in AMS with EPAP intervention (14% EPAP vs. 17% placebo; p=0.65; risk difference (-)3.15%, 95% CI (-)12.85%-6.56%). While overall AMS severity was not different between groups, EPAP reported decreased incidence of headache (64% vs. 76%; p<0.05, OR 0.51, 95% CI 0.27-0.95) and dizziness (81% vs. 98%; p<0.03, OR 0.29, 95% CI 0.09-0.78). During sleep, EPAP resulted in significant improvements in average peripheral oxygenation (Spo(2)) (80% versus 78%; p<0.01, mean difference=2, 95% CI 0.58-3.63) and a reduced percentage of time below 80% Spo(2) (31% vs. 46%; p<0.03, median difference=16, 95% CI 2.22-28.18). This lightweight and inexpensive EPAP device did not prevent acute mountain sickness, but did reduce the subgroup incidence of

  20. [EzPAP® therapy of postoperative hypoxemia in the recovery room : experiences with the new compact system of end-expiratory positive airway pressure].

    PubMed

    Rieg, A D; Stoppe, C; Rossaint, R; Coburn, M; Hein, M; Schälte, G

    2012-10-01

    Postoperative hypoxemia is a common complication in the anesthesia recovery room (ARR), which is predominantly based on the development of atelectasis, excessive intraoperative fluid shift and insufficient ventilation. The goal of this prospective observational study was to compare the effect of standard oxygen administration via a face mask with oxygen administration using the EzPAP® system, a device which additionally provides a positive end-expiratory pressure (PEEP). This study included 210 patients with postoperative hypoxemia (S(p)O(2) < 93%) subdivided into the control group (105 patients) and the EzPAP group (105 patients). Postoperative residual paralysis was excluded using relaxometry and a train of four (TOF) ratio of 0.9 was assumed to ensure sufficient recovery of respiratory function from neuromuscular blockade. Patients who received a reversal of neuromuscular blockade were excluded. In cases of hypoxemia (S(p)O(2) < 93%) control patients were treated with oxygen (6 l/min) using a face mask, whereas the EzPAP group received oxygen using the EzPAP® system. In order to adjust the PEEP in the EzPAP group, the O(2) flow was verified and measured by a manometer. After 1 h of oxygen therapy, the oxygen supply was stopped. In cases of reoccurring hypoxemia (S(p)O(2) < 93%, persistence > 5 min), the oxygen therapy was restarted in both groups via a facemask. Both groups were compared using repeat measurement analysis of variance (ANOVA), the unpaired t-test, the Mann-Whitney U-test, Fisher's exact test and the χ(2)-test. The correlation of O(2) flow and PEEP was evaluated by regression analysis and p < 0.05 was considered to be statistically significant. Apart from this a subgroup analysis was performed depending on body-mass index (BMI), American Society of Anesthesiologists (ASA) classification, intraoperative airway management, the use of neuromuscular blocking agents and co-existing disorders, e.g. chronic obstructive lung disease (COLD

  1. CPAP of 4 cm H(2)O Has no short-term benefit at term in infants with BPD.

    PubMed

    Sandberg, Kenneth L; Hjalmarson, Ola

    2012-01-01

    Lung development and function is compromised at term in infants with bronchopulmonary dysplasia (BPD), characterized by reduced functional residual capacity (FRC) and impaired gas-mixing efficiency in distal airways. To determine whether continuous positive airway pressure (CPAP) improves FRC, ventilation, distal airway function, and gas exchange in spontaneously breathing infants with BPD. Twenty-one infants with BPD (median birth weight 0.72 kg (range 0.50-1.27) and median gestational age 26 weeks (range 23-28)) were studied before and after CPAP of 4 cm H(2)O was applied by a facemask system. A multiple-breath nitrogen washout method was used to assess FRC, ventilation, and gas-mixing efficiency. Moment analysis and lung clearance index was calculated from the nitrogen-decay curve for assessment of gas-mixing efficiency. Transcutaneous (Tc) PO(2)/PCO(2) was monitored during stable infant conditions before each washout test. When CPAP was raised from 0 to 4 cm H(2)O, FRC increased significantly together with a significant increase in moment ratios (M(1)/M(0) and M(2)/M(0)). Tc PO(2) decreased significantly and the breathing pattern changed, with significantly reduced respiratory rate, minute ventilation, and alveolar ventilation. There was also an increase in tidal volume and dead space. CPAP of 4 cm H(2)O applied with a facemask at term to infants with BPD did not improve ventilation, gas-mixing efficiency in distal airways, or oxygenation despite an increase in FRC. We speculate that instead of promoting recruitment of unventilated lung volumes, increasing the end-expiratory pressure in infants with BPD may lead to an overexpansion of already ventilated parts of the lung, causing further compromise of lung function. Copyright © 2012 S. Karger AG, Basel.

  2. Positive expiratory pressure - Common clinical applications and physiological effects.

    PubMed

    Fagevik Olsén, Monika; Lannefors, Louise; Westerdahl, Elisabeth

    2015-03-01

    Breathing out against resistance, in order to achieve positive expiratory pressure (PEP), is applied by many patient groups. Pursed lips breathing and a variety of devices can be used to create the resistance giving the increased expiratory pressure. Effects on pulmonary outcomes have been discussed in several publications, but the expected underlying physiology of the effect is seldom discussed. The aim of this article is to describe the purpose, performance, clinical application and underlying physiology of PEP when it is used to increase lung volumes, decrease hyperinflation or improve airway clearance. In clinical practice, the instruction how to use an expiratory resistance is of major importance since it varies. Different breathing patterns during PEP increase or reduce expiratory flow, result in movement of EPP centrally or peripherally and can increase or decrease lung volume. It is therefore necessary to give the right instructions to obtain the desired effects. As the different PEP techniques are being used by diverse patient groups it is not possible to give standard instructions. Based on the information given in this article the instructions have to be adjusted to give the optimal effect. There is no consensus regarding optimal treatment frequency and number of cycles included in each treatment session and must also be individualized. In future research, more precise descriptions are needed about physiological aims and specific instructions of how the treatments have been performed to assure as good treatment quality as possible and to be able to evaluate and compare treatment effects. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Unidirectional Expiratory Valve Method to Assess Maximal Inspiratory Pressure in Individuals without Artificial Airway.

    PubMed

    Grams, Samantha Torres; Kimoto, Karen Yumi Mota; Azevedo, Elen Moda de Oliveira; Lança, Marina; Albuquerque, André Luis Pereira de; Brito, Christina May Moran de; Yamaguti, Wellington Pereira

    2015-01-01

    Maximal Inspiratory Pressure (MIP) is considered an effective method to estimate strength of inspiratory muscles, but still leads to false positive diagnosis. Although MIP assessment with unidirectional expiratory valve method has been used in patients undergoing mechanical ventilation, no previous studies investigated the application of this method in subjects without artificial airway. This study aimed to compare the MIP values assessed by standard method (MIPsta) and by unidirectional expiratory valve method (MIPuni) in subjects with spontaneous breathing without artificial airway. MIPuni reproducibility was also evaluated. This was a crossover design study, and 31 subjects performed MIPsta and MIPuni in a random order. MIPsta measured MIP maintaining negative pressure for at least one second after forceful expiration. MIPuni evaluated MIP using a unidirectional expiratory valve attached to a face mask and was conducted by two evaluators (A and B) at two moments (Tests 1 and 2) to determine interobserver and intraobserver reproducibility of MIP values. Intraclass correlation coefficient (ICC[2,1]) was used to determine intraobserver and interobserver reproducibility. The mean values for MIPuni were 14.3% higher (-117.3 ± 24.8 cmH2O) than the mean values for MIPsta (-102.5 ± 23.9 cmH2O) (p<0.001). Interobserver reproducibility assessment showed very high correlation for Test 1 (ICC[2,1] = 0.91), and high correlation for Test 2 (ICC[2,1] = 0.88). The assessment of the intraobserver reproducibility showed high correlation for evaluator A (ICC[2,1] = 0.86) and evaluator B (ICC[2,1] = 0.77). MIPuni presented higher values when compared with MIPsta and proved to be reproducible in subjects with spontaneous breathing without artificial airway.

  4. Hemodynamic differences between continual positive and two types of negative pressure ventilation.

    PubMed

    Lockhat, D; Langleben, D; Zidulka, A

    1992-09-01

    In seven anesthetized dogs, ventilated with matching lung volumes, tidal volumes, and respiratory rates, we compared the effects on cardiac output (CO), arterial venous oxygen saturation difference (SaO2 - SVO2), and femoral and inferior vena cava pressure (1) intermittent positive pressure ventilation with positive end-expiratory pressure (CPPV); (2) iron-lung ventilation with negative end-expiratory pressure (ILV-NEEP); (3) grid and wrap ventilation with NEEP applied to the thorax and upper abdomen (G&W-NEEP). The values of CO and SaO2 - SVO2 with ILV-NEEP were similar to those with CPPV. However, with G&W-NEEP as compared with ILV-NEEP, mean CO was greater (2.9 versus 2.6 L/min, p = 0.02) and mean (SaO2 - SVO2) was lower (26.6% versus 28.3%, p = NS). Mean PFEM-IVC was higher with G&W-NEEP than with the other types of ventilation. We conclude that (1) ILV-NEEP is hemodynamically equivalent to CPPV and (2) G&W-NEEP has less adverse hemodynamic consequences. has less adverse hemodynamic consequences.

  5. A universal definition of ARDS: the PaO2/FiO2 ratio under a standard ventilatory setting--a prospective, multicenter validation study.

    PubMed

    Villar, Jesús; Pérez-Méndez, Lina; Blanco, Jesús; Añón, José Manuel; Blanch, Lluís; Belda, Javier; Santos-Bouza, Antonio; Fernández, Rosa Lidia; Kacmarek, Robert M

    2013-04-01

    The PaO2/FiO2 is an integral part of the assessment of patients with acute respiratory distress syndrome (ARDS). The American-European Consensus Conference definition does not mandate any standardization procedure. We hypothesized that the use of PaO2/FiO2 calculated under a standard ventilatory setting within 24 h of ARDS diagnosis allows a more clinically relevant ARDS classification. We studied 452 ARDS patients enrolled prospectively in two independent, multicenter cohorts treated with protective mechanical ventilation. At the time of ARDS diagnosis, patients had a PaO2/FiO2 ≤ 200. In the derivation cohort (n = 170), we measured PaO2/FiO2 with two levels of positive end-expiratory pressure (PEEP) (≥ 5 and ≥ 10 cmH2O) and two levels of FiO2 (≥ 0.5 and 1.0) at ARDS onset and 24 h later. Dependent upon PaO2 response, patients were reclassified into three groups: mild (PaO2/FiO2 > 200), moderate (PaO2/FiO2 101-200), and severe (PaO2/FiO2 ≤ 100) ARDS. The primary outcome measure was ICU mortality. The standard ventilatory setting that reached the highest significance difference in mortality among these categories was tested in a separate cohort (n = 282). The only standard ventilatory setting that identified the three PaO2/FiO2 risk categories in the derivation cohort was PEEP ≥ 10 cmH2O and FiO2 ≥ 0.5 at 24 h after ARDS onset (p = 0.0001). Using this ventilatory setting, patients in the validation cohort were reclassified as having mild ARDS (n = 47, mortality 17 %), moderate ARDS (n = 149, mortality 40.9 %), and severe ARDS (n = 86, mortality 58.1 %) (p = 0.00001). Our method for assessing PaO2/FiO2 greatly improved risk stratification of ARDS and could be used for enrolling appropriate ARDS patients into therapeutic clinical trials.

  6. H-TiO(2) @MnO(2) //H-TiO(2) @C core-shell nanowires for high performance and flexible asymmetric supercapacitors.

    PubMed

    Lu, Xihong; Yu, Minghao; Wang, Gongming; Zhai, Teng; Xie, Shilei; Ling, Yichuan; Tong, Yexiang; Li, Yat

    2013-01-11

    A flexible solid-state asymmetric supercapacitor device with H-TiO(2) @MnO(2) core-shell NWs as the positive electrode and H-TiO(2) @C core-shell NWs as the negative electrode is developed. This device operates in a 1.8 V voltage window and is able to deliver a high specific capacitance of 139.6 F g(-1) and maximum volumetric energy density of 0.30 mWh cm(-3) with excellent cycling performance and good flexibility. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Crystal structures of NiSO4·9H2O and NiSO4·8H2O: magnetic properties, stability with respect to morenosite (NiSO4·7H2O), the solid-solution series (Mg x Ni1-x )SO4·9H2O

    NASA Astrophysics Data System (ADS)

    Fortes, A. D.; Knight, K. S.; Gibbs, A. S.; Wood, I. G.

    2018-02-01

    exists between Mg and Ni enneahydrate end-members where we observe preferential partitioning of Ni2+ into the octahedral sites on the 2c Wyckoff positions rather than the 2a sites. The solution is slightly non-ideal, as indicated by the small positive excess volume of mixing. Measurements of the DC magnetisation of quenched NiSO4 solutions reveal anomalies in the molar susceptibility on warming through the region from 221 to 225 K, probably due to devitrification of the (assumed) glassy specimen into a mixture of NiSO4·9H2O + ice Ih. Further temperature-dependent measurements on repeated warming and cooling provide no evidence of magnetic ordering and indicate a weak ferromagnetic coupling between neighbouring Ni2+ ions, likely via super-exchange through the H-bond between neighbouring Ni(H2O)6 octahedra.

  8. Is increased positive end-expiratory pressure the culprit? Autoresuscitation in a 44-year-old man after prolonged cardiopulmonary resuscitation: a case report.

    PubMed

    Hagmann, Henning; Oelmann, Katrin; Stangl, Robert; Michels, Guido

    2016-12-20

    The phenomenon of autoresuscitation is rare, yet it is known to most emergency physicians. However, the pathophysiology of the delayed return of spontaneous circulation remains enigmatic. Among other causes hyperinflation of the lungs and excessively high positive end-expiratory pressure have been suggested, but reports including cardiopulmonary monitoring during cardiopulmonary resuscitation are scarce to support this hypothesis. We report a case of autoresuscitation in a 44-year-old white man after 80 minutes of advanced cardiac life support accompanied by continuous capnometry and repeated evaluation by ultrasound and echocardiography. After prolonged cardiopulmonary resuscitation, refractory electromechanical dissociation on electrocardiogram and ventricular akinesis were recorded. In addition, a precipitous drop in end-tidal partial pressure of carbon dioxide was noted and cardiopulmonary resuscitation was discontinued. Five minutes after withdrawal of all supportive measures his breathing resumed and a perfusing rhythm ensued. Understanding the underlying pathophysiology of autoresuscitation is hampered by a lack of reports including extensive cardiopulmonary monitoring during cardiopulmonary resuscitation in a preclinical setting. In this case, continuous capnometry was combined with repetitive ultrasound evaluation, which ruled out most assumed causes of autoresuscitation. Our observation of a rapid decline in end-tidal partial pressure of carbon dioxide supports the hypothesis of increased intrathoracic pressure. Continuous capnometry can be performed easily during cardiopulmonary resuscitation, also in a preclinical setting. Knowledge of the pathophysiologic mechanisms may lead to facile interventions to be incorporated into cardiopulmonary resuscitation algorithms. A drop in end-tidal partial pressure of carbon dioxide, for example, might prompt disconnection of the ventilation to allow left ventricular filling. Further reports and research on this topic

  9. Influence of the upper airway on breathing pattern and expiratory time constant in unanesthetized dog pups.

    PubMed

    England, S J; Stogryn, H A

    1986-11-01

    Unanesthetized dog pups (2 to 31 days old) respond to sudden opening of a tracheal cannula to atmospheric pressure with a marked increase in breathing frequency. This response is achieved with a 25% decrease in inspiratory and 40% decrease in expiratory times. Expiratory thyroarytenoid muscle activity increased concomitantly, while inspiratory diaphragmatic and posterior cricoarytenoid muscle activities were reduced. These responses are interpreted as a compensatory mechanism for maintenance of an elevated end-expiratory lung volume with functional loss of the upper airway. The changes in expiratory time and thyroarytenoid muscle activity were not observed when positive pressure was applied at the trachea. The expiratory time constant was assessed during spontaneous breathing. The mean value was twice as long during nasal breathing than during tracheal breathing. The nasal value was substantially increased when the thyroarytenoid muscle was active during expiration.

  10. Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

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

    Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

    2009-03-15

    Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

  11. The effect of closed system suction on airway pressures when using the Servo 300 ventilator.

    PubMed

    Frengley, R W; Closey, D N; Sleigh, J W; Torrance, J M

    2001-12-01

    To measure airway pressures during closed system suctioning with the ventilator set to three differing modes of ventilation. Closed system suctioning was conducted in 16 patients following cardiac surgery. Suctioning was performed using a 14 French catheter with a vacuum level of -500 cmH2O through an 8.0 mm internal diameter endotracheal tube. The lungs were mechanically ventilated with a Servo 300 ventilator set to one of three ventilation modes: volume-control, pressure-control or CPAP/pressure support. Airway pressures were measured via a 4 French electronic pressure transducer in both proximal and distal airways. Following insertion of the suction catheter, end-expiratory pressure increased significantly (p < 0.001) in both pressure-control and volume-control ventilation. This increase was greatest (p = 0.018) in volume-control mode (2.7 +/- 1.7 cmH2O). On performing a five second suction, airway pressure decreased in all modes, however the lowest airway pressure in volume-control mode (-4.9 +/- 4.0 cmH2O) was significantly (p = 0.001) less than the lowest airway pressure recorded in either pressure-control (0.8 +/- 1.9 cmH2O) or CPAP/pressure support (0.4 +/- 2.8 cmH2O) modes. In CPAP/pressure support mode, 13 of the 16 patients experienced a positive pressure 'breath' at the end of suctioning with airway pressures rising to 21 +/- 1.6 cmH2O. Closed system suctioning in volume control ventilation may result in elevations of end-expiratory pressure following catheter insertion and subatmospheric airway pressures during suctioning. Pressure control ventilation produces less elevation of end-expiratory pressure following catheter insertion and is less likely to be associated with subatmospheric airway pressures during suctioning. CPAP/pressure support has no effect on end-expiratory pressure following catheter insertion and subatmospheric airway pressures are largely avoided during suctioning.

  12. New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

    NASA Astrophysics Data System (ADS)

    Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

    2012-04-01

    Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

  13. The effects of intraoperative lung protective ventilation with positive end-expiratory pressure on blood loss during hepatic resection surgery: A secondary analysis of data from a published randomised control trial (IMPROVE).

    PubMed

    Neuschwander, Arthur; Futier, Emmanuel; Jaber, Samir; Pereira, Bruno; Eurin, Mathilde; Marret, Emmanuel; Szymkewicz, Olga; Beaussier, Marc; Paugam-Burtz, Catherine

    2016-04-01

    During high-risk abdominal surgery the use of a multi-faceted lung protective ventilation strategy composed of low tidal volumes, positive end-expiratory pressure (PEEP) and recruitment manoeuvres, has been shown to improve clinical outcomes. It has been speculated, however, that mechanical ventilation using PEEP might increase intraoperative bleeding during liver resection. To study the impact of mechanical ventilation with PEEP on bleeding during hepatectomy. Post-hoc analysis of a randomised controlled trial. Seven French university teaching hospitals from January 2011 to August 2012. Patients scheduled for liver resection surgery. In the Intraoperative Protective Ventilation trial, patients scheduled for major abdominal surgery were randomly assigned to mechanical ventilation using low tidal volume, PEEP between 6 and 8  cmH2O and recruitment manoeuvres (lung protective ventilation strategy) or higher tidal volume, zero PEEP and no recruitment manoeuvres (non-protective ventilation strategy). The primary endpoint was intraoperative blood loss volume. A total of 79 (19.8%) patients underwent liver resections (41 in the lung protective and 38 in the non-protective group). The median (interquartile range) amount of intraoperative blood loss was 500 (200 to 800)  ml and 275 (125 to 800)  ml in the non-protective and lung protective ventilation groups, respectively (P = 0.47). Fourteen (35.0%) and eight (21.5%) patients were transfused in the non-protective and lung protective groups, respectively (P = 0.17), without a statistically significant difference in the median (interquartile range) number of red blood cells units transfused [2.5 (2 to 4) units and 3 (2 to 6) units in the two groups, respectively; P = 0.54]. During hepatic surgery, mechanical ventilation using PEEP within a multi-faceted lung protective strategy was not associated with increased bleeding compared with non-protective ventilation using zero PEEP. The current study was not

  14. Intra-operative protective mechanical ventilation in lung transplantation: a randomised, controlled trial.

    PubMed

    Verbeek, G L; Myles, P S; Westall, G P; Lin, E; Hastings, S L; Marasco, S F; Jaffar, J; Meehan, A C

    2017-08-01

    Primary graft dysfunction occurs in up to 25% of patients after lung transplantation. Contributing factors include ventilator-induced lung injury, cardiopulmonary bypass, ischaemia-reperfusion injury and excessive fluid administration. We evaluated the feasibility, safety and efficacy of an open-lung protective ventilation strategy aimed at reducing ventilator-induced lung injury. We enrolled adult patients scheduled to undergo bilateral sequential lung transplantation, and randomly assigned them to either a control group (volume-controlled ventilation with 5 cmH 2 O, positive end-expiratory pressure, low tidal volumes (two-lung ventilation 6 ml.kg -1 , one-lung ventilation 4 ml.kg -1 )) or an alveolar recruitment group (regular step-wise positive end-expiratory pressure-based alveolar recruitment manoeuvres, pressure-controlled ventilation set at 16 cmH 2 O with 10 cmH 2 O positive end-expiratory pressure). Ventilation strategies were commenced from reperfusion of the first lung allograft and continued for the duration of surgery. Regular PaO 2 /F I O 2 ratios were calculated and venous blood samples collected for inflammatory marker evaluation during the procedure and for the first 24 h of intensive care stay. The primary end-point was the PaO 2 /F I O 2 ratio at 24 h after first lung reperfusion. Thirty adult patients were studied. The primary outcome was not different between groups (mean (SD) PaO 2 /F I O 2 ratio control group 340 (111) vs. alveolar recruitment group 404 (153); adjusted p = 0.26). Patients in the control group had poorer mean (SD) PaO 2 /F I O 2 ratios at the end of the surgical procedure and a longer median (IQR [range]) time to tracheal extubation compared with the alveolar recruitment group (308 (144) vs. 402 (154) (p = 0.03) and 18 (10-27 [5-468]) h vs. 15 (11-36 [5-115]) h (p = 0.01), respectively). An open-lung protective ventilation strategy during surgery for lung transplantation is feasible, safe and achieves favourable

  15. The Mobilome; A Major Contributor to Escherichia coli stx2-Positive O26:H11 Strains Intra-Serotype Diversity.

    PubMed

    Delannoy, Sabine; Mariani-Kurkdjian, Patricia; Webb, Hattie E; Bonacorsi, Stephane; Fach, Patrick

    2017-01-01

    Shiga toxin-producing Escherichia coli of serotype O26:H11/H- constitute a diverse group of strains and several clones with distinct genetic characteristics have been identified and characterized. Whole genome sequencing was performed using Illumina and PacBio technologies on eight stx2 -positive O26:H11 strains circulating in France. Comparative analyses of the whole genome of the stx2 -positive O26:H11 strains indicate that several clones of EHEC O26:H11 are co-circulating in France. Phylogenetic analysis of the French strains together with stx2 -positive and stx -negative E. coli O26:H11 genomes obtained from Genbank indicates the existence of four clonal complexes (SNP-CCs) separated in two distinct lineages, one of which comprises the "new French clone" (SNP-CC1) that appears genetically closely related to stx -negative attaching and effacing E. coli (AEEC) strains. Interestingly, the whole genome SNP (wgSNP) phylogeny is summarized in the cas gene phylogeny, and a simple qPCR assay targeting the CRISPR array specific to SNP-CC1 (SP_O26-E) can distinguish between the two main lineages. The PacBio sequencing allowed a detailed analysis of the mobile genetic elements (MGEs) of the strains. Numerous MGEs were identified in each strain, including a large number of prophages and up to four large plasmids, representing overall 8.7-19.8% of the total genome size. Analysis of the prophage pool of the strains shows a considerable diversity with a complex history of recombination. Each clonal complex (SNP-CC) is characterized by a unique set of plasmids and phages, including stx -prophages, suggesting evolution through separate acquisition events. Overall, the MGEs appear to play a major role in O26:H11 intra-serotype clonal diversification.

  16. The Mobilome; A Major Contributor to Escherichia coli stx2-Positive O26:H11 Strains Intra-Serotype Diversity

    PubMed Central

    Delannoy, Sabine; Mariani-Kurkdjian, Patricia; Webb, Hattie E.; Bonacorsi, Stephane; Fach, Patrick

    2017-01-01

    Shiga toxin-producing Escherichia coli of serotype O26:H11/H- constitute a diverse group of strains and several clones with distinct genetic characteristics have been identified and characterized. Whole genome sequencing was performed using Illumina and PacBio technologies on eight stx2-positive O26:H11 strains circulating in France. Comparative analyses of the whole genome of the stx2-positive O26:H11 strains indicate that several clones of EHEC O26:H11 are co-circulating in France. Phylogenetic analysis of the French strains together with stx2-positive and stx-negative E. coli O26:H11 genomes obtained from Genbank indicates the existence of four clonal complexes (SNP-CCs) separated in two distinct lineages, one of which comprises the “new French clone” (SNP-CC1) that appears genetically closely related to stx-negative attaching and effacing E. coli (AEEC) strains. Interestingly, the whole genome SNP (wgSNP) phylogeny is summarized in the cas gene phylogeny, and a simple qPCR assay targeting the CRISPR array specific to SNP-CC1 (SP_O26-E) can distinguish between the two main lineages. The PacBio sequencing allowed a detailed analysis of the mobile genetic elements (MGEs) of the strains. Numerous MGEs were identified in each strain, including a large number of prophages and up to four large plasmids, representing overall 8.7–19.8% of the total genome size. Analysis of the prophage pool of the strains shows a considerable diversity with a complex history of recombination. Each clonal complex (SNP-CC) is characterized by a unique set of plasmids and phages, including stx-prophages, suggesting evolution through separate acquisition events. Overall, the MGEs appear to play a major role in O26:H11 intra-serotype clonal diversification. PMID:28932209

  17. The roles of two O-donor ligands in the Fe2+-binding and H2O2-sensing by the Fe2+-dependent H2O2 sensor PerR.

    PubMed

    Ji, Chang-Jun; Yang, Yoon-Mo; Kim, Jung-Hoon; Ryu, Su-Hyun; Youn, Hwan; Lee, Jin-Won

    2018-05-10

    PerR is a metal-dependent peroxide sensing transcription factor which controls the expression of genes involved in peroxide resistance. The function of Bacillus subtilis PerR is mainly dictated by the regulatory metal ion (Fe 2+ or Mn 2+ ) coordinated by three N-donor ligands (His37, His91, and His93) and two O-donor ligands (Asp85 and Asp104). While H 2 O 2 sensing by PerR is mediated by Fe 2+ -dependent oxidation of N-donor ligand (either His37 or His91), one of the O-donor ligands (Asp104), but not Asp85, has been proposed as the key residue that regulates the sensitivity of PerR to H 2 O 2 . Here we systematically investigated the relative roles of two O-donor ligands of PerR in metal-binding affinity and H 2 O 2 sensitivity in vivo and in vitro. Consistent with the previous report, in vitro the D104E-PerR could not sense low levels of H 2 O 2 in the presence of excess Fe 2+ sufficient for the formation of the Fe 2+ -bound D104E-PerR. However, the expression of PerR-regulated reporter fusion was not repressed by D104E-PerR in the presence of Fe 2+ , suggesting that Fe 2+ is not an effective corepressor for this mutant protein in vivo. Furthermore, in vitro metal titration assays indicate that D104E-PerR has a significantly reduced affinity for Fe 2+ , but not for Mn 2+ , when compared to wild type PerR. These data indicate that the type of O-donor ligand (Asp vs. Glu) at position 104 is an important determinant in providing high Fe 2+ -binding affinity required for the sensing of the physiologically relevant Fe 2+ -levels, in addition to its role in rendering PerR highly sensitive to physiological levels of H 2 O 2 . In comparison, the D85E-PerR did not show a perturbed change in Fe 2+ -binding affinity, however, it displayed a slightly decreased sensitivity to H 2 O 2 both in vivo and in vitro, suggesting that the type of O-donor ligand (Asp vs. Glu) at position 85 may be important for the fine-tuning of H 2 O 2 sensitivity. Copyright © 2018 Elsevier

  18. Lung recruitment manoeuvres are effective in regaining lung volume and oxygenation after open endotracheal suctioning in acute respiratory distress syndrome

    PubMed Central

    Dyhr, Thomas; Bonde, Jan; Larsson, Anders

    2003-01-01

    Introduction Lung collapse is a contributory factor in the hypoxaemia that is observed after open endotracheal suctioning (ETS) in patients with acute lung injury and acute respiratory distress syndrome. Lung recruitment (LR) manoeuvres may be effective in rapidly regaining lung volume and improving oxygenation after ETS. Materials and method A prospective, randomized, controlled study was conducted in a 15-bed general intensive care unit at a university hospital. Eight consecutive mechanically ventilated patients with acute lung injury or acute respiratory distress syndrome were included. One of two suctioning procedures was performed in each patient. In the first procedure, ETS was performed followed by LR manoeuvre and reconnection to the ventilator with positive end-expiratory pressure set at 1 cmH2O above the lower inflexion point, and after 60 min another ETS (but without LR manoeuvre) was performed followed by reconnection to the ventilator with similar positive end-expiratory pressure; the second procedure was the same as the first but conducted in reverse order. Before (baseline) and over 25 min following each ETS procedure, partial arterial oxygen tension (PaO2) and end-expiratory lung volume were measured. Results After ETS, PaO2 decreased by 4.3(0.9–9.7)kPa (median and range; P < 0.005). After LR manoeuvre, PaO2 recovered to baseline. Without LR manoeuvre, PaO2 was reduced (P = 0.05) until 7 min after ETS. With LR manoeuvre end-expiratory lung volume was unchanged after ETS, whereas without LR manoeuvre end-expiratory lung volume was still reduced (approximately 10%) at 5 and 15 min after ETS (P = 0.01). Discussion A LR manoeuvre immediately following ETS was, as an adjunct to positive end-expiratory pressure, effective in rapidly counteracting the deterioration in PaO2 and lung volume caused by open ETS in ventilator-treated patients with acute lung injury or acute respiratory distress syndrome. PMID:12617741

  19. Expiratory Flow Limitation as a Risk Factor for Pulmonary Complications After Major Abdominal Surgery.

    PubMed

    Spadaro, Savino; Caramori, Gaetano; Rizzuto, Chiara; Mojoli, Francesco; Zani, Gianluca; Ragazzi, Riccardo; Valpiani, Giorgia; Dalla Corte, Francesca; Marangoni, Elisabetta; Volta, Carlo Alberto

    2017-02-01

    Postoperative pulmonary complications are major causes of postoperative morbidity and mortality. Although several risk factors have been associated with postoperative pulmonary complications, they are not consistent between studies and, even in those studies in which these factors were identified, the predictive power is low. We hypothesized that postoperative pulmonary complications would correlate with the presence of intraoperative expiratory flow limitation. Candidates for this prospective observational study were patients undergoing general anesthesia for major abdominal surgery. Preoperative data collection included age, body mass index, American Society of Anesthesiologists class, smoking and dyspnea history, and room air PO2. Expiratory flow limitation was assessed intraoperatively using the positive end-expiratory pressure test. Postoperative data collection included the incidence of postoperative pulmonary complications. Of the 330 patients we enrolled, 31% exhibited expiratory flow limitation. On univariate analysis, patients with expiratory flow limitation were more likely to have postoperative pneumonia (5% vs 0%, P < .001) and acute respiratory failure (11% vs 1%, P < .001) and a longer length of hospital stay (7 vs 9 days, P < .01). Multivariate analysis identified that expiratory flow limitation increased the risk of developing postoperative pulmonary complications by >50% (risk ratio, 2.7; 95% confidence interval, 1.7-4.2). Age and Medical Research Council dyspnea score were also significant multivariate risk factors for pulmonary complications. Our results show that intraoperative expiratory flow limitation correlates with that of postoperative pulmonary complication after major abdominal surgery. Further work is needed to better understand the relevance of expiratory flow limitation on postoperative pulmonary outcomes.

  20. Degradation of 5-FU by means of advanced (photo)oxidation processes: UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2--Comparison of transformation products, ready biodegradability and toxicity.

    PubMed

    Lutterbeck, Carlos Alexandre; Wilde, Marcelo Luís; Baginska, Ewelina; Leder, Christoph; Machado, Ênio Leandro; Kümmerer, Klaus

    2015-09-15

    The present study investigates the degradation of the antimetabolite 5-fluorouracil (5-FU) by three different advanced photo oxidation processes: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. Prescreening experiments varying the H2O2 and TiO2 concentrations were performed in order to set the best catalyst concentrations in the UV/H2O2 and UV/TiO2 experiments, whereas the UV/Fe(2+)/H2O2 process was optimized varying the pH, Fe(2+) and H2O2 concentrations by means of the Box-Behnken design (BBD). 5-FU was quickly removed in all the irradiation experiments. The UV/Fe(2+)/H2O2 and UV/TiO2 processes achieved the highest degree of mineralization, whereas the lowest one resulted from the UV/H2O2 treatment. Six transformation products were formed during the advanced (photo)oxidation processes and identified using low and high resolution mass spectrometry. Most of them were formed and further eliminated during the reactions. The parent compound of 5-FU was not biodegraded, whereas the photolytic mixture formed in the UV/H2O2 treatment after 256 min showed a noticeable improvement of the biodegradability in the closed bottle test (CBT) and was nontoxic towards Vibrio fischeri. In silico predictions showed positive alerts for mutagenic and genotoxic effects of 5-FU. In contrast, several of the transformation products (TPs) generated along the processes did not provide indications for mutagenic or genotoxic activity. One exception was TP with m/z 146 with positive alerts in several models of bacterial mutagenicity which could demand further experimental testing. Results demonstrate that advanced treatment can eliminate parent compounds and its toxicity. However, transformation products formed can still be toxic. Therefore toxicity screening after advanced treatment is recommendable. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Global Flux Balance in the Terrestrial H2O Cycle: Reconsidering the Post-Arc Subducted H2O Flux

    NASA Astrophysics Data System (ADS)

    Parai, R.; Mukhopadhyay, S.

    2010-12-01

    Quantitative estimates of H2O fluxes between the mantle and the exosphere (i.e., the atmosphere, oceans and crust) are critical to our understanding of the chemistry and dynamics of the solid Earth: the abundance and distribution of water in the mantle has dramatic impacts upon mantle melting, degassing history, structure and style of convection. Water is outgassed from the mantle is association with volcanism at mid-ocean ridges, ocean islands and convergent margins. H2O is removed from the exosphere at subduction zones, and some fraction of the subducted flux may be recycled past the arc into the Earth’s deep interior. Estimates of the post-arc subducted H2O flux are primarily based on the stability of hydrous phases at subduction zone pressures and temperatures (e.g. Schmidt and Poli, 1998; Rüpke et al., 2004; Hacker, 2008). However, the post-arc H2O flux remains poorly quantified, in part due to large uncertainties in the water content of the subducting slab. Here we evaluate estimated post-arc subducted fluxes in the context of mantle-exosphere water cycling, using a Monte Carlo simulation of the global H2O cycle. Literature estimates of primary magmatic H2O abundances and magmatic production rates at different tectonic settings are used with estimates of the total subducted H2O flux to establish the parameter space under consideration. Random sampling of the allowed parameter space affords insight into which input and output fluxes satisfy basic constraints on global flux balance, such as a limit on sea-level change over time. The net flux of H2O between mantle and exosphere is determined by the total mantle output flux (via ridges and ocean islands, with a small contribution from mantle-derived arc output) and the input flux subducted beyond the arc. Arc and back-arc output is derived mainly from the slab, and therefore cancels out a fraction of the trench intake in an H2O subcycle. Limits on sea-level change since the end of the Archaean place

  2. Microchannel Reactor System Design & Demonstration For On-Site H2O2 Production by Controlled H2/O2 Reaction

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

    Adeniyi Lawal

    We successfully demonstrated an innovative hydrogen peroxide (H2O2) production concept which involved the development of flame- and explosion-resistant microchannel reactor system for energy efficient, cost-saving, on-site H2O2 production. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for controlled direct combination of H2 and O2 in all proportions including explosive regime, at a low pressure and a low temperature to produce about 1.5 wt% H2O2 as proposed. In the second phase of the program, as a prelude to full-scale commercialization, we demonstrated our H2O2 production approach by ‘numbering up’ the channels in a multi-channel microreactor-based pilot plant tomore » produce 1 kg/h of H2O2 at 1.5 wt% as demanded by end-users of the developed technology. To our knowledge, we are the first group to accomplish this significant milestone. We identified the reaction pathways that comprise the process, and implemented rigorous mechanistic kinetic studies to obtain the kinetics of the three main dominant reactions. We are not aware of any such comprehensive kinetic studies for the direct combination process, either in a microreactor or any other reactor system. We showed that the mass transfer parameter in our microreactor system is several orders of magnitude higher than what obtains in the macroreactor, attesting to the superior performance of microreactor. A one-dimensional reactor model incorporating the kinetics information enabled us to clarify certain important aspects of the chemistry of the direct combination process as detailed in section 5 of this report. Also, through mathematical modeling and simulation using sophisticated and robust commercial software packages, we were able to elucidate the hydrodynamics of the complex multiphase flows that take place in the microchannel. In conjunction with the kinetics information, we were able to validate the experimental data. If fully implemented across the

  3. Effects of pleural effusion drainage on oxygenation, respiratory mechanics, and hemodynamics in mechanically ventilated patients.

    PubMed

    Razazi, Keyvan; Thille, Arnaud W; Carteaux, Guillaume; Beji, Olfa; Brun-Buisson, Christian; Brochard, Laurent; Mekontso Dessap, Armand

    2014-09-01

    In mechanically ventilated patients, the effect of draining pleural effusion on oxygenation is controversial. We investigated the effect of large pleural effusion drainage on oxygenation, respiratory function (including lung volumes), and hemodynamics in mechanically ventilated patients after ultrasound-guided drainage. Arterial blood gases, respiratory mechanics (airway, pleural and transpulmonary pressures, end-expiratory lung volume, respiratory system compliance and resistance), and hemodynamics (blood pressure, heart rate, and cardiac output) were recorded before and at 3 and 24 hours (H24) after pleural drainage. The respiratory settings were kept identical during the study period. The mean volume of effusion drained was 1,579 ± 684 ml at H24. Uncomplicated pneumothorax occurred in two patients. Respiratory mechanics significantly improved after drainage, with a decrease in plateau pressure and a large increase in end-expiratory transpulmonary pressure. Respiratory system compliance, end-expiratory lung volume, and PaO2/FiO2 ratio all improved. Hemodynamics were not influenced by drainage. Improvement in the PaO2/FiO2 ratio from baseline to H24 was positively correlated with the increase in end-expiratory lung volume during the same time frame (r = 0.52, P = 0.033), but not with drained volume. A high value of pleural pressure or a highly negative transpulmonary pressure at baseline predicted limited lung expansion following effusion drainage. A lesser improvement in oxygenation occurred in patients with ARDS. Drainage of large (≥500 ml) pleural effusion in mechanically ventilated patients improves oxygenation and end-expiratory lung volume. Oxygenation improvement correlated with an increase in lung volume and a decrease in transpulmonary pressure, but was less so in patients with ARDS.

  4. H2O Paradox and its Implications on H2O in Moon

    NASA Astrophysics Data System (ADS)

    Zhang, Youxue

    2017-04-01

    The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

  5. Synthesis and structure of heptaaqua(nitrilotris(methylenephosphonato))(dibarium)sodium monohydrate [Na(H{sub 2}O){sub 3}(μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(μ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O

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

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: xps@ftiudm.ru; Zakirova, R. M., E-mail: ftt@udsu.ru

    Crystals of the monohydrate form of heptaaqua(nitrilotris(methylenephosphonato))(dibarium) sodium [Na(H{sub 2}O{sub )3}(µ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(µ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O are obtained; space group P2{sub 1}/c, Z = 4; a = 13.9117(10) Å, b = 11.54030(10) Å, and c = 24.1784(17) Å, ß = 148.785(18)°. The Na atom is coordinated octahedrally by one oxygen atom of a phosphonate group and five water molecules, including two bridging molecules. Ba atoms occupy two inequivalent crystallographic positions with coordination number eight and nine. The coordination spheres of both Ba atoms include two water molecules. Each ligand is bound to one Namore » atom and five Ba atoms forming three Ba–O–P–O and five Ba–O–P–C–N–C–P–O chelate cycles. In addition to the coordination bonds, molecules, including the solvate water molecule, are involved in hydrogen bonds in the crystal packing.« less

  6. Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

    NASA Astrophysics Data System (ADS)

    Roggensack, K.; Allison, C. M.; Clarke, A. B.

    2017-12-01

    A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

  7. Alveolar edema dispersion and alveolar protein permeability during high volume ventilation: effect of positive end-expiratory pressure.

    PubMed

    de Prost, Nicolas; Roux, Damien; Dreyfuss, Didier; Ricard, Jean-Damien; Le Guludec, Dominique; Saumon, Georges

    2007-04-01

    To evaluate whether PEEP affects intrapulmonary alveolar edema liquid movement and alveolar permeability to proteins during high volume ventilation. Experimental study in an animal research laboratory. 46 male Wistar rats. A (99m)Tc-labeled albumin solution was instilled in a distal airway to produce a zone of alveolar flooding. Conventional ventilation (CV) was applied for 30 min followed by various ventilation strategies for 3 h: CV, spontaneous breathing, and high volume ventilation with different PEEP levels (0, 6, and 8 cmH(2)O) and different tidal volumes. Dispersion of the instilled liquid and systemic leakage of (99m)Tc-albumin from the lungs were studied by scintigraphy. The instillation protocol produced a zone of alveolar flooding that stayed localized during CV or spontaneous breathing. High volume ventilation dispersed alveolar liquid in the lungs. This dispersion was prevented by PEEP even when tidal volume was the same and thus end-inspiratory pressure higher. High volume ventilation resulted in the leakage of instilled (99m)Tc-albumin from the lungs. This increase in alveolar albumin permeability was reduced by PEEP. Albumin permeability was more affected by the amplitude of tidal excursions than by overall lung distension. PEEP prevents the dispersion of alveolar edema liquid in the lungs and lessens the increase in alveolar albumin permeability due to high volume ventilation.

  8. Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

    NASA Astrophysics Data System (ADS)

    Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

    1996-11-01

    The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

  9. USE OF POSITIVE PRESSURE IN THE BARIATRIC SURGERY AND EFFECTS ON PULMONARY FUNCTION AND PREVALENCE OF ATELECTASIS: RANDOMIZED AND BLINDED CLINICAL TRIAL

    PubMed Central

    BALTIERI, Letícia; SANTOS, Laisa Antonela; RASERA-JUNIOR, Irineu; MONTEBELO, Maria Imaculada Lima; PAZZIANOTTO-FORTI, Eli Maria

    2014-01-01

    Background In surgical procedures, obesity is a risk factor for the onset of intra and postoperative respiratory complications. Aim Determine what moment of application of positive pressure brings better benefits on lung function, incidence of atelectasis and diaphragmatic excursion, in the preoperative, intraoperative or immediate postoperative period. Method Randomized, controlled, blinded study, conducted in a hospital and included subjects with BMI between 40 and 55 kg/m2, 25 and 55 years, underwent bariatric surgery by laparotomy. They were underwent preoperative and postoperative evaluations. They were allocated into four different groups: 1) Gpre: treated with positive pressure in the BiPAP mode (Bi-Level Positive Airway Pressure) before surgery for one hour; 2) Gpos: BIPAP after surgery for one hour; 3) Gintra: PEEP (Positive End Expiratory Pressure) at 10 cmH2O during the surgery; 4) Gcontrol: only conventional respiratory physiotherapy. The evaluation consisted of anthropometric data, pulmonary function tests and chest radiography. Results Were allocated 40 patients, 10 in each group. There were significant differences for the expiratory reserve volume and percentage of the predicted expiratory reserve volume, in which the groups that received treatment showed a smaller loss in expiratory reserve volume from the preoperative to postoperative stages. The postoperative radiographic analysis showed a 25% prevalence of atelectasis for Gcontrol, 11.1% for Gintra, 10% for Gpre, and 0% for Gpos. There was no significant difference in diaphragmatic mobility amongst the groups. Conclusion The optimal time of application of positive pressure is in the immediate postoperative period, immediately after extubation, because it reduces the incidence of atelectasis and there is reduction of loss of expiratory reserve volume. PMID:25409961

  10. Use of positive pressure in the bariatric surgery and effects on pulmonary function and prevalence of atelectasis: randomized and blinded clinical trial.

    PubMed

    Baltieri, Letícia; Santos, Laisa Antonela; Rasera, Irineu; Montebelo, Maria Imaculada Lima; Pazzianotto-Forti, Eli Maria

    2014-01-01

    In surgical procedures, obesity is a risk factor for the onset of intra and postoperative respiratory complications. Determine what moment of application of positive pressure brings better benefits on lung function, incidence of atelectasis and diaphragmatic excursion, in the preoperative, intraoperative or immediate postoperative period. Randomized, controlled, blinded study, conducted in a hospital and included subjects with BMI between 40 and 55 kg/m2, 25 and 55 years, underwent bariatric surgery by laparotomy. They were underwent preoperative and postoperative evaluations. They were allocated into four different groups: 1) Gpre: treated with positive pressure in the BiPAP mode (Bi-Level Positive Airway Pressure) before surgery for one hour; 2) Gpos: BIPAP after surgery for one hour; 3) Gintra: PEEP (Positive End Expiratory Pressure) at 10 cmH2O during the surgery; 4) Gcontrol: only conventional respiratory physiotherapy. The evaluation consisted of anthropometric data, pulmonary function tests and chest radiography. Were allocated 40 patients, 10 in each group. There were significant differences for the expiratory reserve volume and percentage of the predicted expiratory reserve volume, in which the groups that received treatment showed a smaller loss in expiratory reserve volume from the preoperative to postoperative stages. The postoperative radiographic analysis showed a 25% prevalence of atelectasis for Gcontrol, 11.1% for Gintra, 10% for Gpre, and 0% for Gpos. There was no significant difference in diaphragmatic mobility amongst the groups. The optimal time of application of positive pressure is in the immediate postoperative period, immediately after extubation, because it reduces the incidence of atelectasis and there is reduction of loss of expiratory reserve volume.

  11. Pleural effusion in patients with acute lung injury: a CT scan study.

    PubMed

    Chiumello, Davide; Marino, Antonella; Cressoni, Massimo; Mietto, Cristina; Berto, Virna; Gallazzi, Elisabetta; Chiurazzi, Chiara; Lazzerini, Marco; Cadringher, Paolo; Quintel, Michael; Gattinoni, Luciano

    2013-04-01

    Pleural effusion is a frequent finding in patients with acute respiratory distress syndrome. To assess the effects of pleural effusion in patients with acute lung injury on lung volume, respiratory mechanics, gas exchange, lung recruitability, and response to positive end-expiratory pressure. A total of 129 acute lung injury or acute respiratory distress syndrome patients, 68 analyzed retrospectively and 61 prospectively, studied at two University Hospitals. Whole-lung CT was performed during two breath-holding pressures (5 and 45 cm H2O). Two levels of positive end-expiratory pressure (5 and 15 cm H2O) were randomly applied. Pleural effusion volume was determined on each CT scan section; respiratory system mechanics, gas exchange, and hemodynamics were measured at 5 and 15 cm H2O positive end-expiratory pressure. In 60 patients, elastances of lung and chest wall were computed, and lung and chest wall displacements were estimated. Patients were divided into higher and lower pleural effusion groups according to the median value (287 mL). Patients with higher pleural effusion were older (62±16 yr vs. 54±17 yr, p<0.01) with a lower minute ventilation (8.8±2.2 L/min vs. 10.1±2.9 L/min, p<0.01) and respiratory rate (16±5 bpm vs. 19±6 bpm, p<0.01) than those with lower pleural effusion. Both at 5 and 15 cm H2O of positive end-expiratory pressure PaO2/FIO2, respiratory system elastance, lung weight, normally aerated tissue, collapsed tissue, and lung and chest wall elastances were similar between the two groups. The thoracic cage expansion (405±172 mL vs. 80±87 mL, p<0.0001, for higher pleural effusion group vs. lower pleural effusion group) was greater than the estimated lung compression (178±124 mL vs. 23±29 mL, p<0.0001 for higher pleural effusion group vs. lower pleural effusion group, respectively). Pleural effusion in acute lung injury or acute respiratory distress syndrome patients is of modest entity and leads to a greater chest wall expansion than lung

  12. End-systolic pressure-volume relationships in dogs during ventilation with PEEP.

    PubMed

    Crottogini, A J; Willshaw, P; Barra, J G; Breitbart, G J; Pichel, R H

    1988-04-01

    Whether left ventricular (LV) contractility changes during ventilation with positive end-expiratory pressure (PEEP) remains controversial. To assess LV inotropic state during PEEP using a load-independent index, we generated end-systolic pressure-volume relationships (ESPVRs) in eight closed-chest, chronically instrumented, anesthetized dogs undergoing 0 [zero end-expiratory pressure for the 1st time (ZEEP1)], 5 (PEEP-5), 10 (PEEP-10), and again 0 (ZEEP2) cmH2O PEEP. LV volume was calculated from three orthogonal internal diameters (sonomicrometry), and LV pressure was measured using an implanted transducer. ESPVRs at each level of PEEP were generated by transient inflation of a vena caval occluder. Despite significant decreases in cardiac output with PEEP-5 (1.81 +/- 0.38 l/min, means +/- SE; P less than 0.05) and PEEP-10 (1.70 +/- 0.46; P less than 0.01) with respect to ZEEP1 (2.12 +/- 0.41), no change was found in the slope (ZEEP1: 6.99 +/- 1.03 mmHg/ml; PEEP-5: 7.48 +/- 1.20; PEEP-10: 7.17 +/- 1.02; ZEEP2: 7.38 +/- 1.02), the volume intercept (ZEEP1: 7.4 +/- 3.4 ml; PEEP-5: 6.6 +/- 3.0; PEEP-10: 7.2 +/- 4.0; ZEEP2: 6.6 +/- 3.6), or the new index area beneath the ESPVR (ZEEP1: 304 +/- 98; PEEP-5: 329 +/- 104; PEEP-10: 310 +/- 98; ZEEP2: 343 +/- 114). We conclude that these levels of PEEP do not affect LV contractility as assessed by the ESPVR.

  13. Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13.

    PubMed

    Tang, Jian; McKellar, A R W

    2005-09-15

    High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.

  14. Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

    PubMed

    Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2012-02-20

    Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

  15. Infrared Spectroscopy of the H2/HD/D2-O2 Van Der Waals Complexes

    NASA Astrophysics Data System (ADS)

    Raston, Paul; Bunn, Hayley

    2016-06-01

    Hydrogen is the most abundant element in the universe and oxygen is the third, so understanding the interaction between the two in their different forms is important to understanding astrochemical processes. The interaction between H2 and O2 has been explored in low energy scattering experiments and by far infrared synchrotron spectroscopy of the van der Waals complex. The far infrared spectra suggest a parallel stacked average structure with seven bound rotationally excited states. Here, we present the far infrared spectrum of HD/D2-O2 and the mid infrared spectrum of H2-O2 at 80 K, recorded at the infrared beamline facility of the Australian Synchrotron. We observed 'sharp' peaks in the mid infrared region, corresponding to the end over end rotation of H2-O2, that are comparatively noisier than analogous peaks in the far infrared where the synchrotron light is brightest. The larger reduced mass of HD and D2 compared to H2 is expected to result in more rotational bound states and narrower bands. The latest results in our ongoing efforts to explore this system will be presented. Y. Kalugina, et al., Phys. Chem. Chem. Phys. 14, 16458 (2012) S. Chefdeville et al. Science 341, 1094 (2013) H. Bunn et al. ApJ 799, 65 (2015)

  16. Prevalence of tidal expiratory flow limitation in preschool children with and without respiratory symptoms: application of the negative expiratory pressure (NEP) method.

    PubMed

    JIRICKOVA, A; SULC, J; POHUNEK, P; KITTNAR, O; DOHNALOVA, A; KOFRANEK, J

    2009-01-01

    Negative expiratory pressure (NEP) applied at the mouth during tidal expiration provides a non-invasive method for detecting expiratory flow limitation. Forty-two children were studied, i.e. 25 children with different respiratory symptoms (R) and 17 without any respiratory symptoms (NR). Children were examined without any sedation. A preset NEP of -5 cm H(2)O was applied; its duration did not exceed duration of tidal expiration. A significance of FL was judged by determining of a flow-limited range (in % of tidal volume). FL was found in 48 % children of R group. No patient of the NR group elicited FL (P<0.001 R vs. NR). The frequency of upper airway collapses was higher in R group (12 children) than in NR group (5 children). In conclusion, a high frequency of tidal FL in the R group was found, while it was not present in NR group. A relatively high frequency of expiratory upper airway collapses was found in both groups, but it did not differ significantly. NEP method represents a reasonable approach for tidal flow limitation testing in non-sedated preschool children.

  17. Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

    NASA Astrophysics Data System (ADS)

    Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

    1994-05-01

    Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

  18. Work of breathing using different interfaces in spontaneous positive pressure ventilation: helmet, face-mask, and endotracheal tube.

    PubMed

    Oda, Shinya; Otaki, Kei; Yashima, Nozomi; Kurota, Misato; Matsushita, Sachiko; Kumasaka, Airi; Kurihara, Hutaba; Kawamae, Kaneyuki

    2016-08-01

    Noninvasive positive pressure ventilation (NPPV) using a helmet is expected to cause inspiratory trigger delay due to the large collapsible and compliant chamber. We compared the work of breathing (WOB) of NPPV using a helmet or a full face-mask with that of invasive ventilation by tracheal intubation. We used a lung model capable of simulating spontaneous breathing (LUNGOO; Air Water Inc., Japan). LUNGOO was set at compliance (C) = 50 mL/cmH2O and resistance (R) = 5 cmH2O/L/s for normal lung simulation, C = 20 mL/cmH2O and R = 5 cmH2O/L/s for restrictive lung, and C = 50 mL/cmH2O and R = 20 cmH2O/L/s for obstructive lung. Muscle pressure was fixed at 25 cmH2O and respiratory rate at 20 bpm. Pressure support ventilation and continuous positive airway pressure were performed with each interface placed on a dummy head made of reinforced plastic that was connected to LUNGOO. We tested the inspiratory WOB difference between the interfaces with various combinations of ventilator settings (positive end-expiratory pressure 5 cmH2O; pressure support 0, 5, and 10 cmH2O). In the normal lung and restrictive lung models, WOB decreased more with the face-mask than the helmet, especially when accompanied by the level of pressure support. In the obstructive lung model, WOB with the helmet decreased compared with the other two interfaces. In the mixed lung model, there were no significant differences in WOB between the three interfaces. NPPV using a helmet is more effective than the other interfaces for WOB in obstructive lung disease.

  19. X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

    NASA Technical Reports Server (NTRS)

    Romanova, A. V.; Skryshevskiy, A. F.

    1979-01-01

    Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

  20. The Paradox of a Wet (High H2O) and Dry (Low H2O/Ce) Mantle: High Water Concentrations in Mantle Garnet Pyroxenites from Hawaii

    NASA Technical Reports Server (NTRS)

    Peslier, Anne H.; Bizimis, Michael

    2013-01-01

    Water dissolved as trace amounts in anhydrous minerals has a large influence on the melting behavior and physical properties of the mantle. The water concentration of the oceanic mantle is inferred from the analyses of Mid-Ocean Ridge Basalt (MORB) and Oceanic Island Basalt (OIB). but there is little data from actual mantle samples. Moreover, enriched mineralogies (pyroxenites, eclogites) are thought as important sources of heterogeneity in the mantle, but their water concentrations and their effect on the water budget and cycling in the mantle are virtually unknown. Here, we analyzed by FTIR water in garnet clinopyroxenite xenoliths from Salt Lake Crater, Oahu, Hawaii. These pyroxenites are high-pressure (>20kb) crystal fractionates from alkalic melts. The clinopyroxenes (cpx) have 260 to 576 ppm wt H2O, with the least differentiated samples (Mg#>0.8) in the 400-500 ppm range. Orthopyroxene (opx) contain 117-265 ppm H2O, about half of that of cpx, consistent with other natural sample studies, but lower than cpx/opx equilibrium from experimental data. The pyroxenite cpx and opx H2O concentrations are at the high-end of on-and off-craton peridotite xenolith concentrations and those of Hawaiian spinel peridotites. In contrast, garnet has extremely low water contents (<5ppm H2O). There is no correlation between H2O in cpx and lithophile element concentrations. Phlogopite is present in some samples, and its modal abundance shows a positive correlation in Mg# with cpx, implying equilibrium. However, there is no correlation between H2O concentrations and or the presence of phlogopite. These data imply that cpx and opx may be at water saturation, far lower than experimental data suggest. Reconstructed bulk rock pyroxenite H2O ranges from 200-460 ppm (average 331 +/- 75 ppm), 2 to 8 times higher than H2O estimates for the MORB source (50-200 ppm), but in the range of E-MORB, OIB and the source of rejuvenated Hawaiian magmas. The average bulk rock pyroxenite H2O/Ce is 69

  1. Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

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

    Miliordos, Evangelos; Xantheas, Sotiris S.

    We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as theymore » contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

  2. Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

    PubMed Central

    Yang, Jingbin; Li, Dongxu; Fang, Yuan

    2017-01-01

    C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

  3. Hemodynamic effects of external continuous negative pressure ventilation compared with those of continuous positive pressure ventilation in dogs with acute lung injury.

    PubMed

    Skaburskis, M; Helal, R; Zidulka, A

    1987-10-01

    Patients with noncardiogenic pulmonary edema requiring ventilatory assistance are usually supported with CPPV using positive end-expiratory pressure (PEEP), but CPPV requires endotracheal intubation and may decrease cardiac output (QT). The purpose of this study was to examine thoracoabdominal continuous negative pressure ventilation (CNPV) using external negative end-expiratory pressure (NEEP). The effects on gas exchange and hemodynamics were compared with those of CPPV with PEEP, with the premise that CNPV might sustain venous return and improve QT. In 6 supine, anesthetized and paralyzed dogs with oleic-acid-induced pulmonary edema, 30 min of CNPV was alternated twice with 30 min of CPPV. Positive and negative pressure ventilation were carefully matched for fractional inspired oxygen concentration (FIO2 = 0.56), breathing frequency, and tidal volume. In addition, we matched the increase in delta FRC obtained with the constant distending pressures produced by both modes of ventilation. An average of -9 cm H2O of NEEP produced the same delta FRC as 10.8 cm H2O of PEEP. Gas exchange did not differ significantly between the 2 modes. However, QT was 15.8% higher during CNPV than during CPPV (p less than 0.02). Mixed venous oxygen saturation also improved during CNPV compared with that during CPPV (58.3 versus 54.5%, p less than 0.01). Negative pressure ventilation using NEEP may be a viable alternative to positive pressure ventilation with PEEP in the management of critically ill patients with noncardiogenic pulmonary edema. It offers comparable improvement in gas exchange with the advantages of less cardiac depression and the possible avoidance of endotracheal intubation.

  4. History of mechanical ventilation may affect respiratory mechanics evolution in acute respiratory distress syndrome.

    PubMed

    Koutsoukou, Antonia; Perraki, Helen; Orfanos, Stylianos E; Koulouris, Nikolaos G; Tromaropoulos, Andreas; Sotiropoulou, Christina; Roussos, Charis

    2009-12-01

    The aim of this study was to investigate the effect of mechanical ventilation (MV) before acute respiratory distress syndrome (ARDS) on subsequent evolution of respiratory mechanics and blood gases in protectively ventilated patients with ARDS. Nineteen patients with ARDS were stratified into 2 groups according to ARDS onset relative to the onset of MV: In group A (n = 11), MV was applied at the onset of ARDS; in group B (n = 8), MV had been initiated before ARDS. Respiratory mechanics and arterial blood gas were assessed in early (positive end-expiratory pressure and positive end-expiratory pressure of 10 cm H(2)O. In group A, Pao(2)/fractional inspired oxygen concentration increased (121 +/- 43 vs 161 +/- 60 mm Hg) and minimal resistance of respiratory system decreased (8.3 +/- 1.8 vs 6.0 +/- 2.1 cm H(2)O L(-1) s(-1)) from early to late ARDS. In group B, static elastance of respiratory system increased in the late stage (30.4 +/- 7.8 vs 36.4 +/- 9.9 cm H(2)O/L). In both groups, positive end-expiratory pressure application resulted in Pao(2)/fractional inspired oxygen concentration improvement and minimal resistance of respiratory system decreases in both stages. In protectively ventilated patients with ARDS, late alteration of respiratory mechanics occurs more commonly in patients who have been ventilated before ARDS onset, suggesting that the history of MV affects the subsequent progress of ARDS even when using protective ventilation.

  5. [Spontaneous ventilation in positive expiratory pressure in cardiogenic pulmonary edema. Prospective study].

    PubMed

    Bouquin, V; L'Her, E; Moriconi, M; Jobic, Y; Maheu, B; Guillo, P; Paris, A; Pennec, P Y; Boles, J M; Blanc, J J

    1998-10-01

    New equipment facilitating the use of spontaneous ventilation with positive expiratory pressure (PEP) has become available in France since January 1996. This technique was applied in 38 patients with severe cardiogenic pulmonary oedema and persistent respiratory distress despite high flow classical oxygen therapy and standard treatment. After 1 hour of ventilation with a flow of 220 l/min of 100% oxygen with an average PEP of 7.7 cm H20, a significant improvement of clinical (heart and respiratory rate) and biological parameters (arterial gases) was observed. There were no side effects. Four patients died during the hospital period and only 1 was intubated. Spontaneous ventilation with PEP is a simple technique for coronary care units and, compared with conventional oxygen therapy, it rapidly improves arterial oxygenation, reduces respiratory work and improves conditions of cardiac load. Acute severe cardiogenic pulmonary oedema seems to be an indication of choice, especially in the elderly, where it may help avoid an often controversial intubation.

  6. Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

    NASA Astrophysics Data System (ADS)

    Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

    2012-02-01

    We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

  7. Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

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

    Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

    2012-08-08

    Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

  8. Isotope exchange in reactions between D2O and size-selected ionic water clusters containing pyridine, H+ (pyridine)m(H2O)n.

    PubMed

    Ryding, Mauritz Johan; Zatula, Alexey S; Andersson, Patrik Urban; Uggerud, Einar

    2011-01-28

    Pyridine containing water clusters, H(+)(pyridine)(m)(H(2)O)(n), have been studied both experimentally by a quadrupole time-of-flight mass spectrometer and by quantum chemical calculations. In the experiments, H(+)(pyridine)(m)(H(2)O)(n) with m = 1-4 and n = 0-80 are observed. For the cluster distributions observed, there are no magic numbers, neither in the abundance spectra, nor in the evaporation spectra from size selected clusters. Experiments with size-selected clusters H(+)(pyridine)(m)(H(2)O)(n), with m = 0-3, reacting with D(2)O at a center-of-mass energy of 0.1 eV were also performed. The cross-sections for H/D isotope exchange depend mainly on the number of water molecules in the cluster and not on the number of pyridine molecules. Clusters having only one pyridine molecule undergo D(2)O/H(2)O ligand exchange, while H(+)(pyridine)(m)(H(2)O)(n), with m = 2, 3, exhibit significant H/D scrambling. These results are rationalized by quantum chemical calculations (B3LYP and MP2) for H(+)(pyridine)(1)(H(2)O)(n) and H(+)(pyridine)(2)(H(2)O)(n), with n = 1-6. In clusters containing one pyridine, the water molecules form an interconnected network of hydrogen bonds associated with the pyridinium ion via a single hydrogen bond. For clusters containing two pyridines, the two pyridine molecules are completely separated by the water molecules, with each pyridine being positioned diametrically opposite within the cluster. In agreement with experimental observations, these calculations suggest a "see-saw mechanism" for pendular proton transfer between the two pyridines in H(+)(pyridine)(2)(H(2)O)(n) clusters.

  9. Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

    PubMed

    Srithep, Sirinthip; Phattarapattamawong, Songkeart

    2017-06-01

    The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Gadolinium prevents high airway pressure-induced permeability increases in isolated rat lungs.

    PubMed

    Parker, J C; Ivey, C L; Tucker, J A

    1998-04-01

    To determine the initial signaling event in the vascular permeability increase after high airway pressure injury, we compared groups of lungs ventilated at different peak inflation pressures (PIPs) with (gadolinium group) and without (control group) infusion of 20 microM gadolinium chloride, an inhibitor of endothelial stretch-activated cation channels. Microvascular permeability was assessed by using the capillary filtration coefficient (Kfc), a measure of capillary hydraulic conductivity. Kfc was measured after ventilation for 30-min periods with 7, 20, and 30 cmH2O PIP with 3 cmH2O positive end-expiratory pressure and with 35 cmH2O PIP with 8 cmH2O positive end-expiratory pressure. In control lungs, Kfc increased significantly to 1.8 and 3.7 times baseline after 30 and 35 cmH2O PIP, respectively. In the gadolinium group, Kfc was unchanged from baseline (0.060 +/- 0.010 ml . min-1 . cmH2O-1 . 100 g-1) after any PIP ventilation period. Pulmonary vascular resistance increased significantly from baseline in both groups before the last Kfc measurement but was not different between groups. These results suggest that microvascular permeability is actively modulated by a cellular response to mechanical injury and that stretch-activated cation channels may initiate this response through increases in intracellular calcium concentration.

  11. Vibrational energy transfer and relaxation in O2 and H2O.

    PubMed

    Huestis, David L

    2006-06-01

    Near-resonant vibrational energy exchange between oxygen and water molecules is an important process in the Earth's atmosphere, combustion chemistry, and the chemical oxygen iodine laser (COIL). The reactions in question are (1) O2(1) + O2(0) --> O2(0) + O2(0); (2) O2(1) + H2O(000) --> O2(0) + H2O(000); (3) O2(1) + H2O(000) <--> O2(0) + H2O(010); (4) H2O(010) + H2O(000) --> H2O(000) + H2O(000); and (5) H2O(010) + O2(0) --> H2O(000) + O2(0). Reanalysis of the data available in the chemical kinetics literature provides reliable values for rate coefficients for reactions 1 and 4 and strong evidence that reactions 2 and 5 are slow in comparison with reaction 3. Analytical solution of the chemical rate equations shows that previous attempts to measure the rate of reaction 3 are unreliable unless the water mole fraction is higher than 1%. Reanalysis of data from the only experiment satisfying this constraint provides a rate coefficient of (5.5 +/- 0.4) x 10(-13) cm3/s at room temperature, between the values favored by the atmospheric and laser modeling communities.

  12. Measurement of H2O and other trace gases in the stratosphere using a high resolution far-infrared spectrometer at 28 km

    NASA Technical Reports Server (NTRS)

    Traub, W. A.; Chance, K. V.

    1984-01-01

    Data analysis results from the 1983 BIC 1 and 2 balloon flights are presented, with emphasis on H2O2, OH, HCL, O3, O2, and H2O. A 2 sigma limit on H2O2 abundance was set, as a function of altitude. This is comparable to or less than the theoretically predicted winter abundances from the 2-D models of Dupont, with a large enough summer maximum to facilitate concentration profile measurements. There is a definite drop in OH concentration from day to night following two model profiles. There was general agreement between HF measurements. The dominant role of the far wings of H2O lines in low altitude spectra was recognized. The strength of these wings exceeds that of many molecular line cores, including O3 and O2, especially near the long wavelength end of the spectra (100 cm (-1)). Newly measured positions for O3 and H2O were obtained.

  13. Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

  14. Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

    NASA Technical Reports Server (NTRS)

    Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

    1988-01-01

    A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

  15. Reduction in central H2O2 levels prevents voluntary ethanol intake in mice: a role for the brain catalase-H2O2 system in alcohol binge drinking.

    PubMed

    Ledesma, Juan Carlos; Baliño, Pablo; Aragon, Carlos M G

    2014-01-01

    Hydrogen peroxide (H2 O2 ) is the cosubstrate used by the enzyme catalase to form Compound I (the catalase-H2 O2 system), which is the major pathway for the conversion of ethanol (EtOH) into acetaldehyde in the brain. This centrally formed acetaldehyde has been shown to be involved in some of the psychopharmacological effects induced by EtOH in rodents, including voluntary alcohol intake. It has been observed that different levels of this enzyme in the central nervous system (CNS) result in variations in the amount of EtOH consumed. This has been interpreted to mean that the brain catalase-H2 O2 system, by determining EtOH metabolism, mediates alcohol self-administration. To date, however, the role of H2 O2 in voluntary EtOH drinking has not been investigated. In the present study, we explored the consequence of a reduction in cerebral H2 O2 levels in volitional EtOH ingestion. With this end in mind, we injected mice of the C57BL/6J strain intraperitoneally with the H2 O2 scavengers alpha-lipoic acid (LA; 0 to 50 mg/kg) or ebselen (Ebs; 0 to 25 mg/kg) 15 or 60 minutes, respectively, prior to offering them an EtOH (10%) solution following a drinking-in-the-dark procedure. The same procedure was followed to assess the selectivity of these compounds in altering EtOH intake by presenting mice with a (0.1%) solution of saccharin. In addition, we indirectly tested the ability of LA and Ebs to reduce brain H2 O2 availability. The results showed that both LA and Ebs dose-dependently reduced voluntary EtOH intake, without altering saccharin consumption. Moreover, we demonstrated that these treatments decreased the central H2 O2 levels available to catalase. Therefore, we propose that the amount of H2 O2 present in the CNS, by determining brain acetaldehyde formation by the catalase-H2 O2 system, could be a factor that determines an animal's propensity to consume EtOH. Copyright © 2013 by the Research Society on Alcoholism.

  16. Decreased N2O reduction by low soil pH causes high N2O emissions in a riparian ecosystem.

    PubMed

    Van den Heuvel, R N; Bakker, S E; Jetten, M S M; Hefting, M M

    2011-05-01

    Quantification of harmful nitrous oxide (N(2)O) emissions from soils is essential for mitigation measures. An important N(2)O producing and reducing process in soils is denitrification, which shows deceased rates at low pH. No clear relationship between N(2)O emissions and soil pH has yet been established because also the relative contribution of N(2)O as the denitrification end product decreases with pH. Our aim was to show the net effect of soil pH on N(2)O production and emission. Therefore, experiments were designed to investigate the effects of pH on NO(3)(-) reduction, N(2)O production and reduction and N(2) production in incubations with pH values set between 4 and 7. Furthermore, field measurements of soil pH and N(2)O emissions were carried out. In incubations, NO(3)(-) reduction and N(2) production rates increased with pH and net N(2)O production rate was highest at pH 5. N(2)O reduction to N(2) was halted until NO(3)(-) was depleted at low pH values, resulting in a built up of N(2)O. As a consequence, N(2)O:N(2) production ratio decreased exponentially with pH. N(2)O reduction appeared therefore more important than N(2)O production in explaining net N(2)O production rates. In the field, a negative exponential relationship for soil pH against N(2)O emissions was observed. Soil pH could therefore be used as a predictive tool for average N(2)O emissions in the studied ecosystem. The occurrence of low pH spots may explain N(2)O emission hotspot occurrence. Future studies should focus on the mechanism behind small scale soil pH variability and the effect of manipulating the pH of soils. © 2011 Blackwell Publishing Ltd.

  17. Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

  18. Odin observations of H2O and O2 in comets and interstellar clouds

    NASA Astrophysics Data System (ADS)

    Hjalmarson, Åke; Odin Team

    2002-11-01

    We here report on results from single-position observations, and in some cases also mapping, of the 557 GHz ortho-H2O line in several comets and in many interstellar molecular clouds by the Odin sub-millimetre wave spectroscopy satellite. The H2O production rates have been accurately determined in four comets, C/2001 A2 (LINEAR), 19P/Borrelly, C/2000 WM1 (LINEAR), and 153P/2002 C1 (Ikeya-Zhang). In comet Ikeya-Zhang our detection at a low level of the corresponding H218O emission line verifies the H2O production rate (which depends upon the assumed radiative and collisional excitation and also upon radiative transfer modelling) and is consistent with a nearly terrestrial 16O/18O-isotope ratio. In an astrobiological context, the cometary H2O production rates are especially important as reference levels for comparison with abundances of other molecules simultaneously observed with ground-based telescopes. In interstellar clouds the observed gas-phase H2O abundances (vs H2) range from 5×10-4 in the Orion KL outflow/shock region (where essentially all oxygen is locked up in H2O) to circa 10-8 in quiescent cloud regions (where H2O) is just one of many trace molecules). From an astrobiological point of view, the molecular abundances in star forming clouds are important in terms of initial conditions for the chemistry in proto-planetary disks ("proto-solar nebulae"), the formation sites of new planetary systems. In simultaneous observations, Odin has also detected the 572 GHz ortho-NH3 line in cold and warm clouds as well as in the Orion outflow and Bar/PDR regions (an area of increased ionisation caused by the intense UV flux from newly born massive stars). In other simultaneous observations, we have performed sensitive searches for O2 at 119 GHz. Although no detection can be reported as yet, the resulting very low abundance limits (<10-7) are very intriguing when they are compared with current "standard" model expectations, which fall in the range 10-5-10-4.

  19. Comparison of simultaneous CO2 and H2O observations of Venus

    NASA Technical Reports Server (NTRS)

    Barker, E. S.

    1975-01-01

    Results are reported for 115 pairs of CO2 and H2O abundance determinations made with the coude scanner of a 2.7 m reflector. The pairs of observations were made over the same area of the illuminated disk of Venus with the guiding, seeing and slit-placement errors less than 15 per cent of the disk diameter. A correlation analysis of the pairs of observations grouping them into eight periods of time which corresponded to telescope observing runs or periods of similar phase angle shows a lack of correlation in all except one period. For this set, the H2O abundances were positively correlated with the relative CO2 line strengths for measurements of the 8689-A and 7820-A CO2 bands made on the same day. Comparison of abundances on some 25 individual days shows a positive correlation on one day and a marginal negative correlation on two days, with no correlation on the remaining 22 days. On the basis of the lack of correlations, it is concluded that either the H2O level of line formation does not fluctuate in phase with the observed CO2 absorption fluctuations or the horizontal distribution of the H2O vapor must be inhomogeneous.

  20. A continuous [15O]H2O production and infusion system for PET imaging

    NASA Astrophysics Data System (ADS)

    Sajjad, Munawwar; Liow, Jeih-San

    1999-06-01

    A system for continuous production and infusion of [15O]H2O has been designed for PET cerebral blood flow studies. The injection system consists of a four-port-two-position valve, two Horizon Nxt infusion pumps, and a sterile 50 ml vial. The variation of the production of [15O]H2O was <1%. The variation of activity delivered measured by scanner counts during the steady state period was <2%.

  1. Chlorogenic acid analogues from Gynura nepalensis protect H9c2 cardiomyoblasts against H2O2-induced apoptosis

    PubMed Central

    Yu, Bang-wei; Li, Jin-long; Guo, Bin-bin; Fan, Hui-min; Zhao, Wei-min; Wang, He-yao

    2016-01-01

    Aim: Chlorogenic acid has shown protective effect on cardiomyocytes against oxidative stress-induced damage. Herein, we evaluated nine caffeoylquinic acid analogues (1–9) isolated from the leaves of Gynura nepalensis for their protective effect against H2O2-induced H9c2 cardiomyoblast damage and explored the underlying mechanisms. Methods: H9c2 cardiomyoblasts were exposed to H2O2 (0.3 mmol/L) for 3 h, and cell viability was detected with MTT assay. Hoechst 33342 staining was performed to evaluate cell apoptosis. MMPs (mitochondrial membrane potentials) were measured using a JC-1 assay kit, and ROS (reactive oxygen species) generation was measured using CM-H2 DCFDA. The expression levels of relevant proteins were detected using Western blot analysis. Results: Exposure to H2O2 markedly decreased the viability of H9c2 cells and catalase activity, and increased LDH release and intracellular ROS production; accompanied by a loss of MMP and increased apoptotic rate. Among the 9 chlorogenic acid analogues as well as the positive control drug epigallocatechin gallate (EGCG) tested, compound 6 (3,5-dicaffeoylquinic acid ethyl ester) was the most effective in protecting H9c2 cells from H2O2-induced cell death. Pretreatment with compound 6 (1.56–100 μmol/L) dose-dependently alleviated all the H2O2-induced detrimental effects. Moreover, exposure to H2O2 significantly increased the levels of Bax, p53, cleaved caspase-8, and cleaved caspase-9, and decreased the level of Bcl-2, resulting in cell apoptosis. Exposure to H2O2 also significantly increased the phosphorylation of p38, JNK and ERK in the H9c2 cells. Pretreatment with compound 6 (12.5 and 25 μmol/L) dose-dependently inhibited the H2O2-induced increase in the level of cleaved caspase-9 but not of cleaved caspase-8. It also dose-dependently suppressed the H2O2-induced phosphorylation of JNK and ERK but not that of p38. Conclusion: Compound 6 isolated from the leaves of Gynura nepalensis potently protects H9c2

  2. VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

    USGS Publications Warehouse

    Newman, S.; Lowenstern, J. B.

    2002-01-01

    We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

  3. Impact of continuous positive airway pressure on the pulmonary changes promoted by immersion in water

    PubMed Central

    Rizzetti, Danize Aparecida; Quadros, Janayna Rodembuch Borba; Ribeiro, Bruna Esmerio; Callegaro, Letícia; Veppo, Aline Arebalo; Wiggers, Giulia Alessandra; Peçanha, Franck Maciel

    2017-01-01

    ABSTRACT Objective: To determine whether different levels of CPAP improve the lung volumes and capacities of healthy subjects immersed in water. Methods: This was a randomized clinical trial, conducted between April and June of 2016, involving healthy female volunteers who were using oral contraceptives. Three 20-min immersion protocols were applied: control (no CPAP); CPAP5 (CPAP at 5 cmH2O); and CPAP10 (CPAP at 10 cmH2O). We evaluated HR, SpO2, FVC, FEV1, the FEV1/FVC ratio, peak expiratory flow rate (PEFR), and FEF25-75%) at three time points: pre-immersion; 10 min after immersion; and 10 min after the end of each protocol. Results: We evaluated 13 healthy volunteers. The CPAP10 protocol reversed the restrictive pattern of lung function induced by immersion in water, maintaining pulmonary volumes and capacities for a longer period than did the CPAP5 protocol. Conclusions: When the hemodynamic change causing a persistent lung disorder, only the application of higher positive pressures is effective in maintaining long-term improvements in the pulmonary profile. PMID:29340488

  4. Impact of continuous positive airway pressure on the pulmonary changes promoted by immersion in water.

    PubMed

    Rizzetti, Danize Aparecida; Quadros, Janayna Rodembuch Borba; Ribeiro, Bruna Esmerio; Callegaro, Letícia; Veppo, Aline Arebalo; Wiggers, Giulia Alessandra; Peçanha, Franck Maciel

    2017-01-01

    To determine whether different levels of CPAP improve the lung volumes and capacities of healthy subjects immersed in water. This was a randomized clinical trial, conducted between April and June of 2016, involving healthy female volunteers who were using oral contraceptives. Three 20-min immersion protocols were applied: control (no CPAP); CPAP5 (CPAP at 5 cmH2O); and CPAP10 (CPAP at 10 cmH2O). We evaluated HR, SpO2, FVC, FEV1, the FEV1/FVC ratio, peak expiratory flow rate (PEFR), and FEF25-75%) at three time points: pre-immersion; 10 min after immersion; and 10 min after the end of each protocol. We evaluated 13 healthy volunteers. The CPAP10 protocol reversed the restrictive pattern of lung function induced by immersion in water, maintaining pulmonary volumes and capacities for a longer period than did the CPAP5 protocol. When the hemodynamic change causing a persistent lung disorder, only the application of higher positive pressures is effective in maintaining long-term improvements in the pulmonary profile.

  5. Pressure-Stabilized Cubic Perovskite Oxyhydride BaScO2H.

    PubMed

    Goto, Yoshihiro; Tassel, Cédric; Noda, Yasuto; Hernandez, Olivier; Pickard, Chris J; Green, Mark A; Sakaebe, Hikari; Taguchi, Noboru; Uchimoto, Yoshiharu; Kobayashi, Yoji; Kageyama, Hiroshi

    2017-05-01

    We report a scandium oxyhydride BaScO 2 H prepared by solid state reaction under high pressure. Rietveld refinements against powder synchrotron X-ray and neutron diffraction data revealed that BaScO 2 H adopts the ideal cubic perovskite structure (Pm3̅m), where oxide (O 2- ) and hydride (H - ) anions are disordered. 1 H nuclear magnetic resonance (NMR) spectroscopy provides a positive chemical shift of about +4.4 ppm, which can be understood by the distance to the nearest (and possibly the next nearest) cation from the H nucleus. A further analysis of the NMR data and calculations based on ab initio random structure searches suggest a partial cis preference in ScO 4 H 2 octahedra. The present oxyhydride, if compositionally or structurally tuned, may become a candidate for H - conductors.

  6. Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

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

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen

    2015-08-28

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are comparedmore » to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.« less

  7. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1).

    PubMed

    Li, Xiang; Wang, Haopeng; Bowen, Kit H

    2010-10-14

    The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  8. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.

    2010-10-01

    The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  9. Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

    PubMed

    Mizuse, Kenta; Fujii, Asuka

    2011-04-21

    Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

  10. Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

    PubMed

    Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

    2014-08-30

    The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Near infrared overtone (vOH = 2 ← 0) spectroscopy of Ne-H2O clusters

    NASA Astrophysics Data System (ADS)

    Ziemkiewicz, Michael P.; Pluetzer, Christian; Wojcik, Michael; Loreau, Jérôme; van der Avoird, Ad; Nesbitt, David J.

    2017-03-01

    Vibrationally state selective overtone spectroscopy and dynamics of weakly bound Ne-H2O complexes (D0(para) = 31.67 cm-1, D0(ortho) = 34.66 cm-1) are reported for the first time, based on near infrared excitation of van der Waals cluster bands correlating with vOH = 2 ← 0 overtone transitions (|02-⟩←|00+⟩ and |02+⟩ ←|00+⟩ ) out of the ortho (101) and para (000) internal rotor states of the H2O moiety. Quantum theoretical calculations for nuclear motion on a high level ab initio potential energy surface (CCSD(T)/VnZ-f12 (n = 3,4), corrected for basis set superposition error and extrapolated to the complete basis set limit) are employed for assignment of Σ ←Σ ,Π ←Σ , and Σ ←Π infrared bands in the overtone spectra, where Σ ( K = 0) and Π (K = 1) represent approximate projections (K) of the body angular momentum along the Ne-H2O internuclear axis. End-over-end tumbling of the ortho Ne-H2O cluster is evident via rotational band contours observed, with band origins and rotational progressions in excellent agreement with ab initio frequency and intensity predictions. A clear Q branch in the corresponding |02+⟩fΠ (111) ←eΣ (000) para Ne-H2O spectrum provides evidence for a novel e/f parity-dependent metastability in these weakly bound clusters, in agreement with ab initio bound state calculations and attributable to the symmetry blocking of an energetically allowed channel for internal rotor predissociation. Finally, Boltzmann analysis of the rotational spectra reveals anomalously low jet temperatures (Trot ≈ 4(1) K), which are attributed to "evaporative cooling" of weakly bound Ne-H2O clusters and provide support for similar cooling dynamics in rare gas-tagging studies.

  12. On the role of the termolecular reactions 2O2 + H22HO2 and 2O2 + H2H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

    PubMed

    Monge-Palacios, M; Rafatijo, Homayoon

    2017-01-18

    We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 22HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2H + HO 2 + O 2 and two for 2O 2 + H 22HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 22HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2H + HO 2 only at sufficiently high pressures.

  13. Incorporation of μ3-CO3 into an MnIII/MnIV Mn12 cluster: {[(cyclam)MnIV(μ-O)2MnIII(H2O)(μ-OH)]6(μ3-CO3)2}Cl8·24H2O

    PubMed Central

    Levaton, Ben B.; Olmstead, Marilyn M.

    2010-01-01

    The centrosymmetric title cluster, hexa­aquadi-μ3-carbonato-hexa­cyclamhexa-μ2-hydroxido-dodeca-μ2-oxido-hexa­mang­an­ese(IV)hexa­manganese(III) octa­chloride tetra­cosa­hydrate, [Mn12(CO3)2O12(OH)6(C10H24N4)6(H2O)6]Cl8·24H2O, has two μ3-CO3 groups that not only bridge octahedrally coordinated MnIII ions but also act as acceptors to two different kinds of hydrogen bonds. The carbonate anion is planar within experimental error and has an average C—O distance of 1.294 (4) Å. The crystal packing is stabilized by O—H⋯Cl, O—H⋯O, N—H⋯Cl and N—H⋯O hydrogen bonds. Two of the four independent chloride ions are disordered over five positions, and eight of the 12 independent water mol­ecules are disordered over 21 positions. PMID:21587382

  14. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2011-03-01

    "H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

  15. An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

    2012-12-01

    The crystal chemistry of armenite, ideally BaCa2Al6Si9O30.2H2O, a double-ring structure belonging to the milarite group, was studied to better understand the nature of extra-framework "Ca-oxygen-anion-H2O-molecule quasi-clusters" and H bonding behavior in microporous silicates. Neutron and X-ray single-crystal diffraction and IR powder and 1H NMR spectroscopic measurements were made. Four crystallographically independent Ca and H2O molecule sites were refined from the diffraction data, whereby both sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming a quasi cluster around it. The neutron results give the first static description of the protons in armenite, allowing bond distances and angles relating to the H2O molecules and H bonds to be determined. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two broad bands at roughly 3470 and 3410 cm-1 and by a single H2O bending mode at 1654 cm-1. At 10 K four intense OH bands are located at 3479, 3454, 3401 and 3384 cm-1 and two H2O bending modes at 1650 and 1606 cm-1. The 1H MAS NMR spectrum shows a single strong resonance near 5.3 ppm and a smaller one near 2.7 ppm. The former can be assigned to H2O molecules bonded to Ca and the latter to weakly bonded H2O located at a site at the center of the structural double ring and it is partially occupied. The nature of H bonding in the microporous Ca-bearing zeolites scolecite, wairakite and epistilbite are also analyzed. The average OH stretching wavenumber shown by the IR spectra of armenite (~3435 cm-1) and scolecite (~3430 cm-1) are similar, while the average OH wavenumbers for wairakite (~3475 cm-1) and epistilbite (~3500 cm-1) are greater. In all cases the average OH stretching wavenumber is more similar to that of liquid water (~3400 cm-1) than of ice (~3220 cm-1). The

  16. Expiratory rib cage compression in mechanically ventilated adults: systematic review with meta-analysis

    PubMed Central

    Borges, Lúcia Faria; Saraiva, Mateus Sasso; Saraiva, Marcos Ariel Sasso; Macagnan, Fabrício Edler; Kessler, Adriana

    2017-01-01

    Objective To review the literature on the effects of expiratory rib cage compression on ventilatory mechanics, airway clearance, and oxygen and hemodynamic indices in mechanically ventilated adults. Methods Systematic review with meta-analysis of randomized clinical trials in the databases MEDLINE (via PubMed), EMBASE, Cochrane CENTRAL, PEDro, and LILACS. Studies on adult patients hospitalized in intensive care units and under mechanical ventilation that analyzed the effects of expiratory rib cage compression with respect to a control group (without expiratory rib cage compression) and evaluated the outcomes static and dynamic compliance, sputum volume, systolic blood pressure, diastolic blood pressure, mean arterial pressure, heart rate, peripheral oxygen saturation, and ratio of arterial oxygen partial pressure to fraction of inspired oxygen were included. Experimental studies with animals and those with incomplete data were excluded. Results The search strategy produced 5,816 studies, of which only three randomized crossover trials were included, totaling 93 patients. With respect to the outcome of heart rate, values were reduced in the expiratory rib cage compression group compared with the control group [-2.81 bpm (95% confidence interval [95%CI]: -4.73 to 0.89; I2: 0%)]. Regarding dynamic compliance, there was no significant difference between groups [-0.58mL/cmH2O (95%CI: -2.98 to 1.82; I2: 1%)]. Regarding the variables systolic blood pressure and diastolic blood pressure, significant differences were found after descriptive evaluation. However, there was no difference between groups regarding the variables secretion volume, static compliance, ratio of arterial oxygen partial pressure to fraction of inspired oxygen, and peripheral oxygen saturation. Conclusion There is a lack of evidence to support the use of expiratory rib cage compression in routine care, given that the literature on this topic offers low methodological quality and is inconclusive. PMID

  17. Esophageal and transpulmonary pressures in acute respiratory failure*

    PubMed Central

    Talmor, Daniel; Sarge, Todd; O’Donnell, Carl R.; Ritz, Ray; Malhotra, Atul; Lisbon, Alan; Loring, Stephen H.

    2008-01-01

    Objective Pressure inflating the lung during mechanical ventilation is the difference between pressure applied at the airway opening (Pao) and pleural pressure (Ppl). Depending on the chest wall’s contribution to respiratory mechanics, a given positive end-expiratory and/or end-inspiratory plateau pressure may be appropriate for one patient but inadequate or potentially injurious for another. Thus, failure to account for chest wall mechanics may affect results in clinical trials of mechanical ventilation strategies in acute respiratory distress syndrome. By measuring esophageal pressure (Pes), we sought to characterize influence of the chest wall on Ppl and transpulmonary pressure (PL) in patients with acute respiratory failure. Design Prospective observational study. Setting Medical and surgical intensive care units at Beth Israel Deaconess Medical Center. Patients Seventy patients with acute respiratory failure. Interventions: Placement of esophageal balloon-catheters. Measurements and Main Results Airway, esophageal, and gastric pressures recorded at end-exhalation and end-inflation Pes averaged 17.5 ± 5.7 cm H2O at end-expiration and 21.2 ± 7.7 cm H2O at end-inflation and were not significantly correlated with body mass index or chest wall elastance. Estimated PL was 1.5 ± 6.3 cm H2O at end-expiration, 21.4 ± 9.3 cm H2O at end-inflation, and 18.4 ± 10.2 cm H2O (n = 40) during an end-inspiratory hold (plateau). Although PL at end-expiration was significantly correlated with positive end-expiratory pressure (p < .0001), only 24% of the variance in PL was explained by Pao (R2 = .243), and 52% was due to variation in Pes. Conclusions In patients in acute respiratory failure, elevated esophageal pressures suggest that chest wall mechanical properties often contribute substantially and unpredictably to total respiratory impedance, and therefore Pao may not adequately predict PL or lung distention. Systematic use of esophageal manometry has the potential to

  18. Comparison of O2 and H2O as oxygen source for homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Konishi, Keita; Goto, Ken; Togashi, Rie; Murakami, Hisashi; Higashiwaki, Masataka; Kuramata, Akito; Yamakoshi, Shigenobu; Monemar, Bo; Kumagai, Yoshinao

    2018-06-01

    Homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy (HVPE) using O2 or H2O as an oxygen source was investigated by thermodynamic analysis, and compared with measured properties after growth. The thermodynamic analysis revealed that Ga2O3 growth is expected even at 1000 °C using both oxygen sources due to positive driving forces for Ga2O3 deposition. The experimental results for homoepitaxial growth on (0 0 1) β-Ga2O3 substrates showed that the surfaces of the layers grown with H2O were smoother than those grown with O2, although the growth rate with H2O was approximately half that with O2. However, in the homoepitaxial layer grown using H2O, incorporation of Si impurities with a concentration almost equal to the effective donor concentration (2 × 1016 cm-3) was confirmed, which was caused by decomposition of the quartz glass reactor due to the presence of hydrogen in the system.

  19. Pilot study of nasal expiratory positive airway pressure devices for the treatment of childhood obstructive sleep apnea syndrome.

    PubMed

    Kureshi, Suraiya A; Gallagher, Paul R; McDonough, Joseph M; Cornaglia, Mary Anne; Maggs, Jill; Samuel, John; Traylor, Joel; Marcus, Carole L

    2014-06-15

    Alternative therapies for childhood obstructive sleep apnea syndrome (OSAS) are needed as OSAS may persist despite adenotonsillectomy, and continuous positive airway pressure (CPAP) adherence is low. Nasal expiratory positive airway pressure (NEPAP) devices have not been studied in children. We hypothesized that NEPAP would result in polysomnographic improvement. Further, we aimed to determine NEPAP adherence, effects on sleepiness, behavior, and quality of life. A randomized, double-blind, placebo-controlled, crossover pilot study was performed. CPAP candidates, 8-16 years old, underwent NEPAP and placebo polysomnograms. Subjects with ≥ 50% reduction in the apnea hypopnea index (AHI) from placebo to NEPAP night or AHI < 5/h on NEPAP night wore NEPAP at home for 30 days. Adherence was assessed by daily phone calls/emails and collecting used devices. Fourteen subjects (age 13.4 ± 1.9 years, BMI z-scores 2.2 ± 1 [mean ± SD]) were studied. There was significant improvement in the obstructive apnea index with NEPAP vs. placebo: 0.6 (0-21.1)/h vs. 4.2 (0-41.9)/h (median [range], p = 0.010) and trends for improvement in other polysomnographic parameters. However, responses were variable, with 3 subjects not improving and 2 worsening. Older children and those with less hypercapnia had a better response. Eight subjects were sent home with devices; one was lost to follow-up, and adherence in the remainder was 83% of nights; these subjects had a significant improvement in sleepiness and quality of life. NEPAP devices are a potential alternative therapy for OSAS in a small subset of children. Due to variability in individual responses, efficacy of NEPAP should be evaluated with polysomnography. www.clinicaltrials.gov, identifier: NCT01768065.

  20. Airway pressure release ventilation and biphasic positive airway pressure: a systematic review of definitional criteria.

    PubMed

    Rose, Louise; Hawkins, Martyn

    2008-10-01

    The objective of this study was to identify the definitional criteria for the pressure-limited and time-cycled modes: airway pressure release ventilation (APRV) and biphasic positive airway pressure (BIPAP) available in the published literature. Systematic review. Medline, PubMed, Cochrane, and CINAHL databases (1982-2006) were searched using the following terms: APRV, BIPAP, Bilevel and lung protective strategy, individually and in combination. Two independent reviewers determined the paper eligibility and abstracted data from 50 studies and 18 discussion articles. Of the 50 studies, 39 (78%) described APRV, and 11 (22%) described BIPAP. Various study designs, populations, or outcome measures were investigated. Compared to BIPAP, APRV was described more frequently as extreme inverse inspiratory:expiratory ratio [18/39 (46%) vs. 0/11 (0%), P = 0.004] and used rarely as a noninverse ratio [2/39 (5%) vs. 3/11 (27%), P = 0.06]. One (9%) BIPAP and eight (21%) APRV studies used mild inverse ratio (>1:1 to < or =2:1) (P = 0.7), plus there was increased use of 1:1 ratio [7 (64%) vs. 12 (31%), P = 0.08] with BIPAP. In adult studies, the mean reported set inspiratory pressure (PHigh) was 6 cm H2O greater with APRV when compared to reports of BIPAP (P = 0.3). For both modes, the mean reported positive end expiratory pressure (PLow) was 5.5 cm H2O. Thematic review identified inconsistency of mode descriptions. Ambiguity exists in the criteria that distinguish APRV and BIPAP. Commercial ventilator branding may further add to confusion. Generic naming of modes and consistent definitional parameters may improve consistency of patient response for a given mode and assist with clinical implementation.

  1. Development and Evaluation of New Products for the Far-Forward Care of Combat Casualties with Acute Lung Injury

    DTIC Science & Technology

    2006-02-01

    pulmonary artery wedge pressure (PAWP) were determined at each time point. Electrocardiogram (ECG), pulse oximetry ( SpO2 ) (Datex Ohmeda True Tech Plus...cm H2O positive end expiratory pressure (PEEP) and a goal for oxygenation of at least 90% by arterial 8 blood hemoglobin O2 saturation ( SpO2 and...or SaO2). The fraction of inspired O2 concentration was 21% and was adjusted as necessary to maintain SpO2 ≥ 90% and partial pressure of O2 in

  2. A Novel Nasal Expiratory Positive Airway Pressure (EPAP) Device for the Treatment of Obstructive Sleep Apnea: A Randomized Controlled Trial

    PubMed Central

    Berry, Richard B.; Kryger, Meir H.; Massie, Clifford A.

    2011-01-01

    Study Objectives: Investigate the efficacy of a novel nasal expiratory positive airway pressure (EPAP) device as a treatment for obstructive sleep apnea (OSA). Design: A prospective, multicenter, sham-controlled, parallel-group, randomized, double-blind clinical trial. Setting: 19 sites including both academic and private sleep disorder centers Patients: Obstructive sleep apnea with a pre-study AHI ≥ 10/hour Interventions: Treatment with a nasal EPAP device (N = 127) or similar appearing sham device (N = 123) for 3 months. Polysomnography (PSG) was performed on 2 non-consecutive nights (random order: device-on, device-off) at week 1 and after 3 months of treatment. Analysis of an intention to treat group (ITT) (patients completing week 1 PSGs) (EPAP N = 119, sham N = 110) was performed. Measurements and Results: At week 1, the median AHI value (device-on versus device-off) was significantly lower with EPAP (5.0 versus 13.8 events/h, P < 0.0001) but not sham (11.6 versus 11.1 events/h, P = NS); the decrease in the AHI (median) was greater (−52.7% vs. −7.3%, P < 0.0001) for the ITT group. At month 3, the percentage decrease in the AHI was 42.7% (EPAP) and 10.1% (sham), P < 0.0001. Over 3 months of EPAP treatment the Epworth Sleepiness Scale decreased (9.9 ± 4.7 to 7.2 ± 4.2, P < 0.0001), and the median percentage of reported nights used (entire night) was 88.2%. Conclusions: The nasal EPAP device significantly reduced the AHI and improved subjective daytime sleepiness compared to the sham treatment in patients with mild to severe OSA with excellent adherence. Clinical Trial Information: Registrations: ClinicalTrials.gov. Trial name: Randomized Study of Provent Versus Sham Device to Treat Obstructive Sleep Apnea (AERO). URL: http://www.clinicaltrials.gov/ct2/show/NCT00772044?term=Ventus&rank=1. Registration Number: NCT00772044. Citation: Berry RB; Kryger MH; Massie CA. A novel nasal expiratory positive airway pressure (EPAP) device for the treatment of

  3. Effect of substituent groups (R= sbnd CH3, sbnd Br and sbnd CF3) on the structure, stability and redox property of [Cr(R-pic)2(H2O)2]NO3·H2O complexes

    NASA Astrophysics Data System (ADS)

    Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

    2017-12-01

    Complexes [Cr(3-CH3-pic)2(H2O)2]NO3·H2O (1), [Cr(5-Br-pic)2(H2O)2]NO3·H2O (2) and [Cr(5-CF3-pic)2(H2O)2]NO3·H2O (3) were synthesized (pic = pyridine-2-carboxylic acid) and characterized by X-ray crystal diffraction. Crystal structure indicates that two bidentate ligands occupy equatorial position and two H2O occupy axial positions in trans-configuration. (i) Decomposition of complexes 1, 2 and 3 in different medium (phosphate buffered saline (PBS), apo-ovotransferrin (apootf) and EDTA) indicates that decomposition rate constants of these complexes follow the sequence of 1 < 2 < 3. (ii) The redox potential of Cr(III)/Cr(II) by cyclic voltammetry follows the sequence of 1 (-1.20 V) > 3 (-1.29 V) > 2 (-1.31 V). (iii) In addition, ·OH-generation of the new synthesized complexes was determined by Fenton-like reaction in comparison with Cr(pic)3, and it may be related to the reduction potential of the complexes. (iv) Moreover, Hammett substituent constants σp (inductive) and σm (resonance) (R = 3-CH3, 5-Br, 5-CF3) were introduced to evaluate the impact of substituent groups on the bond length and decomposition kinetics. The substituent group on the ligand has great effect on the properties of the complexes.

  4. Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction.

    PubMed

    Siu, Chi-Kit; Liu, Zhi-Feng; Tse, John S

    2002-09-11

    We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations

  5. Cross sections for Scattering and Mobility of OH- and H3 O+ ions in H2 O

    NASA Astrophysics Data System (ADS)

    Petrovic, Zoran; Stojanovic, Vladimir; Maric, Dragana; Jovanovic, Jasmina

    2016-05-01

    Modelling of plasmas in liquids and in biological and medical applications requires data for scattering of all charged and energetic particles in water vapour. We present swarm parameters for OH- and H3 O+, as representatives of principal negative and positive ions at low pressures in an attempt to provide the data that are not yet available. We applied Denpoh-Nanbu procedure to calculate cross section sets for collisions of OH- and H3 O+ ions with H2 O molecule. Swarm parameters for OH- and H3 O+ ions in H2 O are calculated by using a well tested Monte Carlo code for a range of E / N(E -electric field, N-gas density) at temperature T = 295 K, in the low pressure limit. Non-conservative processes were shown to strongly influence the transport properties even for OH- ions above the average energy of 0.2 eV(E / N >200 Td). The data are valid for low pressure water vapour or small amounts in mixtures. They will provide a basis for calculating properties of ion-water molecule clusters that are most commonly found at higher pressures and for modelling of discharges in liquids. Acknowledgment to Ministry of Education, Science and Technology of Serbia.

  6. [Mechanism and performance of styrene oxidation by O3/H2O2].

    PubMed

    He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

    2013-10-01

    It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

  7. V OLATILEC ALC: a silicate melt-H 2O-CO 2 solution model written in Visual Basic for excel

    NASA Astrophysics Data System (ADS)

    Newman, Sally; Lowenstern, Jacob B.

    2002-06-01

    We present solution models for the rhyolite-H 2O-CO 2 and basalt-H 2O-CO 2 systems at magmatic temperatures and pressures below ˜5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within Microsoft ® Excel (Office'98 and 2000). The series of macros, entitled V OLATILEC ALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H 2O and CO 2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H 2O and CO 2 vapors at magmatic temperatures. The basalt-H 2O-CO 2 macros in V OLATILEC ALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar.

  8. Fiber-optic thermometry using thermal radiation from Tm end doped SiO{sub 2} fiber sensor

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

    Morita, Kentaro; Katsumata, Toru; Komuro, Shuji

    2014-04-15

    Fiber-optic thermometry based on temperature dependence of thermal radiation from Tm{sup 3+} ions was studied using Tm end doped SiO{sub 2} fiber sensor. Visible light radiation peaks due to f-f transition of Tm{sup 3+} ion were clearly observed at λ = 690 and 790 nm from Tm end doped SiO{sub 2} fibers sensor at the temperature above 600 °C. Thermal radiation peaks are assigned with f-f transition of Tm{sup 3+} ion, {sup 1}D{sub 2}-{sup 3}H{sub 6}, and {sup 1}G{sub 4}-{sup 3}H{sub 6}. Peak intensity of thermal radiation from Tm{sup 3+} ion increases with temperature. Intensity ratio of thermal radiation peaks atmore » λ = 690 nm against that at λ = 790 nm, I{sub 790/690}, is suitable for the temperature measurement above 750 °C. Two-dimensional temperature distribution in a flame is successfully evaluated by Tm end doped SiO{sub 2} fiber sensor.« less

  9. Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

    PubMed

    Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

    2016-04-05

    UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

  10. Positive expiratory pressure in patients with chronic obstructive pulmonary disease--a systematic review.

    PubMed

    Fagevik Olsén, Monika; Westerdahl, Elisabeth

    2009-01-01

    Breathing exercises against a resistance during expiration are often used as treatment for patients with chronic obstructive pulmonary disease (COPD). Controversy still exists regarding the clinical application and efficacy. The aim of this systematic review was to determine the effects of chest physiotherapy techniques with positive expiratory pressure (PEP) for the prevention and treatment of pulmonary impairment in adults with COPD. The review was conducted on randomised, controlled clinical trials in which breathing exercises with positive expiratory pressure were compared with other chest physical therapy techniques or with no treatment, in adult patients with COPD. A computer-assisted literature search of available databases from 1970 to January 2008 was performed. Two reviewers extracted data independently and assessed the trials systematically with an instrument for measuring methodological quality. In total, 11 trials met the inclusion criteria, of which 5 reached an adequate level of internal validity. Several kinds of PEP techniques with a diversity of intensities and durations of treatment have been evaluated with different outcome measures and follow-up periods. Benefits of PEP were found in isolated outcome measures in separate studies with a follow-up period <1 month. Concerning long-term effects, the results are contradictory. Prior to widespread prescription of long-term PEP treatment, more research is required to establish the benefit of the technique in patients with COPD. (c) 2008 S. Karger AG, Basel.

  11. Submillimeter H2O and H2O+emission in lensed ultra- and hyper-luminous infrared galaxies at z 2-4

    NASA Astrophysics Data System (ADS)

    Yang, C.; Omont, A.; Beelen, A.; González-Alfonso, E.; Neri, R.; Gao, Y.; van der Werf, P.; Weiß, A.; Gavazzi, R.; Falstad, N.; Baker, A. J.; Bussmann, R. S.; Cooray, A.; Cox, P.; Dannerbauer, H.; Dye, S.; Guélin, M.; Ivison, R.; Krips, M.; Lehnert, M.; Michałowski, M. J.; Riechers, D. A.; Spaans, M.; Valiante, E.

    2016-11-01

    We report rest-frame submillimeter H2O emission line observations of 11 ultra- or hyper-luminous infrared galaxies (ULIRGs or HyLIRGs) at z 2-4 selected among the brightest lensed galaxies discovered in the Herschel-Astrophysical Terahertz Large Area Survey (H-ATLAS). Using the IRAM NOrthern Extended Millimeter Array (NOEMA), we have detected 14 new H2O emission lines. These include five 321-312ortho-H2O lines (Eup/k = 305 K) and nine J = 2 para-H2O lines, either 202-111(Eup/k = 101 K) or 211-202(Eup/k = 137 K). The apparent luminosities of the H2O emission lines are μLH2O 6-21 × 108 L⊙ (3 <μ< 15, where μ is the lens magnification factor), with velocity-integrated line fluxes ranging from 4-15 Jy km s-1. We have also observed CO emission lines using EMIR on the IRAM 30 m telescope in seven sources (most of those have not yet had their CO emission lines observed). The velocity widths for CO and H2O lines are found to be similar, generally within 1σ errors in the same source. With almost comparable integrated flux densities to those of the high-J CO line (ratios range from 0.4 to 1.1), H2O is found to be among the strongest molecular emitters in high-redshift Hy/ULIRGs. We also confirm our previously found correlation between luminosity of H2O (LH2O) and infrared (LIR) that LH2O LIR1.1-1.2, with ournew detections. This correlation could be explained by a dominant role of far-infrared pumping in the H2O excitation. Modelling reveals that the far-infrared radiation fields have warm dust temperature Twarm 45-75 K, H2O column density per unit velocity interval NH2O /ΔV ≳ 0.3 × 1015 cm-2 km-1 s and 100 μm continuum opacity τ100> 1 (optically thick), indicating that H2O is likely to trace highly obscured warm dense gas. However, further observations of J ≥ 4 H2O lines are needed to better constrain the continuum optical depth and other physical conditions of the molecular gas and dust. We have also detected H2O+ emission in three sources. A tight correlation

  12. Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

    PubMed

    Garcia, J C; Oliveira, J L; Silva, A E C; Oliveira, C C; Nozaki, J; de Souza, N E

    2007-08-17

    This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

  13. LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

    NASA Astrophysics Data System (ADS)

    Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

    2016-01-01

    Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

  14. Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

    PubMed Central

    Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

    2010-01-01

    Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

  15. Auto-trilevel versus bilevel positive airway pressure ventilation for hypercapnic overlap syndrome patients.

    PubMed

    Su, Mei; Huai, De; Cao, Juan; Ning, Ding; Xue, Rong; Xu, Meijie; Huang, Mao; Zhang, Xilong

    2018-03-01

    Although bilevel positive airway pressure (Bilevel PAP) therapy is usually used for overlap syndrome (OS), there is still a portion of OS patients in whom Bilevel PAP therapy could not simultaneously eliminate residual apnea events and hypercapnia. The current study was expected to explore whether auto-trilevel positive airway pressure (auto-trilevel PAP) therapy with auto-adjusting end expiratory positive airway pressure (EEPAP) can serve as a better alternative for these patients. From January of 2014 to June of 2016, 32 hypercapnic OS patients with stable chronic obstructive pulmonary diseases (COPD) and moderate-to-severe obstructive sleep apnea syndrome (OSAS) were recruited. Three variable modes of positive airway pressure (PAP) from the ventilator (Prisma25ST, Weinmann Inc., Germany) were applicated for 8 h per night. We performed the design of each mode at each night with an interval of two nights with no PAP treatment as a washout period among different modes. In Bilevel-1 mode (Bilevel-1), the expiratory positive airway pressure (EPAP) delivered from Bilevel PAP was always set as the lowest PAP for abolishment of snoring. For each patient, the inspiratory positive airway pressure (IPAP) was constantly set the same as the minimal pressure for keeping end-tidal CO 2 (ETCO 2 ) ≤45 mmHg for all three modes. However, the EPAP issued by Bilevel PAP in Bilevel-2 mode (Bilevel-2) was kept 3 cmH 2 O higher than that in Bilevel-1. In auto-trilevel mode (auto-trilevel) with auto-trilevel PAP, the initial part of EPAP was fixed at the same PAP as that in Bilevel-1 while the EEPAP was automatically regulated to rise at a range of ≤4 cmH 2 O based on nasal airflow wave changes. Comparisons were made for parameters before and during or following treatment as well as among different PAP therapy modes. The following parameters were compared such as nocturnal apnea hypopnea index (AHI), minimal SpO 2 (minSpO 2 ), arousal index, sleep structure and efficiency

  16. Studies of proton irradiated H2O + CO2 and H2O + CO ices and analysis of synthesized molecules

    NASA Technical Reports Server (NTRS)

    Moore, M. H.; Khanna, R.; Donn, B.

    1991-01-01

    Infrared spectra of H2O + CO2 and H2O + CO ices before and after proton irradiation showed that a major reaction in both mixtures was the interconversion of CO2 yields CO. Radiation synthesized organic compounds such as carbonic acid were identified in the H2O + CO2 ice. Different chemical pathways dominate in the H2O + CO ice in which formaldehyde, methanol, ethanol, and methane were identified. Sublimed material was also analyzed using a mass spectrometer. Implications of these results are discussed in reference to comets.

  17. Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

    NASA Astrophysics Data System (ADS)

    Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

    2016-12-01

    Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

  18. Mechanical breath profile of airway pressure release ventilation: the effect on alveolar recruitment and microstrain in acute lung injury.

    PubMed

    Kollisch-Singule, Michaela; Emr, Bryanna; Smith, Bradford; Roy, Shreyas; Jain, Sumeet; Satalin, Joshua; Snyder, Kathy; Andrews, Penny; Habashi, Nader; Bates, Jason; Marx, William; Nieman, Gary; Gatto, Louis A

    2014-11-01

    Improper mechanical ventilation settings can exacerbate acute lung injury by causing a secondary ventilator-induced lung injury. It is therefore important to establish the mechanism by which the ventilator induces lung injury to develop protective ventilation strategies. It has been postulated that the mechanism of ventilator-induced lung injury is the result of heterogeneous, elevated strain on the pulmonary parenchyma. Acute lung injury has been associated with increases in whole-lung macrostrain, which is correlated with increased pathology. However, the effect of mechanical ventilation on alveolar microstrain remains unknown. To examine whether the mechanical breath profile of airway pressure release ventilation (APRV), consisting of a prolonged pressure-time profile and brief expiratory release phase, reduces microstrain. In a randomized, nonblinded laboratory animal study, rats were randomized into a controlled mandatory ventilation group (n = 3) and an APRV group (n = 3). Lung injury was induced by polysorbate lavage. A thoracotomy was performed and an in vivo microscope was placed on the lungs to measure alveolar mechanics. In the controlled mandatory ventilation group, multiple levels of positive end-expiratory pressure (PEEP; 5, 10, 16, 20, and 24 cm H2O) were tested. In the APRV group, decreasing durations of expiratory release (time at low pressure [T(low)]) were tested. The T(low) was set to achieve ratios of termination of peak expiratory flow rate (T-PEFR) to peak expiratory flow rate (PEFR) of 10%, 25%, 50%, and 75% (the smaller this ratio is [ie, 10%], the more time the lung is exposed to low pressure during the release phase, which decreases end-expiratory lung volume and potentiates derecruitment). Alveolar perimeters were measured at peak inspiration and end expiration using digital image analysis, and strain was calculated by normalizing the change in alveolar perimeter length to the original length. Macrostrain was measured by volume

  19. Lung volumes and lung volume recruitment in ARDS: a comparison between supine and prone position.

    PubMed

    Aguirre-Bermeo, Hernan; Turella, Marta; Bitondo, Maddalena; Grandjean, Juan; Italiano, Stefano; Festa, Olimpia; Morán, Indalecio; Mancebo, Jordi

    2018-02-14

    The use of positive end-expiratory pressure (PEEP) and prone position (PP) is common in the management of severe acute respiratory distress syndrome patients (ARDS). We conducted this study to analyze the variation in lung volumes and PEEP-induced lung volume recruitment with the change from supine position (SP) to PP in ARDS patients. The investigation was conducted in a multidisciplinary intensive care unit. Patients who met the clinical criteria of the Berlin definition for ARDS were included. The responsible physician set basal PEEP. To avoid hypoxemia, FiO 2 was increased to 0.8 1 h before starting the protocol. End-expiratory lung volume (EELV) and functional residual capacity (FRC) were measured using the nitrogen washout/washin technique. After the procedures in SP, the patients were turned to PP and 1 h later the same procedures were made in PP. Twenty-three patients were included in the study, and twenty were analyzed. The change from SP to PP significantly increased FRC (from 965 ± 397 to 1140 ± 490 ml, p = 0.008) and EELV (from 1566 ± 476 to 1832 ± 719 ml, p = 0.008), but PEEP-induced lung volume recruitment did not significantly change (269 ± 186 ml in SP to 324 ± 188 ml in PP, p = 0.263). Dynamic strain at PEEP decreased with the change from SP to PP (0.38 ± 0.14 to 0.33 ± 0.13, p = 0.040). As compared to supine, prone position increases resting lung volumes and decreases dynamic lung strain.

  20. Single-ended mid-infrared laser-absorption sensor for simultaneous in situ measurements of H2O, CO2, CO, and temperature in combustion flows.

    PubMed

    Peng, Wen Yu; Goldenstein, Christopher S; Mitchell Spearrin, R; Jeffries, Jay B; Hanson, Ronald K

    2016-11-20

    The development and demonstration of a four-color single-ended mid-infrared tunable laser-absorption sensor for simultaneous measurements of H2O, CO2, CO, and temperature in combustion flows is described. This sensor operates by transmitting laser light through a single optical port and measuring the backscattered radiation from within the combustion device. Scanned-wavelength-modulation spectroscopy with second-harmonic detection and first-harmonic normalization (scanned-WMS-2f/1f) was used to account for variable signal collection and nonabsorption losses in the harsh environment. Two tunable diode lasers operating near 2551 and 2482 nm were utilized to measure H2O concentration and temperature, while an interband cascade laser near 4176 nm and a quantum cascade laser near 4865 nm were used for measuring CO2 and CO, respectively. The lasers were modulated at either 90 or 112 kHz and scanned across the peaks of their respective absorption features at 1 kHz, leading to a measurement rate of 2 kHz. A hybrid demultiplexing strategy involving both spectral filtering and frequency-domain demodulation was used to decouple the backscattered radiation into its constituent signals. Demonstration measurements were made in the exhaust of a laboratory-scale laminar methane-air flat-flame burner at atmospheric pressure and equivalence ratios ranging from 0.7 to 1.2. A stainless steel reflective plate was placed 0.78 cm away from the sensor head within the combustion exhaust, leading to a total absorption path length of 1.56 cm. Detection limits of 1.4% H2O, 0.6% CO2, and 0.4% CO by mole were reported. To the best of the authors' knowledge, this work represents the first demonstration of a mid-infrared laser-absorption sensor using a single-ended architecture in combustion flows.

  1. Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

    PubMed Central

    Paschalidis, Damianos G.; Harrison, William T. A.

    2016-01-01

    The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

  2. Ventilation practices in the neonatal intensive care unit: a cross-sectional study.

    PubMed

    van Kaam, Anton H; Rimensberger, Peter C; Borensztajn, Dorine; De Jaegere, Anne P

    2010-11-01

    To assess current ventilation practices in newborn infants. We conducted a 2-point cross-sectional study in 173 European neonatal intensive care units, including 535 infants (mean gestational age 28 weeks and birth weight 1024 g). Patient characteristics, ventilator settings, and measurements were collected bedside from endotracheally ventilated infants. A total of 457 (85%) patients were conventionally ventilated. Time cycled pressure-limited ventilation was used in 59% of these patients, most often combined with synchronized intermittent mandatory ventilation (51%). Newer conventional ventilation modes like volume targeted and pressure support ventilation were used in, respectively, 9% and 7% of the patients. The mean tidal volume, measured in 84% of the conventionally ventilated patients, was 5.7 ± 2.3 ml/kg. The mean positive end-expiratory pressure was 4.5 ± 1.1 cmH(2)O and rarely exceeded 7 cmH(2)O. Time cycled pressure-limited ventilation is the most commonly used mode in neonatal ventilation. Tidal volumes are usually targeted between 4 to 7 mL/kg and positive end-expiratory pressure between 4 to 6 cmH(2)O. Newer ventilation modes are only used in a minority of patients. Copyright © 2010 Mosby, Inc. All rights reserved.

  3. High-Level ab initio electronic structure calculations of Water Clusters (H2O)16 and (H2O)17: a new global minimum for (H2O)16

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

    Yoo, Soohaeng; Apra, Edoardo; Zeng, Xiao Cheng

    The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at the MP2 and CCSD(T) levels of theory and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17 the CCSD(T) calculations confirm the previously found at the MP2 level of theory "interior" arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum.

  4. High-Level ab-initio Electronic Structure Calculations of Water Clusters (H2O)16 and (H2O)17 : a New Global Minimum for (H2O)16

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

    Yoo, Soohaeng; Apra, Edoardo; Zeng, X.C.

    The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at both the MP2 and CCSD(T) levels of theory, and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17, the CCSD(T) calculations confirm the previously found at the MP2 level of theory interior arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum

  5. The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

    NASA Astrophysics Data System (ADS)

    Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

    2018-07-01

    The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

  6. Deep breathing exercises with positive expiratory pressure at a higher rate improve oxygenation in the early period after cardiac surgery--a randomised controlled trial.

    PubMed

    Urell, Charlotte; Emtner, Margareta; Hedenström, Hans; Tenling, Arne; Breidenskog, Marie; Westerdahl, Elisabeth

    2011-07-01

    In addition to early mobilisation, a variety of breathing exercises are used to prevent postoperative pulmonary complications after cardiac surgery. The optimal duration of the treatment is not well evaluated. The aim of this study was to determine the effect of 30 versus 10 deep breaths hourly, while awake, with positive expiratory pressure on oxygenation and pulmonary function the first days after cardiac surgery. A total of 181 patients, undergoing cardiac surgery, were randomised into a treatment group, performing 30 deep breaths hourly the first postoperative days, or into a control group performing 10 deep breaths hourly. The main outcome measurement arterial blood gases and the secondary outcome pulmonary function, evaluated with spirometry, were determined on the second postoperative day. Preoperatively, both study groups were similar in terms of age, SpO(2), forced expiratory volume in 1s and New York Heart Association classification. On the second postoperative day, arterial oxygen tension (PaO(2)) was 8.9 ± 1.7 kPa in the treatment group and 8.1 ± 1.4 kPa in the control group (p = 0.004). Arterial oxygen saturation (SaO(2)) was 92.7 ± 3.7% in the treatment group and 91.1 ± 3.8% in the control group (p = 0.016). There were no differences in measured lung function between the groups or in compliance to the breathing exercises. Compliance was 65% of possible breathing sessions. A significantly increased oxygenation was found in patients performing 30 deep breaths the first two postoperative days compared with control patients performing 10 deep breaths hourly. These results support the implementation of a higher rate of deep breathing exercises in the initial phase after cardiac surgery. Copyright © 2010 European Association for Cardio-Thoracic Surgery. Published by Elsevier B.V. All rights reserved.

  7. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2013-03-01

    ''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

  8. The dependency of expiratory airway collapse on pump system and flow rate in liquid ventilated rabbits.

    PubMed

    Meinhardt, J P; Ashton, B A; Annich, G M; Quintel, M; Hirschl, R B

    2003-05-30

    To evaluate the influence of pump system and flow pattern on expiratory airway collapse (EAC) in total perfluorocarbon ventilation. - Prospective, controlled, randomized animal trial for determination of (1) post-mortem changes by repeated expiration procedures (EP) with a constant flow piston pump (PP) before and after sacrifice (n = 8 rabbits), (2) differences between pump systems by subjecting animals to both PP and roller pump (RP) circuits for expiration (n = 16 rabbits). EP were performed using a servo-controlled shut-off at airway pressures < 25 cm H subset 2O randomly with either pump at different flows. - Expired volumes before and after sacrifice were not significantly different. PP and RP revealed identical mean flows, while significantly more liquid was drained using PP (p<0.05). Increasing differences towards higher flow rates indicated profound flow pulsatility in RP. - (1) post-mortem changes in expired volumes are not significant, (2) EAC is related to flow rate and pump system; (3) relationship between expiratory flow rate and drainable liquid volume is linear inverse; (4) PP provides higher drainage than RP. - Expiratory airway collapse is related to flow rate and pump system, post mortem changes in expirable volumes are not significant. Relationship between expiratory flow rate and drainable liquid volume is linear inverse, piston pump expiration provides higher drainage volumes than roller pump expiration.

  9. Open Lung Approach for the Acute Respiratory Distress Syndrome: A Pilot, Randomized Controlled Trial.

    PubMed

    Kacmarek, Robert M; Villar, Jesús; Sulemanji, Demet; Montiel, Raquel; Ferrando, Carlos; Blanco, Jesús; Koh, Younsuck; Soler, Juan Alfonso; Martínez, Domingo; Hernández, Marianela; Tucci, Mauro; Borges, Joao Batista; Lubillo, Santiago; Santos, Arnoldo; Araujo, Juan B; Amato, Marcelo B P; Suárez-Sipmann, Fernando

    2016-01-01

    The open lung approach is a mechanical ventilation strategy involving lung recruitment and a decremental positive end-expiratory pressure trial. We compared the Acute Respiratory Distress Syndrome network protocol using low levels of positive end-expiratory pressure with open lung approach resulting in moderate to high levels of positive end-expiratory pressure for the management of established moderate/severe acute respiratory distress syndrome. A prospective, multicenter, pilot, randomized controlled trial. A network of 20 multidisciplinary ICUs. Patients meeting the American-European Consensus Conference definition for acute respiratory distress syndrome were considered for the study. At 12-36 hours after acute respiratory distress syndrome onset, patients were assessed under standardized ventilator settings (FIO2≥0.5, positive end-expiratory pressure ≥10 cm H2O). If Pao2/FIO2 ratio remained less than or equal to 200 mm Hg, patients were randomized to open lung approach or Acute Respiratory Distress Syndrome network protocol. All patients were ventilated with a tidal volume of 4 to 8 ml/kg predicted body weight. From 1,874 screened patients with acute respiratory distress syndrome, 200 were randomized: 99 to open lung approach and 101 to Acute Respiratory Distress Syndrome network protocol. Main outcome measures were 60-day and ICU mortalities, and ventilator-free days. Mortality at day-60 (29% open lung approach vs. 33% Acute Respiratory Distress Syndrome Network protocol, p = 0.18, log rank test), ICU mortality (25% open lung approach vs. 30% Acute Respiratory Distress Syndrome network protocol, p = 0.53 Fisher's exact test), and ventilator-free days (8 [0-20] open lung approach vs. 7 [0-20] d Acute Respiratory Distress Syndrome network protocol, p = 0.53 Wilcoxon rank test) were not significantly different. Airway driving pressure (plateau pressure - positive end-expiratory pressure) and PaO2/FIO2 improved significantly at 24, 48 and 72 hours in patients

  10. I + (H2O)2 → HI + (H2O)OH Forward and Reverse Reactions. CCSD(T) Studies Including Spin-Orbit Coupling.

    PubMed

    Wang, Hui; Li, Guoliang; Li, Qian-Shu; Xie, Yaoming; Schaefer, Henry F

    2016-03-03

    The potential energy profile for the atomic iodine plus water dimer reaction I + (H2O)2 → HI + (H2O)OH has been explored using the "Gold Standard" CCSD(T) method with quadruple-ζ correlation-consistent basis sets. The corresponding information for the reverse reaction HI + (H2O)OH → I + (H2O)2 is also derived. Both zero-point vibrational energies (ZPVEs) and spin-orbit (SO) coupling are considered, and these notably alter the classical energetics. On the basis of the CCSD(T)/cc-pVQZ-PP results, including ZPVE and SO coupling, the forward reaction is found to be endothermic by 47.4 kcal/mol, implying a significant exothermicity for the reverse reaction. The entrance complex I···(H2O)2 is bound by 1.8 kcal/mol, and this dissociation energy is significantly affected by SO coupling. The reaction barrier lies 45.1 kcal/mol higher than the reactants. The exit complex HI···(H2O)OH is bound by 3.0 kcal/mol relative to the asymptotic limit. At every level of theory, the reverse reaction HI + (H2O)OH → I + (H2O)2 proceeds without a barrier. Compared with the analogous water monomer reaction I + H2O → HI + OH, the additional water molecule reduces the relative energies of the entrance stationary point, transition state, and exit complex by 3-5 kcal/mol. The I + (H2O)2 reaction is related to the valence isoelectronic bromine and chlorine reactions but is distinctly different from the F + (H2O)2 system.

  11. Synthesis and characterization of polymer eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O as well as the interaction of [Y III(pdta)(H 2O)] 22- with BSA

    NASA Astrophysics Data System (ADS)

    Liu, Bin; Wang, Jun; Wang, Xin; Liu, Bing-Mi; He, Ling-Ling; Xu, Shu-Kun

    2010-12-01

    The eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O (en = ethylenediamine and H 4pdta = 1,3-propylenediamine- N, N, N', N'-tetraacetic acid) was synthesized, meanwhile its molecular and crystal structures were determined by single-crystal X-ray diffraction technology. The interaction between [Y III(pdta)(H 2O)] 22- and bovine serum albumin (BSA) was investigated by UV-vis and fluorescence spectra. The results indicate that [Y III(pdta)(H 2O)] 22- quenched effectively the intrinsic fluorescence of BSA via a static quenching process with the binding constant ( Ka) of the order of 10 4. Meanwhile, the binding and damaging sites to BSA molecules were also estimated by synchronous fluorescence. Results indicate that the hydrophobic environments around Trp and Tyr residues were all slightly changed. The thermodynamic parameters (Δ G = -25.20 kJ mol -1, Δ H = -26.57 kJ mol -1 and Δ S = -4.58 J mol -1 K -1) showed that the reaction was spontaneous and exothermic. What is more, both Δ H and Δ S were negative values indicated that hydrogen bond and Van der Waals forces were the predominant intermolecular forces between [Y III(pdta)(H 2O)] 22- and BSA.

  12. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Lyons, M.; Siegel, E.

    2010-03-01

    ``Water water everywhere; ne'er a drop to drink''[Coleridg(1798)]; now:``Hydrogen hydrogen everywhere;STILL ne'er a drop to drink'': ONLY H2 can be ``FLYING-WATER''/``chemical-rain-in-pipelines''/ ``Hindenberg-effect (H2-UP;H2O-DOWN): atomic-weights ratio: O/H2O=[16]/[18]˜90%; O already in air uphill; NO H2O pumping need! In water-starved glacial-melting world, rescue ONLY by Siegel[3rd Intl.Conf.Alt.Energy,Hemisphere/Springer(1980)- vol.5/ p.459]Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating- system. Rosenfeld[Sci.315,1396(3/9/2007)]-Biello[Sci.Am.(3/9/ 2007)]crucial geomorphology which ONLY maximal-buoyancy light- est-element H2 can exploit, to again make ``Mountains into Fount- ains": Siegel ``terra-forming''(and ocean-rebasificaton!!!) long pre-``Holdren''-``Ciccerine" ``geo-enginering'', only via Siegel proprietary magnetic-hydrogen-valve permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Sci.300,1740(03)]global-pandemics (cancers/blindness/famine)dire-warning about H2-(ALONE)economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!

  13. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

  14. Catalase activity is stimulated by H2O2 in rich culture medium and is required for H2O2 resistance and adaptation in yeast☆

    PubMed Central

    Martins, Dorival; English, Ann M.

    2014-01-01

    Catalases are efficient scavengers of H2O2 and protect cells against H2O2 stress. Examination of the H2O2 stimulon in Saccharomyces cerevisiae revealed that the cytosolic catalase T (Ctt1) protein level increases 15-fold on H2O2 challenge in synthetic complete media although previous work revealed that deletion of the CCT1 or CTA1 genes (encoding peroxisomal/mitochondrial catalase A) does not increase the H2O2 sensitivity of yeast challenged in phosphate buffer (pH 7.4). This we attributed to our observation that catalase activity is depressed when yeast are challenged with H2O2 in nutrient-poor media. Hence, we performed a systematic comparison of catalase activity and cell viability of wild-type yeast and of the single catalase knockouts, ctt1∆ and cta1∆, following H2O2 challenge in nutrient-rich medium (YPD) and in phosphate buffer (pH 7.4). Ctt1 but not Cta1 activity is strongly induced by H2O2 when cells are challenged in YPD but suppressed when cells are challenged in buffer. Consistent with the activity results, exponentially growing ctt1∆ cells in YPD are more sensitive to H2O2 than wild-type or cta1∆ cells, whereas in buffer all three strains exhibit comparable H2O2 hypersensitivity. Furthermore, catalase activity is increased during adaptation to sublethal H2O2 concentrations in YPD but not in buffer. We conclude that induction of cytosolic Ctt1 activity is vital in protecting yeast against exogenous H2O2 but this activity is inhibited by H2O2 when cells are challenged in nutrient-free media. PMID:24563848

  15. X-ray-induced dissociation of H.sub.2O and formation of an O.sub.2-H.sub.2 alloy at high pressure

    DOEpatents

    Mao, Ho-kwang [Washington, DC; Mao, Wendy L [Washington, DC

    2011-11-29

    A novel molecular alloy of O.sub.2 and H.sub.2 and a method of producing such a molecular alloy are provided. When subjected to high pressure and extensive x-radiation, H.sub.2O molecules cleaved, forming O--O and H--H bonds. In the method of the present invention, the O and H framework in ice VII was converted into a molecular alloy of O.sub.2 and H.sub.2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrate that this crystalline solid differs from previously known phases.

  16. The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

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

    Davidson, Stephen D.; Sun, Junming; Wang, Yong

    The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway,more » evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.« less

  17. The reaction of H2O2 with NO2 and NO

    NASA Technical Reports Server (NTRS)

    Gray, D.; Lissi, E.; Heicklen, J.

    1972-01-01

    The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

  18. Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

    PubMed

    Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

    2012-04-19

    The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

  19. Effects of nasal positive expiratory pressure on dynamic hyperinflation and 6-minute walk test in patients with COPD.

    PubMed

    Wibmer, Thomas; Rüdiger, Stefan; Heitner, Claudia; Kropf-Sanchen, Cornelia; Blanta, Ioanna; Stoiber, Kathrin M; Rottbauer, Wolfgang; Schumann, Christian

    2014-05-01

    Dynamic hyperinflation is an important target in the treatment of COPD. There is increasing evidence that positive expiratory pressure (PEP) could reduce dynamic hyperinflation during exercise. PEP application through a nasal mask and a flow resistance device might have the potential to be used during daily physical activities as an auxiliary strategy of ventilatory assistance. The aim of this study was to determine the effects of nasal PEP on lung volumes during physical exercise in patients with COPD. Twenty subjects (mean ± SD age 69.4 ± 6.4 years) with stable mild-to-severe COPD were randomized to undergo physical exercise with nasal PEP breathing, followed by physical exercise with habitual breathing, or vice versa. Physical exercise was induced by a standard 6-min walk test (6 MWT) protocol. PEP was applied by means of a silicone nasal mask loaded with a fixed-orifice flow resistor. Body plethysmography was performed immediately pre-exercise and post-exercise. Differences in mean pre- to post-exercise changes in total lung capacity (-0.63 ± 0.80 L, P = .002), functional residual capacity (-0.48 ± 0.86 L, P = .021), residual volume (-0.56 ± 0.75 L, P = .004), S(pO2) (-1.7 ± 3.4%, P = .041), and 6 MWT distance (-30.8 ± 30.0 m, P = .001) were statistically significant between the experimental and the control interventions. The use of flow-dependent expiratory pressure, applied with a nasal mask and a PEP device, might promote significant reduction of dynamic hyperinflation during walking exercise. Further studies are warranted addressing improvements in endurance performance under regular application of nasal PEP during physical activities.

  20. New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

    2006-01-01

    We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

  1. Cells with impaired mitochondrial H2O2 sensing generate less •OH radicals and live longer.

    PubMed

    Martins, Dorival; Titorenko, Vladimir I; English, Ann M

    2014-10-01

    Mitochondria are major sites of reactive oxygen species (ROS) generation, and adaptive mitochondrial ROS signaling extends longevity. We aim at linking the genetic manipulation of mitochondrial H2O2 sensing in live cells to mechanisms driving aging in the model organism, Saccharomyces cerevisiae. To this end, we compare in vivo ROS (O2(•-), H2O2 and (•)OH) accumulation, antioxidant enzyme activities, labile iron levels, GSH depletion, and protein oxidative damage during the chronological aging of three yeast strains: ccp1Δ that does not produce the mitochondrial H2O2 sensor protein, cytochrome c peroxidase (Ccp1); ccp1(W191F) that produces a hyperactive variant of this sensor protein (Ccp1(W191F)); and the isogenic wild-type strain. Since they possess elevated manganese superoxide dismutase (Sod2) activity, young ccp1Δ cells accumulate low mitochondrial superoxide (O2(•-)) levels but high H2O2 levels. These cells exhibit stable aconitase activity and contain low amounts of labile iron and hydroxyl radicals ((•)OH). Furthermore, they undergo late glutathione (GSH) depletion, less mitochondrial protein oxidative damage and live longer than wild-type cells. In contrast, young ccp1(W191F) cells accumulate little H2O2, possess depressed Sod2 activity, enabling their O2(•-) level to spike and deactivate aconitase, which, ultimately, leads to greater mitochondrial oxidative damage, early GSH depletion, and a shorter lifespan than wild-type cells. Modulation of mitochondrial H2O2 sensing offers a novel interventional approach to alter mitochondrial H2O2 levels in live cells and probe the pro- versus anti-aging effects of ROS. The strength of mitochondrial H2O2 sensing modulates adaptive mitochondrial ROS signaling and, hence, lifespan.

  2. Application of H2O and UV/H2O2 processes for enhancing the biodegradability of reactive black 5 dye.

    PubMed

    Kalpana, S Divya; Kalyanaraman, Chitra; Gandhi, N Nagendra

    2011-07-01

    Leather processing is a traditional activity in India during which many organic and inorganic chemicals are added while part of it is absorbed by the leather, the remaining chemicals are discharged along with the effluent. The effluent contains both easily biodegradable and not easily biodegradable synthetic organics like dyes, syntans. Easily biodegradable organics are removed in the existing biological treatment units whereas synthetic organics present in the wastewater are mostly adsorbed over the microbes. As the tannery effluent contains complex chemicals, it is difficult to ascertain the degradation of specific pollutants. To determine the increase in the biodegradability, one of the complex and synthetic organic chemical like dye used in the tanning operation was selected for Advanced Oxidation Process (AOPs) treatment for cleaving complex organics and its subsequent treatment in aerobic process. In the present study, Reactive Black 5 Dye used in the tanning operation was selected for Hydrogen Peroxide (H2O2) and UV/H2O2 pre-treatment for different operating conditions like pH, contact time and different volume of H2O2. A comparison was made between the untreated, Hydrogen Peroxide (H2O2) and UV/H2O2 treated effluent in order to ascertain the influence of AOP on the improvement of biodegradability of effluent. An increase in the BOD5/COD ratio from 0.21 to 0.435 was achieved in the UV/H2O2 pre-treatment process. This pre-treated effluent was further subjected to aerobic process. Biochemical Oxygen Demand (BOD5) and Chemical Oxygen Demand (COD) removal efficiency of the UV/H2O2 pre-treated dye solution in the aerobic process was found to be 86.39% and 77.82% when compared to 52.43% of BOD5 and 51.55% of COD removal efficiency without any pre-treatment. Hence from these results, to increase the biodegradability of Reactive Black 5 dye pre-treatment methods like H2O2 and UV/H2O2 can be used prior to biological treatment process.

  3. Degradation mechanism of cyanide in water using a UV-LED/H2O2/Cu2+ system.

    PubMed

    Kim, Tae-Kyoung; Kim, Taeyeon; Jo, Areum; Park, Suhyun; Choi, Kyungho; Zoh, Kyung-Duk

    2018-06-01

    In this study, we developed a UV-LED/H 2 O 2 /Cu 2+ system to remove cyanide, which is typically present in metal electroplating wastewater. The results showed the synergistic effects of UV-LED, H 2 O 2 , and Cu 2+ ions on cyanide removal in comparison with UV-LED photolysis, H 2 O 2 oxidation, UV-LED/H 2 O 2 , and H 2 O 2 /Cu 2+ systems. Cyanide was removed completely in 30 min in the UV-LED/H 2 O 2 /Cu 2+ system, and its loss followed pseudo-first order kinetics. Statistically, both H 2 O 2 and Cu 2+ ions showed positive effects on cyanide removal, but Cu 2+ ions exhibited a greater effect. The highest cyanide removal rate constant (k = 0.179 min -1 ) was achieved at pH 11, but the lowest was achieved at pH 12.5 (k = 0.064 min -1 ) due to the hydrolysis of H 2 O 2 (pK a of H 2 O 2  = 11.75). The presence of dissolved organic matter (DOM) inhibited cyanide removal, and the removal rate constant exhibited a negative linear correlation with DOM (R 2  = 0.987). The removal rate of cyanide was enhanced by the addition of Zn 2+ ions (from 0.179 to 0.457 min -1 ), while the co-existence of Ni 2+ or Cr +6 ion with Cu 2+ ion reduced cyanide removal. The formation of OH radicals in the UV-LED/H 2 O 2 /Cu 2+ system was verified using an aminophenyl fluorescence (APF) probe. Cyanate ions and ammonia were detected as the byproducts of cyanide decomposition. Finally, an acute toxicity reduction of 64.6% was achieved in the system within 1 h, despite a high initial cyanide concentration (100 mg/L). In terms of removal efficiency and toxicity reduction, the UV-LED/H 2 O 2 /Cu 2+ system may be an alternative method of cyanide removal from wastewaters. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. New experimental constraints on liquidi, critical mixing, and the second critical end point in the system albite-H2O

    NASA Astrophysics Data System (ADS)

    Makhluf, A. R.; Newton, R. C.; Manning, C. E.

    2013-12-01

    Supercritical fluids in rock-H2O systems have been proposed to be important agents of mass transfer in high-pressure environments such as subduction zones. We conducted new experimental studies of the important model system H2O-albite (NaAlSi3O8). Equilibrium phase relations were determined in isobaric T-XH2O binaries at 10.0, 12.5, 14.0, 16.0, and 17.0 kbar, at 600-1060 °C and H2O mole fractions (XH2O) of 0.35 to 0.99. All experiments were conducted in a piston-cylinder apparatus. Stabilities of hydrous albite liquid (L) and H2O-rich vapor (V) were determined from textural analysis of run products by binocular, petrographic and scanning electron microscopy. At each pressure, the experiments bracketed the liquidus curve, the topology of the L+V miscibility gap, and the temperature of critical mixing (TC). The bulk composition at critical mixing of L+V is ~50 wt% H2O at all pressures investigated. The P-T trace of the critical curve is described by the equation TC = -59.9P + 1650 (R2=0.998) where T is in °C and P is in kbar, and the equation is valid over the investigated P and T. The results indicate a critical endpoint on the hydrous melting curve at 16.3 kbar and 667 °C. Our results agree reasonably well with the work of Burnham and Jahns (1962, Am. Journal of Sci., 260, 721) and Shen and Keppler (1997, Nature, 385, 710). The constraints on the phase equilibria allow derivation of a thermodynamic model using a modified version of the Redlich-Kister method (1948, Indus. and Eng. Chem., 40b, 345) which allows quantification of the NaAlSi3O8 activity, aAb, and H2O activity, aH2O, over the entire composition range at each of the above listed pressures, between the solidus temperatures and critical temperatures. The results provide fundamental constraints on the physical chemical controls on the generation and solution properties of supercritical and subcritical fluids in the albite-H2O system.

  5. Influence of Ar/O2/H2O Feed Gas and N2/O2/H2O Environment on the Interaction of Time Modulated MHz Atmospheric Pressure Plasma Jet (APPJ) with Model Polymers

    NASA Astrophysics Data System (ADS)

    Oehrlein, Gottlieb; Luan, Pingshan; Knoll, Andrew; Kondeti, Santosh; Bruggeman, Peter

    2016-09-01

    An Ar/O2/H2O fed time modulated MHz atmospheric pressure plasma jet (APPJ) in a sealed chamber was used to study plasma interaction with model polymers (polystyrene, poly-methyl methacrylate, etc.). The amount of H2O in the feed gas and/or present in the N2, O2, or N2/O2 environment was controlled. Short lived species such as O atoms and OH radicals play a crucial role in polymer etching and surface modifications (obtained from X-ray photoelectron spectroscopy of treated polymers without additional atmospheric exposure). Polymer etching depth for Ar/air fed APPJ mirrors the decay of gas phase O atoms with distance from the APPJ nozzle in air and is consistent with the estimated O atom flux at the polymer surface. Furthermore, whereas separate O2 or H2O admixture to Ar enhances polymer etching, simultaneous addition of O2 and H2O to Ar quenches polymer etching. This can be explained by the mutual quenching of O with OH, H and HO2 in the gas phase. Results where O2 and/or H2O in the environment were varied are consistent with these mechanisms. All results will be compared with measured and simulated species densities reported in the literature. We gratefully acknowledge funding from US Department of Energy (DE-SC0001939) and National Science Foundation (PHY-1415353).

  6. ESR investigation of ROS generated by H2O2 bleaching with TiO2 coated HAp.

    PubMed

    Saita, Makiko; Kobayashi, Kyo; Kobatashi, Kyou; Yoshino, Fumihiko; Hase, Hiriko; Nonami, Toru; Kimoto, Katsuhiko; Lee, Masaichi-Chang-il

    2012-01-01

    It is well known that clinical bleaching can be achieved with a solution of 30% hydrogen peroxide (H2O2) or H2O2/titanium dioxide (TiO2) combination. This study examined the hypothesis that TiO2 coated with hydroxyapatite (HAp-TiO2) can generate reactive oxygen species (ROS). ROS are generated via photocatalysis using electron spin resonance (ESR). The bleaching properties of HAp-TiO2 in the presence of H2O2 can be measured using hematoporphyrin litmus paper and extracted teeth. We demonstrate that superoxides (O2(•-)) and hydroxyl radicals (HO(•)) can be generated through excitation of anatase TiO2, rutile TiO2, anatase HAp-TiO2, and rutile HAp-TiO2 in the presence of H2O2. The combination of R HAp-TiO2 with H2O2 produced the highest level of HO(•) generation and the most marked bleaching effects of all the samples. The superior bleaching effects exhibited by R HAp-TiO2 with H2O2 suggest that this combination may lead to novel methods for the clinical application of bleaching treatments.

  7. A Computational Investigation of the Oxidative Deboronation of BoroGlycine, H2N–CH2–B(OH)2, Using H2O and H2O2

    PubMed Central

    Larkin, Joseph D.; Markham, George D.; Milkevitch, Matt; Brooks, Bernard R.; Bock, Charles W.

    2014-01-01

    We report results from a computational investigation of the oxidative deboronation of BoroGlycine, H2N–CH2–B(OH)2, using H2O and H2O2 as the reactive oxygen species (ROS) to yield aminomethanol, H2N–CH2–OH; these results complement our study on the protodeboronation of BoroGlycine to produce methylamine, H2N–CH3 (Larkin et al. J. Phys. Chem. A, 111, 6489–6500, 2007). Second-order Møller-Plesset (MP2) perturbation theory with Dunning-Woon correlation-consistent (cc) basis sets were used for the calculations with comparisons made to results from Density Functional Theory (DFT) at the PBE1PBE/6-311++G(d,p)(cc-pVDZ) levels. The effects of a bulk aqueous environment were also incorporated into the calculations employing PCM and CPCM methodology. Using H2O as the ROS, the reaction H2O + H2N–CH2–B(OH)2H2N–CH2–OH + H–B(OH)2 was calculated to be endothermic, the value of ΔH2980 was +12.0 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and +13.7 kcal/mol in PCM aqueous media; the corresponding value for the activation barrier, ΔH‡, was +94.3 kcal/mol relative to the separated reactants in vacuo and +89.9 kcal/mol in PCM aqueous media. In contrast, the reaction H2O2 + H2N–CH2–B(OH)2H2N–CH2–OH + B(OH)3 was calculated to be highly exothermic with a ΔH2980 value of −100.9 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and −99.6 kcal/mol in CPCM aqueous media; the highest-energy transition state for the multi-step process associated with this reaction involved the rearrangement of H2N–CH2–B(OH)(OOH) to H2N–CH2–O–B(OH)2 with a ΔH‡ value of +23.2 kcal/mol in vacuo relative to the separated reactants. These computational results for BoroGlycine are in accord with the experimental observations for the deboronation of the FDA approved anti-cancer drug Bortezomib (Velcade™, PS-341) where it was found to be the principle deactivation pathway. (Labutti et al. Chem. Res. Toxicol., 19, 539–546

  8. Lung gas volumes and expiratory time constant in immature newborn rabbits treated with natural or synthetic surfactant or detergents.

    PubMed

    Bongrani, S; Fornasier, M; Papotti, M; Razzetti, R; Robertson, B

    1994-01-01

    Immature newborn rabbits delivered at a gestational age of 27 days were tracheotomized and treated, via the tracheal cannula, with clinically recommended doses of natural or synthetic surfactant (Curosurf and Exosurf, respectively). Littermates received 0.1% tyloxapol, 5% Tween 20, or saline. The dose volume of Curosurf was 2.5 ml/kg, that of the other materials 5 ml/kg. Animals were kept in a multiplethysmograph system and ventilated for 30 min with a standardized sequence of insufflation pressures. End-expiratory lung gas volume was calculated at the end of the experiment from measurements of lung weight and total lung volume. Tidal volumes were significantly improved in all groups of animals receiving surfactant or detergents. However, expiratory time constant (determined from the tidal volume tracing) was significantly longer, and end-expiratory gas volume significantly larger, in animals treated with Curosurf than in those receiving Exosurf or detergents. These differences were confirmed by semiquantitative evaluation of alveolar air expansion in histological sections. In addition, airway epithelial necrosis was reduced in animals receiving Curosurf, Exosurf, or Tween 20, but not in animals treated with tyloxapol. The discrepancy between improvements in tidal volume, expiratory time constant, and end-expiratory gas volume reflects failure of lung stabilization in animals treated with Exosurf or detergents, probably due to absence of specific hydrophobic proteins in the synthetic products.

  9. Arsenite oxidation by H 2O 2 in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Pettine, Maurizio; Campanella, Luigi; Millero, Frank J.

    1999-09-01

    The rates of the oxidation of As( III) with H 2O 2 were measured in NaCl solutions as a function of pH (7.5-10.3), temperature (10-50C) and ionic strength ( I = 0.01-4). The rate of the oxidation of As( III) with H 2O 2 can be described by the general expression: d[As( III)]/ dt = k[As( III)] [H 2O 2] where k (mol/L -1 min -1) can be determined from (σ = ±0.12) log k=5.29+1.41 pH-0.57 I+1.40 I0.5-4898/ T. The effect of pH on the rates indicates that the reaction is due to AsO( OH) 2-+ H2O2k 1→productsAsO2( OH) 2-+ H2O2k 2→products, AsO33-+ H2O2k 3→products where k = k1 α AsO(OH) 2- + k2 α AsO 2(OH) 2- + k3 α AsO 3 3- and α i are the molar fraction of species i. The values of k1 = 42 ± 20, k2 = (8 ± 1) × 10 4, and k3 = (72 ± 18) × 10 6 mol/L -1 min -1 were found at 25C and I = 0.01 mol/L. The undissociated As(OH) 3 does not react with H 2O 2. The effect of ionic strength on the rate constants has been attributed to the effect of ionic strength on the speciation of As( III). The rate expression has been shown to be valid for NaClO 4 solutions, northern Adriatic sea waters, and Tiber River waters. The cations Fe 2+ and Cu 2+ were found to exert a catalytic effect on the rates. Cu 2+ plays a role at concentration levels (>0.1 μmol/L) which are typical of polluted aquatic systems, while Fe 2+ is important at levels which may be found in lacustrine environments (>5-10 μmol/L). The reaction of As( III) with H 2O 2 may play a role in marine and lacustrine surface waters limiting the accumulation of As( III) resulting from biologically mediated reduction processes of As( V).

  10. High-resolution photoelectron spectroscopy of TiO3H2-: Probing the TiO2- + H2O dissociative adduct

    NASA Astrophysics Data System (ADS)

    DeVine, Jessalyn A.; Abou Taka, Ali; Babin, Mark C.; Weichman, Marissa L.; Hratchian, Hrant P.; Neumark, Daniel M.

    2018-06-01

    Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiO3H2- anions is used to probe the simplest titania/water reaction, TiO20/- + H2O. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH)2- geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO2- monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH)2. The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO2- indicates that reaction with water stabilizes neutral TiO2 more than the anion, providing insight into the fundamental chemical interactions between titania and water.

  11. Physiological Effects of Positive Pressure Ventilation.

    DTIC Science & Technology

    1992-05-01

    function in the patient with respiratory failure . In R. R. Kirby, M. J. Banner, & J. B. Downs (Eds.), Clinical Applications of Ventilatory Su2Rort (pp. 301...G., Blehschmidt, N. G., & Linder, W. J. (1990). Positive-pressure ventilation with positive end-expiratory pressure and atrial natriuretic peptide ...Acute Resniratorv Failure . New York: Churchill Livingstone. Ventilation 1 Physiological Effects of Positive Pressure Ventilation Dennis L. Oakes, RN, BSN

  12. Photoassisted Oxygen Reduction Reaction in H2 -O2 Fuel Cells.

    PubMed

    Zhang, Bingqing; Wang, Shengyang; Fan, Wenjun; Ma, Weiguang; Liang, Zhenxing; Shi, Jingying; Liao, Shijun; Li, Can

    2016-11-14

    The oxygen reduction reaction (ORR) is a key step in H 2 -O 2 fuel cells, which, however, suffers from slow kinetics even for state-of-the-art catalysts. In this work, by making use of photocatalysis, the ORR was significantly accelerated with a polymer semiconductor (polyterthiophene). The onset potential underwent a positive shift from 0.66 to 1.34 V, and the current was enhanced by a factor of 44 at 0.6 V. The improvement was further confirmed in a proof-of-concept light-driven H 2 -O 2 fuel cell, in which the open circuit voltage (V oc ) increased from 0.64 to 1.18 V, and the short circuit current (J sc ) was doubled. This novel tandem structure combining a polymer solar cell and a fuel cell enables the simultaneous utilization of photo- and electrochemical energy, showing promising potential for applications in energy conversion and storage. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis of zinc sulfide nanoparticles during zinc oxidization by H2S and H2S/H2O supercritical fluids

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Fedyaeva, O. N.; Sokol, M. Ya.; Shatrova, A. V.

    2014-12-01

    Formation of zinc sulfide nanoparticles was detected during interaction of bulk samples with hydrogen sulfide at supercritical parameters. Synthesis proceeds with liberation of H2 by the reaction nZn + nH2S = (ZnS) n + nH2. It has been found by the X-ray diffraction method, scanning electron microscopy, and mass spectrometry that the addition of water stimulates coupled reactions of nanoparticle synthesis nZn + nH2O = (ZnO) n + nH2 and (ZnO) n + nH2S = (ZnS) n + nH2O and brings about an increase in the synthesis rate and morphological changes of (ZnS) n nanoparticles.

  14. [{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

    PubMed

    Botar, Bogdan; Kögerler, Paul; Hill, Craig L

    2005-07-07

    Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

  15. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

    PubMed

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-14

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  16. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-01

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  17. 2,4-Dinitrophenylhydrazine, redetermined at 120 K: a three-dimensional framework built from N-H...O, N-H...(O)2, N-H...pi(arene) and C-H...O hydrogen bonds.

    PubMed

    Wardell, James L; Low, John N; Glidewell, Christopher

    2006-06-01

    In the title compound, C6H6N4O4, the bond distances indicate significant bond fixation, consistent with charge-separated polar forms. The molecules are almost planar and there is an intramolecular N-H...O hydrogen bond. The molecules are linked into a complex three-dimensional framework structure by a combination of N-H...O, N-H...(O)2, N-H...pi(arene) and C-H...O hydrogen bonds.

  18. D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

    NASA Astrophysics Data System (ADS)

    Foustoukos, Dionysis I.; Mysen, Bjorn O.

    2012-06-01

    A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

  19. High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Ryu, Si-Ok; Hwang, Soon Muk; Dewitt, Kenneth J.

    1995-01-01

    The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

  20. The effect of body mass and sex on the accuracy of respiratory magnetometers for measurement of end-expiratory lung volumes.

    PubMed

    Avraam, Joanne; Bourke, Rosie; Trinder, John; Nicholas, Christian L; Brazzale, Danny; O'Donoghue, Fergal J; Rochford, Peter D; Jordan, Amy S

    2016-11-01

    Respiratory magnetometers are increasingly being used in sleep studies to measure changes in end-expiratory lung volume (EELV), including in obese obstructive sleep apnea patients. Despite this, the accuracy of magnetometers has not been confirmed in obese patients nor compared between sexes. Thus we compared spirometer-measured and magnetometer-estimated lung volume and tidal volume changes during voluntary end-expiratory lung volume changes of 1.5, 1, and 0.5 l above and 0.5 l below functional respiratory capacity in supine normal-weight [body mass index (BMI) < 25 kg/m] and healthy obese (BMI > 30 kg/m) men and women. Two different magnetometer calibration techniques proposed by Banzett et al. [Banzett RB, Mahan ST, Garner DM, Brughera A, Loring SH. J Appl Physiol (1985) 79: 2169-2176, 1995] and Sackner et al. [Sackner MA, Watson H, Belsito AS, Feinerman D, Suarez M, Gonzalez G, Bizousky F, Krieger B. J Appl Physiol (1985) 66: 410-420, 1989] were assessed. Across all groups and target volumes, magnetometers overestimated spirometer-measured EELV by ~65 ml (<0.001) with no difference between techniques (0.07). The Banzett method overestimated the spirometer EELV change in normal-weight women for all target volumes except +0.5 l, whereas no differences between mass or sex groups were observed for the Sackner technique. The variability of breath-to-breath measures of EELV was significantly higher for obese compared with nonobese subjects and was higher for the Sackner than Banzett technique. On the other hand, for tidal volume, both calibration techniques underestimated spirometer measurements (<0.001), with the underestimation being more marked for the Banzett than Sackner technique (0.03), in obese than normal weight (<0.001) and in men than in women (0.003). These results indicate that both body mass and sex affect the accuracy of respiratory magnetometers in measuring EELV and tidal volume. Copyright © 2016 the American Physiological Society.

  1. Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

  2. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

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

    Smith, R. Scott; Li, Zhenjun; Chen, Long

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupymore » the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.« less

  3. An experimental study on the impacts of inspiratory and expiratory muscles activities during mechanical ventilation in ARDS animal model

    PubMed Central

    Zhang, Xianming; Du, Juan; Wu, Weiliang; Zhu, Yongcheng; Jiang, Ying; Chen, Rongchang

    2017-01-01

    In spite of intensive investigations, the role of spontaneous breathing (SB) activity in ARDS has not been well defined yet and little has been known about the different contribution of inspiratory or expiratory muscles activities during mechanical ventilation in patients with ARDS. In present study, oleic acid-induced beagle dogs’ ARDS models were employed and ventilated with the same level of mean airway pressure. Respiratory mechanics, lung volume, gas exchange and inflammatory cytokines were measured during mechanical ventilation, and lung injury was determined histologically. As a result, for the comparable ventilator setting, preserved inspiratory muscles activity groups resulted in higher end-expiratory lung volume (EELV) and oxygenation index. In addition, less lung damage scores and lower levels of system inflammatory cytokines were revealed after 8 h of ventilation. In comparison, preserved expiratory muscles activity groups resulted in lower EELV and oxygenation index. Moreover, higher lung injury scores and inflammatory cytokines levels were observed after 8 h of ventilation. Our findings suggest that the activity of inspiratory muscles has beneficial effects, whereas that of expiratory muscles exerts adverse effects during mechanical ventilation in ARDS animal model. Therefore, for mechanically ventilated patients with ARDS, the demands for deep sedation or paralysis might be replaced by the strategy of expiratory muscles paralysis through epidural anesthesia. PMID:28230150

  4. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  5. Non-invasive Positive Pressure Ventilation during Sleep at 3800m: relationship to Acute Mountain Sickness and sleeping oxyhemoglobin saturation

    PubMed Central

    Johnson, PL; Popa, DA; Prisk, GK; Sullivan, CE; Edwards, N

    2014-01-01

    Background and objectives Ascent to high altitude results in hypobaric hypoxia and some individuals will develop Acute Mountain Sickness, which has been shown to be associated with low oxyhemoglobin saturation during sleep. Previous research has shown that positive end-expiratory pressure by use of expiratory valves in a face mask while awake, results in a reduction in AMS symptoms and higher oxyhemoglobin saturation. We aimed to test whether pressure ventilation during sleep would prevent AMS by keeping oxyhaemoglobin higher during sleep. Methods We compared sleeping oxyhemoglobin saturation and the incidence and severity of Acute Mountain Sickness in seven subjects sleeping for two consecutive nights at 3800m above sea level using either non-invasive positive pressure ventilation that delivered positive inspiratory and expiratory airway pressure via a face mask, or sleeping without assisted ventilation. The presence and severity of Acute Mountain Sickness was assessed by administration of the Lake Louise questionnaire. Results We found significant increases in the mean and minimum sleeping oxyhemoglobin saturation and decreases in AMS symptoms in subjects who used positive pressure ventilation during sleep. Mean and minimum sleeping SaO2 was lower in subjects who developed AMS after the night spent without positive pressure ventilation. Conclusion The use of positive pressure ventilation during sleep at 3800m significantly increased the sleeping oxygen saturation; we suggest that the marked reduction in symptoms of AMS is due to this higher sleeping SaO2. We agree with the findings from previous studies that the development of AMS is associated with a lower sleeping oxygen saturation. PMID:20051046

  6. Photodegradation of the antineoplastic cyclophosphamide: a comparative study of the efficiencies of UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2 processes.

    PubMed

    Lutterbeck, Carlos Alexandre; Machado, Ênio Leandro; Kümmerer, Klaus

    2015-02-01

    Anticancer drugs are harmful substances that can have carcinogenic, mutagenic, teratogenic, genotoxic, and cytotoxic effects even at low concentrations. More than 50 years after its introduction, the alkylating agent cyclophosphamide (CP) is still one of the most consumed anticancer drug worldwide. CP has been detected in water bodies in several studies and is known as being persistent in the aquatic environment. As the traditional water and wastewater treatment technologies are not able to remove CP from the water, different treatment options such as advanced oxidation processes (AOPs) are under discussion to eliminate these compounds. The present study investigated the degradation of CP by three different AOPs: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. The light source was a Hg medium-pressure lamp. Prescreening tests were carried out and afterwards experiments based on the optimized conditions were performed. The primary elimination of the parent compounds and the detection of transformation products (TPs) were monitored with LC-UV-MS/MS analysis, whereas the degree of mineralization was monitored by measuring the dissolved organic carbon (DOC). Ecotoxicological assays were carried out with the luminescent bacteria Vibrio fischeri. CP was completely degraded in all treatments and UV/Fe(2+)/H2O2 was the fastest process, followed by UV/H2O2 and UV/TiO2. All the reactions obeyed pseudo-first order kinetics. Considering the mineralization UV/Fe(2+)/H2O2 and UV/TiO2 were the most efficient process with mineralization degrees higher than 85%, whereas UV/H2O2 achieved 72.5% of DOC removal. Five transformation products were formed during the reactions and identified. None of them showed significant toxicity against V. fischeri. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Cosmetic wastewater treatment by the ZVI/H2O2 process.

    PubMed

    Bogacki, Jan; Marcinowski, Piotr; Zapałowska, Ewa; Maksymiec, Justyna; Naumczyk, Jeremi

    2017-10-01

    The ZVI/H 2 O 2 process was applied for cosmetic wastewater treatment. Two commercial zero-valent iron (ZVI) types with different granulations were chosen: Hepure Ferrox PRB and Hepure Ferrox Target. In addition, the pH and stirring method influence on ZVI/H 2 O 2 process efficiency was studied. During the ZVI and ZVI/H 2 O 2 processes, linear Fe ions concentration increase was observed. The addition of H 2 O 2 significantly accelerated the iron dissolution process. The highest COD removal was obtained using finer ZVI (Hepure Ferrox Target) for doses of reagents ZVI/H 2 O 2 1500/1600 mg/L, in a H 2 O 2 /COD weight ratio 2:1, at pH 3.0 with stirring on a magnetic stirrer. After 120 min of the process, 84.0% COD removal (from 796 to 127 mg/L) was achieved. It was found that the efficiency of the process depends, as in the case of the Fenton process, on the ratio of the reagents (ZVI/H 2 O 2 ) and their dose in relation to the COD (H 2 O 2 /COD) but does not depend on the dose of the iron itself. Statistical analysis confirms that COD removal efficiency depends primarily on H 2 O 2 /COD ratio and ZVI granulation, but ZVI dose influence is not statistically significant. The head space, solid-phase microextraction, gas chromatography, mass spectrometry results confirm high efficiency of the ZVI/H 2 O 2 process.

  8. TES/Aura L2 Water Vapor (H2O) Limb V6 (TL2H2OL)

    Atmospheric Science Data Center

    2018-03-01

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access: OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  9. SO2-tolerant and H2O-promoting Pt/C catalysts for efficient NO removal via fixed-bed H2-SCR.

    PubMed

    Tu, Baosheng; Shi, Nian; Sun, Wei; Cao, Limei; Yang, Ji

    2017-01-01

    In this paper, Pt supports on carbon black powder (Vulcan XC-72) were synthesized via a hydrothermal method for selective catalytic reduction (SCR) of NO with H 2 in the presence of 2 vol% O 2 over a wide temperature of 20-300 °C. The results showed that the 3 and 5 wt% Pt/C catalysts resulted in high NO conversion (>90 %) over a temperature range of 120 to 300 °C, and the maximum NO conversion of 98.6 % was achieved over 5 wt% Pt/C at 120 °C. Meanwhile, the influence of SO 2 and H 2 O on the catalyst performance of 3 wt% Pt/C was investigated. The catalysts exhibited good SO 2 poisoning resistance when the SO 2 concentration was lower than 260 ppm. Moreover, a positive effect on NO conversion was detected with the addition of 3 and 5 vol% H 2 O in the feed gas stream. Graphical abstract TEM image and good NO conversion performance of the Pt/C catalysts.

  10. Low-Lying Energy Isomers and Global Minima of Aqueous Nanoclusters: Structures and Spectroscopic Features of the Pentagonal Dodecahedron (H2O)20 and (H3O)+(H2O)20

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

    Xantheas, Sotiris S.

    We rely on a hierarchy of methods to identify the low-lying isomers for the pentagonal dodecahedron (H2O)20 and the H3O+(H2O)20 clusters. Initial screening of isomers was performed with classical potentials [TIP4P, TTM2-F, TTM2.1-F for (H2O)20 and ASP for H3O+(H2O)20] and the networks obtained with those potentials were subsequently reoptimized at the DFT (B3LYP) and MP2 levels of theory. For the pentagonal dodecahedron (H2O)20 it was found that DFT (B3LYP) and MP2 produced the same global minimum. However, this was not the case for the H3O+(H2O)20 cluster, for which MP2 produced a different network for the global minimum when compared tomore » DFT (B3LYP). All low-lying minima of H3O+(H2O)20 correspond to hydrogen bonding networks having 9 ''free'' OH bonds and the hydronium ion on the surface of the cluster. The fact that DFT (B3LYP) and MP2 produce different results and issues related to the use of a smaller basis set, explains the discrepancy between the current results and the structure previously suggested [Science 304, 1137 (2004)] for the global minimum of the H3O+(H2O)20 cluster. Additionally, the IR spectra of the MP2 global minimum are closer to the experimentally measured ones than the spectra of the previously suggested DFT global minimum. The latter exhibit additional bands in the most red-shifted region of the OH stretching vibrations (corresponding to the ''fingerprint'' of the underlying hydrogen bonding network), which are absent from both the experimental as well as the spectra of the new structure suggested for the global minimum of this cluster.« less

  11. Hydrogen bonding in goldichite, KFe(SO4)2ṡ4H2O: structure refinement

    NASA Astrophysics Data System (ADS)

    Yang, Zhuming; Giester, Gerald

    2018-02-01

    The crystal structure of goldichite KFe(SO4)2ṡ4H2O was determined on a single crystal from the Baiyinchang copper deposit, Gansu, China. [ P121/ c1, a = 10.395(2), b = 10.475(2), c = 9.0875(18) Å, β = 101.65(3)°, V = 969.1(3) Å3, Z = 4]. All non-H atoms were refined with anisotropic displacement parameters and positions of H-atoms were determined by difference Fourier methods and refined from X-ray diffraction data. The crystal structure of goldichite consists of corrugated sheets parallel to the (100) plane by sharing corners between FeO6 octahedra and SO4 tetrahedra. The interstitial potassium atom exhibits a [KO7(H2O)2] nine-fold coordination, which shares edges to form a column parallel to the c-axis and to build a slab with the corrugated sheet. These slabs are linked in the [100] direction through a network of hydrogen bonds. Three types of hydrogen bonds involve links of slabs: Ow(3)-H(3B)···O(1), Ow(6)-H(6B)···O(11) and Ow(9)-H(9B)···O(11). The FTIR spectrum of goldichite shows a strong absorption between 3384 cm-1 and 3592 cm-1, which is in accordance with the O-H···O distances derived from structure data.

  12. Trapping {BW12}2 tungstoborate: synthesis and crystal structure of hybrid [{(H2BW12O42)2O}{Mo6O6S6(OH)4(H2O)2}]14- anion.

    PubMed

    Korenev, V S; Abramov, P A; Vicent, C; Mainichev, D A; Floquet, S; Cadot, E; Sokolov, M N; Fedin, V P

    2012-12-28

    Reaction between monolacunary {BW(11)} tungstoborate and oxothiocationic building block, {Mo(2)O(2)S(2)}, results in the formation of a new polyoxothiometalate with a unique architecture in which two [H(2)BW(12)O(43)](9-) tungstoborate subunits are linked together with a hexamolybdate [Mo(V)(6)O(6)S(6)(OH)(4)(H(2)O)(2)](2+) bridge.

  13. The paradox of a wet (high H2O) and dry (low H2O/Ce) mantle: High water concentrations in mantle garnet pyroxenites from Hawaii

    NASA Astrophysics Data System (ADS)

    Bizimis, M.; Peslier, A. H.

    2013-12-01

    Water dissolved as trace amounts in anhydrous minerals has a large influence on the melting behavior and physical properties of the mantle. The water concentration of the oceanic mantle is inferred from the analyses of MORB and OIB [1], but there is little data from actual mantle samples. Moreover, enriched mineralogies (pyroxenites, eclogites) are thought as important sources of heterogeneity in the mantle, but their water concentrations and their effect on the water budget and cycling in the mantle are virtually unknown. We analyzed by FTIR water concentrations in garnet clinopyroxenite xenoliths from Salt Lake Crater, Oahu, Hawaii. These pyroxenites are high-pressure (>20kb) crystal fractionates from alkalic melts. The clinopyroxenes (cpx) have 260 to 576 ppm wt. H2O, with the least differentiated samples (Mg#>0.8) in the 400-500 ppm range. Orthopyroxene (opx) contain 117-265 ppm H2O, about half of that of cpx, consistent with other natural sample studies, but lower than experimental cpx/opx equilibrium data. These pyroxenite cpx and opx water concentrations are at the high-end of on-and off-craton peridotite xenolith concentrations and megacrysts from kimberites [2] and those of Hawaiian spinel peridotites. In contrast, garnet has extremely low water contents (<5ppm H2O). There is no correlation between water in cpx and lithophile element concentrations. Phlogopite is present in some samples, and its modal abundance shows a positive correlation in Mg# with cpx, implying equilibrium. However, there is no correlation between water concentrations and the presence of phlogopite. These data imply that cpx and opx water concentrations may be buffered by phlogopite crystallization. Reconstructed bulk rock pyroxenite water concentrations (not including phlogopite, i.e. minimum) range from 200-460 ppm (average 331× 75 ppm), significantly higher than water estimates for the MORB source (50-200 ppm), but in the range of E-MORB, OIB and the source of rejuvenated Hawaiian

  14. Reaction of N2O5 with H2O on carbonaceous surfaces

    NASA Technical Reports Server (NTRS)

    Brouwer, L.; Rossi, M. J.; Golden, D. M.

    1986-01-01

    The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

  15. TES/Aura L2 Water Vapor (H2O) Limb V6 (TL2H2OLS)

    Atmospheric Science Data Center

    2018-03-01

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access:  OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  16. Phylogenetic and functional potential links pH and N2O emissions in pasture soils.

    PubMed

    Samad, Md Sainur; Biswas, Ambarish; Bakken, Lars R; Clough, Timothy J; de Klein, Cecile A M; Richards, Karl G; Lanigan, Gary J; Morales, Sergio E

    2016-10-26

    Denitrification is mediated by microbial, and physicochemical, processes leading to nitrogen loss via N 2 O and N 2 emissions. Soil pH regulates the reduction of N 2 O to N 2 , however, it can also affect microbial community composition and functional potential. Here we simultaneously test the link between pH, community composition, and the N 2 O emission ratio (N 2 O/(NO + N 2 O + N 2 )) in 13 temperate pasture soils. Physicochemical analysis, gas kinetics, 16S rRNA amplicon sequencing, metagenomic and quantitative PCR (of denitrifier genes: nirS, nirK, nosZI and nosZII) analysis were carried out to characterize each soil. We found strong evidence linking pH to both N 2 O emission ratio and community changes. Soil pH was negatively associated with N 2 O emission ratio, while being positively associated with both community diversity and total denitrification gene (nir &nos) abundance. Abundance of nosZII was positively linked to pH, and negatively linked to N 2 O emissions. Our results confirm that pH imposes a general selective pressure on the entire community and that this results in changes in emission potential. Our data also support the general model that with increased microbial diversity efficiency increases, demonstrated in this study with lowered N 2 O emission ratio through more efficient conversion of N 2 O to N 2 .

  17. Phylogenetic and functional potential links pH and N2O emissions in pasture soils

    NASA Astrophysics Data System (ADS)

    Samad, M. D. Sainur; Biswas, Ambarish; Bakken, Lars R.; Clough, Timothy J.; de Klein, Cecile A. M.; Richards, Karl G.; Lanigan, Gary J.; Morales, Sergio E.

    2016-10-01

    Denitrification is mediated by microbial, and physicochemical, processes leading to nitrogen loss via N2O and N2 emissions. Soil pH regulates the reduction of N2O to N2, however, it can also affect microbial community composition and functional potential. Here we simultaneously test the link between pH, community composition, and the N2O emission ratio (N2O/(NO + N2O + N2)) in 13 temperate pasture soils. Physicochemical analysis, gas kinetics, 16S rRNA amplicon sequencing, metagenomic and quantitative PCR (of denitrifier genes: nirS, nirK, nosZI and nosZII) analysis were carried out to characterize each soil. We found strong evidence linking pH to both N2O emission ratio and community changes. Soil pH was negatively associated with N2O emission ratio, while being positively associated with both community diversity and total denitrification gene (nir & nos) abundance. Abundance of nosZII was positively linked to pH, and negatively linked to N2O emissions. Our results confirm that pH imposes a general selective pressure on the entire community and that this results in changes in emission potential. Our data also support the general model that with increased microbial diversity efficiency increases, demonstrated in this study with lowered N2O emission ratio through more efficient conversion of N2O to N2.

  18. Phylogenetic and functional potential links pH and N2O emissions in pasture soils

    PubMed Central

    Samad, M. d. Sainur; Biswas, Ambarish; Bakken, Lars R.; Clough, Timothy J.; de Klein, Cecile A. M.; Richards, Karl G.; Lanigan, Gary J.; Morales, Sergio E.

    2016-01-01

    Denitrification is mediated by microbial, and physicochemical, processes leading to nitrogen loss via N2O and N2 emissions. Soil pH regulates the reduction of N2O to N2, however, it can also affect microbial community composition and functional potential. Here we simultaneously test the link between pH, community composition, and the N2O emission ratio (N2O/(NO + N2O + N2)) in 13 temperate pasture soils. Physicochemical analysis, gas kinetics, 16S rRNA amplicon sequencing, metagenomic and quantitative PCR (of denitrifier genes: nirS, nirK, nosZI and nosZII) analysis were carried out to characterize each soil. We found strong evidence linking pH to both N2O emission ratio and community changes. Soil pH was negatively associated with N2O emission ratio, while being positively associated with both community diversity and total denitrification gene (nir & nos) abundance. Abundance of nosZII was positively linked to pH, and negatively linked to N2O emissions. Our results confirm that pH imposes a general selective pressure on the entire community and that this results in changes in emission potential. Our data also support the general model that with increased microbial diversity efficiency increases, demonstrated in this study with lowered N2O emission ratio through more efficient conversion of N2O to N2. PMID:27782174

  19. Continuous Negative Abdominal Pressure Reduces Ventilator-induced Lung Injury in a Porcine Model.

    PubMed

    Yoshida, Takeshi; Engelberts, Doreen; Otulakowski, Gail; Katira, Bhushan; Post, Martin; Ferguson, Niall D; Brochard, Laurent; Amato, Marcelo B P; Kavanagh, Brian P

    2018-04-27

    In supine patients with acute respiratory distress syndrome, the lung typically partitions into regions of dorsal atelectasis and ventral aeration ("baby lung"). Positive airway pressure is often used to recruit atelectasis, but often overinflates ventral (already aerated) regions. A novel approach to selective recruitment of dorsal atelectasis is by "continuous negative abdominal pressure." A randomized laboratory study was performed in anesthetized pigs. Lung injury was induced by surfactant lavage followed by 1 h of injurious mechanical ventilation. Randomization (five pigs in each group) was to positive end-expiratory pressure (PEEP) alone or PEEP with continuous negative abdominal pressure (-5 cm H2O via a plexiglass chamber enclosing hindlimbs, pelvis, and abdomen), followed by 4 h of injurious ventilation (high tidal volume, 20 ml/kg; low expiratory transpulmonary pressure, -3 cm H2O). The level of PEEP at the start was ≈7 (vs. ≈3) cm H2O in the PEEP (vs. PEEP plus continuous negative abdominal pressure) groups. Esophageal pressure, hemodynamics, and electrical impedance tomography were recorded, and injury determined by lung wet/dry weight ratio and interleukin-6 expression. All animals survived, but cardiac output was decreased in the PEEP group. Addition of continuous negative abdominal pressure to PEEP resulted in greater oxygenation (PaO2/fractional inspired oxygen 316 ± 134 vs. 80 ± 24 mmHg at 4 h, P = 0.005), compliance (14.2 ± 3.0 vs. 10.3 ± 2.2 ml/cm H2O, P = 0.049), and homogeneity of ventilation, with less pulmonary edema (≈10% less) and interleukin-6 expression (≈30% less). Continuous negative abdominal pressure added to PEEP reduces ventilator-induced lung injury in a pig model compared with PEEP alone, despite targeting identical expiratory transpulmonary pressure.

  20. Structure of [M + H - H(2)O](+) from protonated tetraglycine revealed by tandem mass spectrometry and IRMPD spectroscopy.

    PubMed

    Bythell, Benjamin J; Dain, Ryan P; Curtice, Stephanie S; Oomens, Jos; Steill, Jeffrey D; Groenewold, Gary S; Paizs, Béla; Van Stipdonk, Michael J

    2010-04-22

    Multiple-stage tandem mass spectrometry and collision-induced dissociation were used to investigate loss of H(2)O or CH(3)OH from protonated versions of GGGX (where X = G, A, and V), GGGGG, and the methyl esters of these peptides. In addition, wavelength-selective infrared multiple photon dissociation was used to characterize the [M + H - H(2)O](+) product derived from protonated GGGG and the major MS(3) fragment, [M + H - H(2)O - 29](+) of this peak. Consistent with the earlier work [ Ballard , K. D. ; Gaskell , S. J. J. Am. Soc. Mass Spectrom. 1993 , 4 , 477 - 481 ; Reid , G. E. ; Simpson , R. J. ; O'Hair , R. A. J. Int. J. Mass Spectrom. 1999 , 190/191 , 209 -230 ], CID experiments show that [M + H - H(2)O](+) is the dominant peak generated from both protonated GGGG and protonated GGGG-OMe. This strongly suggests that the loss of the H(2)O molecule occurs from a position other than the C-terminal free acid and that the product does not correspond to formation of the b(4) ion. Subsequent CID of [M + H - H(2)O](+) supports this proposal by resulting in a major product that is 29 mass units less than the precursor ion. This is consistent with loss of HN horizontal lineCH(2) rather than loss of carbon monoxide (28 mass units), which is characteristic of oxazolone-type b(n) ions. Comparison between experimental and theoretical infrared spectra for a group of possible structures confirms that the [M + H - H(2)O](+) peak is not a substituted oxazolone but instead suggests formation of an ion that features a five-membered ring along the peptide backbone, close to the amino terminus. Additionally, transition structure calculations and comparison of theoretical and experimental spectra of the [M + H - H(2)O - 29](+) peak also support this proposal.

  1. Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

    PubMed

    Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

    2014-07-17

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

  2. Protective ventilation reduces Pseudomonas aeruginosa growth in lung tissue in a porcine pneumonia model.

    PubMed

    Sperber, Jesper; Nyberg, Axel; Lipcsey, Miklos; Melhus, Åsa; Larsson, Anders; Sjölin, Jan; Castegren, Markus

    2017-08-31

    Mechanical ventilation with positive end expiratory pressure and low tidal volume, i.e. protective ventilation, is recommended in patients with acute respiratory distress syndrome. However, the effect of protective ventilation on bacterial growth during early pneumonia in non-injured lungs is not extensively studied. The main objectives were to compare two different ventilator settings on Pseudomonas aeruginosa growth in lung tissue and the development of lung injury. A porcine model of severe pneumonia was used. The protective group (n = 10) had an end expiratory pressure of 10 cm H 2 O and a tidal volume of 6 ml x kg -1 . The control group (n = 10) had an end expiratory pressure of 5 cm H 2 O and a tidal volume of 10 ml x kg -1 . 10 11 colony forming units of Pseudomonas aeruginosa were inoculated intra-tracheally at baseline, after which the experiment continued for 6 h. Two animals from each group received only saline, and served as sham animals. Lung tissue samples from each animal were used for bacterial cultures and wet-to-dry weight ratio measurements. The protective group displayed lower numbers of Pseudomonas aeruginosa (p < 0.05) in the lung tissue, and a lower wet-to-dry ratio (p < 0.01) than the control group. The control group deteriorated in arterial oxygen tension/inspired oxygen fraction, whereas the protective group was unchanged (p < 0.01). In early phase pneumonia, protective ventilation with lower tidal volume and higher end expiratory pressure has the potential to reduce the pulmonary bacterial burden and the development of lung injury.

  3. H2O2_COD_EPA; MEC_acclimation

    EPA Pesticide Factsheets

    H2O2_COD_EPA: Measurements of hydrogen peroxide and COD concentrations for water samples from the MEC reactors.MEC_acclimation: raw data for current and voltage of the anode in the MEC reactor.This dataset is associated with the following publication:Sim, J., J. An, E. Elbeshbishy, R. Hodon, and H. Lee. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells. Bioresource Technology. Elsevier Online, New York, NY, USA, 195: 31-36, (2015).

  4. Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

    NASA Technical Reports Server (NTRS)

    Carter, H. G.; Bullock, R. E.

    1972-01-01

    Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

  5. Photodegradation of Selected PCBs in the Presence of Nano-TiO2 as Catalyst and H2O2 as an Oxidant

    PubMed Central

    Dasary, Samuel S. R.; Saloni, Julia; Fletcher, Amanda; Anjaneyulu, Yerramilli; Yu, Hongtao

    2010-01-01

    Photodegradation of five strategically selected PCBs was carried out in acetonitrile/water 80:20. Quantum chemical calculations reveal that PCBs without any chlorine on ortho-positions are closer to be planar, while PCBs with at least one chlorine atoms at the ortho-positions causes the two benzene rings to be nearly perpendicular. Light-induced degradation of planar PCBs is much slower than the perpendicular ones. The use of nano-TiO2 speeds up the degradation of the planar PCBs, but slows down the degradation of the non-planar ones. The use of H2O2 speeds up the degradation of planar PCBs greatly (by >20 times), but has little effect on non-planar ones except 2,3,5,6-TCB. The relative photodegradation rate is: 2,2′,4,4′-TCB > 2,3,5,6-TCB > 2,6-DCB ≈ 3,3′,4,4′-TCB > 3,4′,5-TCB. The use of H2O2 in combination with sunlight irradiation could be an efficient and “green” technology for PCB remediation. PMID:21139872

  6. Characterization of a real time H2O2 monitor for use in studies on H2O2 production by antibodies and cells.

    PubMed

    Sharma, Harish A; Balcavage, Walter X; Waite, Lee R; Johnson, Mary T; Nindl, Gabi

    2003-01-01

    It was recently shown that antibodies catalyze a reaction between water and ultraviolet light (UV) creating singlet oxygen and ultimately H2O2. Although the in vivo relevance of these antibody reactions is unclear, it is interesting that among a wide variety of non-antibody proteins tested, the T cell receptor is the only protein with similar capabilities. In clinical settings UV is believed to exert therapeutic effects by eliminating inflammatory epidermal T cells and we hypothesized that UV-triggered H2O2 production is involved in this process. To test the hypothesis we developed tools to study production of H2O2 by T cell receptors with the long-term goal of understanding, and improving, UV phototherapy. Here, we report the development of an inexpensive, real time H2O2 monitoring system having broad applicability. The detector is a Clark oxygen electrode (Pt, Ag/AgCl) modified to detect UV-driven H2O2 production. Modifications include painting the electrode black to minimize UV effects on the Ag/AgCl electrode and the use of hydrophilic, large pore Gelnots electrode membranes. Electrode current was converted to voltage and then amplified and recorded using a digital multimeter coupled to a PC. A reaction vessel with a quartz window was developed to maintain constant temperature while permitting UV irradiation of the samples. The sensitivity and specificity of the system and its use in cell-free and cell-based assays will be presented. In a cellfree system, production of H2O2 by CD3 antibodies was confirmed using our real time H2O2 monitoring method. Additionally we report the finding that splenocytes and Jurkat T cells also produce H2O2 when exposed to UV light.

  7. The effectiveness of nasal mask vs face mask ventilation in anesthetized, apneic pediatric subjects over 2 years of age: a randomized controlled trial.

    PubMed

    Itagaki, Taiga; Gubin, Tatyana A; Sayal, Puneet; Jiang, Yandong; Kacmarek, Robert M; Anderson, Thomas Anthony

    2016-02-01

    We hypothesized that anesthetized, apneic children could be ventilated equivalently or more efficiently by nasal mask ventilation (NMV) than face mask ventilation (FMV). The aim of this randomized controlled study was to test this hypothesis by comparing the expiratory tidal volume (Vte) between NMV and FMV. After the induction of anesthesia, 41 subjects, 3-17 years of age without anticipated difficult mask ventilation, were randomly assigned to receive either NMV or FMV with neck extension. Both groups were ventilated with pressure control ventilation (PCV) at 20 cmH2 O of peak inspiratory pressure (PIP) with positive end-expiratory pressure (PEEP) levels of 0, 5, and 10 cmH2 O. An additional mouth closing maneuver (MCM) was applied for the NMV group. The Vte was higher in the FMV group compared with the NMV group (median difference [95% CI]: 8.4 [5.5-11.6] ml·kg(-1) ; P < 0.001) when MCM was not applied. NMV achieved less PEEP than FMV (median difference [95% CI]: 5.0 [4.3-5.3] cmH2 O at 10 cmH2 O; P < 0.001) though both groups achieved the set PIP level. In the NMV group, MCM markedly increased Vte (median increase [95% CI]: 5.9 [2.5-9.0] ml·kg(-1) ; P < 0.005) and PEEP (median increase [95% CI]: 5.0 [0.6-8.6] cmH2 O at 10 cmH2 O; P < 0.005); however, PEEP was highly variable and lower than that of FMV (median difference [95% CI]: 2.5 [0.8-8.5] cmH2 O at 10 cmH2 O; P < 0.05). In anesthetized, apneic children greater than 2 years of age ventilated with an anesthesia ventilator and neck extension, FMV established a greater Vte than NMV regardless of mouth status. NMV could not maintain the set PEEP level due to an air leak from the mouth. The MCM increased the Vte and PEEP. © 2016 John Wiley & Sons Ltd.

  8. Enhanced Nitrobenzene reduction by zero valent iron pretreated with H2O2/HCl.

    PubMed

    Yang, Zhe; Ma, Xiaowen; Shan, Chao; Fang, Zhuoyao; Pan, Bingcai

    2018-04-01

    In this study a novel iron-based reducing agent of highly effective reduction toward nitrobenzene (NB) was obtained by pretreating zero valent iron (ZVI) with H 2 O 2 /HCl. During the H 2 O 2 /HCl pretreatment, ZVI undergoes an intensive corrosion process with formation of various reducing corrosion products (e.g., Fe 2+ , ferrous oxides/hydroxides, Fe 3 O 4 ), yielding a synergetic system (prtZVI) including liquid, suspensions and solid phase. The pretreatment process remarkably enhances the reductive performance of ZVI, where a rapid reduction of NB (200 mg L -1 ) in the prtZVI suspension was accomplished in a broad pH range (3-9) and at low dosage. Nitrosobenzene and phenylhydroxylamine are identified as the intermediates for NB reduction with the end-product of aniline. Compared with the virgin ZVI as well as another nanosized ZVI, the prtZVI system exhibits much higher electron efficiency for NB reduction as well as higher utilization ratio of Fe 0 . A rapid reduction of various nitroaromatics in an actual pharmaceutical wastewater further demonstrated the feasibility of the prtZVI system in real wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. High-Frequency Percussive Ventilation and Low Tidal Volume Ventilation in Burns: A Randomized Controlled Trial

    DTIC Science & Technology

    2010-01-01

    incidence of ventilator-associated pneumonia ( VAP ) in patients with inha- lation injury when supported with HFPV compared with conventional modes of...mean ratio of PaO2 to FIO2 was 58 6 with a mean positive end- expiratory pressure of 22 2 cm H2O before rescue. Two of these patients were...a sample size of 110 patients in each arm would have been required to detect a difference in VAP with 80% power. A multicentered study would be

  10. The crystal structure of ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5: a possible phase for Pu 4+ incorporation during the oxidation of spent nuclear fuel

    NASA Astrophysics Data System (ADS)

    Burns, Peter C.; Finch, Robert J.; Hawthorne, Frank C.; Miller, Mark L.; Ewing, Rodney C.

    1997-10-01

    Ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, is the only known uranyl oxide hydrate mineral that contains U 4+, and it has been proposed that ianthinite may be an important Pu 4+-bearing phase during the oxidative dissolution of spent nuclear fuel. The crystal structure of ianthinite, orthorhombic, a = 0.7178(2), b = 1.1473(2), c = 3.039(1) nm, V = 2.5027 nm 3Z = 4, space group P2 1cn, has been solved by direct methods and refined by least-squares methods to an R index of 9.7% and a wR index of 12.6% using 888 unique observed [| F| ≥ 5 σ | F|] reflections. The structure contains both U 4+. The U 6+ cations are present as roughly linear (U 6+O 2) 2+ uranyl ion (Ur) that are in turn coordinated by five O 2- and OH - located at the equatorial positions of pentagonal bipyramids. The U 4+ cations are coordinated by O 2-, OH - and H 2O in a distorted octahedral arrangement. The Ur φ5and U 4+| 6 (φ: O 2-, OH -, H 2O) polyhedra l sharing edges to for two symmetrically distinct sheets at z ≈ 0.0 and z ≈ 0.25 that are parallel to (001). The sheets have the β-U 3O 8 sheet anion-topology. There are five symmetrically distinct H 2O groips located at z ≈ 0.125 between the sheets of U φn polyhedra, and the sheets of U φn polyhedra are linked together only by hydrogen bonding to the intersheet H 2O groups. The crystal-chemical requirements of U 4+ and Pu 4+ are very similar, suggesting that extensive Pu 4+ ↔ U 4+ substitution may occur within the sheets of U φn polyhedra in trh structure of ianthinine.

  11. Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu).

    PubMed

    Serezhkin, Viktor N; Grigoriev, Mikhail S; Abdulmyanov, Aleksey R; Fedoseev, Aleksandr M; Savchenkov, Anton V; Serezhkina, Larisa B

    2016-08-01

    Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

  12. (C6N2H16)[Co(H2O)6](SO4)2.2H2O: A new hybrid material based on sulfate templated by diprotonated trans-1,4-diaminocyclohexane

    NASA Astrophysics Data System (ADS)

    Hamdi, N.; Ngopoh, F. A. I.; da Silva, I.; El Bali, B.; Lachkar, M.

    2018-03-01

    Employing trans-1,4-diaminocyclohexane (DACH) as template, the new hybrid sulphate (C6N2H16)[Co(H2O)6](SO4)2.2H2O was prepared in solution. Single-crystal X-ray diffraction analysis shows that it crystallizes in the monoclinic system (S.G.: P 21/n), with the following unit-cell parameters (Å,°): a = 6.2897(2), b = 12.3716(6), c = 13.1996(4), β = 98.091(3) V = 1016.89(7) Å3, Z = 4. Its 3D crystal structure is made upon isolated [Co(H2O)6] octahedra, regular [SO4] tetrahedra, protonated DACH and free H2O molecules, which interact through N-H···O and O-H···O hydrogen bonds. The Fourier transform infrared result exhibits bands corresponding to the vibrations of DACH, sulfate group and water molecules. The thermal decomposition of the phase consists mainly in the loss of the organic moiety and one sulfate group, leading thus to the formation of anhydrous cobalt sulfate.

  13. Tracking the energy flow in the hydrogen exchange reaction OH + H2OH2O + OH.

    PubMed

    Zhu, Yongfa; Ping, Leilei; Bai, Mengna; Liu, Yang; Song, Hongwei; Li, Jun; Yang, Minghui

    2018-05-09

    The prototypical hydrogen exchange reaction OH + H2OH2O + OH has attracted considerable interest due to its importance in a wide range of chemically active environments. In this work, an accurate global potential energy surface (PES) for the ground electronic state was developed based on ∼44 000 ab initio points at the level of UCCSD(T)-F12a/aug-cc-pVTZ. The PES was fitted using the fundamental invariant-neural network method with a root mean squared error of 4.37 meV. The mode specific dynamics was then studied by the quasi-classical trajectory method on the PES. Furthermore, the normal mode analysis approach was employed to calculate the final vibrational state distribution of the product H2O, in which a new scheme to acquire the Cartesian coordinates and momenta of each atom in the product molecule from the trajectories was proposed. It was found that, on one hand, excitation of either the symmetric stretching mode or the asymmetric stretching mode of the reactant H2O promotes the reaction more than the translational energy, which can be rationalized by the sudden vector projection model. On the other hand, the relatively higher efficacy of exciting the symmetric stretching mode than that of the asymmetric stretching mode is caused by the prevalence of the indirect mechanism at low collision energies and the stripping mechanism at high collision energies. In addition, the initial collision energy turns ineffectively into the vibrational energy of the products H2O and OH while a fraction of the energy transforms into the rotational energy of the product H2O. Fundamental excitation of the stretching modes of H2O results in the product H2O having the highest population in the fundamental state of the asymmetric stretching mode, followed by the ground state and the fundamental state of the symmetric stretching mode.

  14. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X=empty, H2O, NH3, H3O+: The importance of O-topology

    NASA Astrophysics Data System (ADS)

    Anick, David J.

    2010-04-01

    For (H2O)20X water clusters consisting of X enclosed by the 512 dodecahedral cage, X=empty, H2O, NH3, and H3O+, databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G∗∗. Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; |M|2, where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus |M| show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X=H3O+, one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H2O)20(NH4+) and (H2O)20(NH4+)(OH-) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H2O)20(NH4+) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low-energy water cluster geometries that may have wide applicability.

  15. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X = empty, H2O, NH3, H3O+: the importance of O-topology.

    PubMed

    Anick, David J

    2010-04-28

    For (H(2)O)(20)X water clusters consisting of X enclosed by the 5(12) dodecahedral cage, X = empty, H(2)O, NH(3), and H(3)O(+), databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G(**). Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; absolute value(M)(2), where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus absolute value(M) show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X = H(3)O(+), one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H(2)O)(20)(NH(4)(+)) and (H(2)O)(20)(NH(4)(+))(OH(-)) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H(2)O)(20)(NH(4)(+)) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low

  16. Luminescence Spectroscopy and Crystal Field Simulations of Europium Propylenediphosphonate EuH[O 3P(CH 2) 3PO 3] and Europium Glutarate [Eu(H 2O)] 2[O 2C(CH 2) 3CO 2] 3·4H 2O

    NASA Astrophysics Data System (ADS)

    Serpaggi, F.; Férey, G.; Antic-Fidancev, E.

    1999-12-01

    The results of investigations on the photoluminescence of two europium hybrid compounds, EuH[O3P(CH2)3PO3] (Eu[diph]) and [Eu(H2O)]2[O2C(CH2)3CO2]3·4H2O (Eu[glut]), are presented. In both compounds one local environment is found for the rare earth (Re) ion and the symmetry of the Re polyhedron is low (Cs) as evidenced by the Eu3+ luminescence studies. The electrostatic crystal field (cf) parameters of the 7F multiplet are obtained by the application of the phenomenological cf theory. The simulations using C2v symmetry for the rare earth ion give good agreement between the calculated and the experimental 7F0-4 energy level schemes. The observed optical data are discussed in relation to the crystal structure of the compounds.

  17. Physical limit of stability in supercooled D2O and D2O+H2O mixtures

    NASA Astrophysics Data System (ADS)

    Kiselev, S. B.; Ely, J. F.

    2003-01-01

    The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O+H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water-high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull's expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS, which lies below the homogeneous nucleation temperature, TH. We show that CP2 always lies inside in the so-called "nonthermodynamic habitat" and physically does not exist. However, the concept of a second "virtual" critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O+H2O mixtures. As an example, we consider here an equimolar D2O+H2O mixture in normal and supercooled states at atmospheric pressure, P=0.1 MPa.

  18. Effects of expiratory ribcage compression before endotracheal suctioning on arterial blood gases in patients receiving mechanical ventilation.

    PubMed

    Kohan, Mahmoud; Rezaei-Adaryani, Morteza; Najaf-Yarandi, Akram; Hoseini, Fatemeh; Mohammad-Taheri, Nahid

    2014-09-01

    To investigate the effects of expiratory ribcage compression (ERCC) before endotracheal suctioning on the arterial blood gases (ABG) in patients receiving mechanical ventilation. Endotracheal suctioning is one of the most frequently used methods for airway clearance in patients receiving mechanical ventilation. Chest physiotherapy techniques such as ERCC before endotracheal suctioning can be used as a means to facilitate mobilizing and removing airway secretions and improving alveolar ventilation. A prospective, randomized, controlled cross-over design. A randomized controlled cross-over trial with a convenience sample of 70 mechanically ventilated patients was conducted from 2006 to 2007. The patients received endotracheal suctioning with (experiment-period) or without (control-period) an antecedent 5-min expiratory ribcage. All the patients experienced both periods with at least a 3-h washed-out interval between the two periods. ABG were measured 5 min before and 25 min after endotracheal suctioning. The statistical tests showed that the levels of partial pressure of oxygen (PaO2 )/fraction of inspired oxygen (FiO2 ), partial pressure of carbon dioxide (PaCO2 ) and arterial oxygen saturation (SaO2 ) in the experimental period at 25 min after the intervention were significantly different from the control period. The tests also revealed that the levels of these variables at 25 min after suctioning were also significantly different from baseline values. However, these differences were clinically significant only for PaO2 /FiO2 . By improving the levels of PaO2 /FiO2 , ERCC can reduce the patients' need for oxygen and hence it can at least reduce the side effects of oxygen therapy. Improving PaO2 /FiO2 levels means less need for oxygen therapy. Hence, by applying ERCC we can at least minimize the side effects of oxygen therapy. © 2014 British Association of Critical Care Nurses.

  19. Morphology-defined interaction of copper phthalocyanine with O2/H2O

    NASA Astrophysics Data System (ADS)

    Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; Gredig, Thomas; Ivanov, Ilia N.

    2016-10-01

    Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but interaction with ambient gas/vapor may lead to changes in its electronic properties and limit OPV device lifetimes. CuPc films of thickness 25 and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. We measured electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. CuPc films deposited at 250°C showed a factor of 5 higher uptake of O2 as detected by a quartz crystal microbalance (QCM), possibly due to the formation of β-CuPc at T>200°C which allows higher O2 mobility between stacked molecules. While weight-based measurements stabilize after ˜10 min of gas exposure, resistance response stabilizes over times >1 h, suggesting that mass change occurs by rapid adsorption at active surface sites whereas resistive response is dominated by slow diffusion of adsorbates into the bulk film. The 25 nm films exhibit higher resistive response than 100 nm films after an hour of O2/H2O exposure due to fast analyte diffusion down to the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold.

  20. The Use of ATP-MgCl2 in the Treatment of Injury and Shock.

    DTIC Science & Technology

    1986-03-11

    that it requires mitochondrially produced ATP for its operation. Studies of the hemodynamic effects of ATP-MgCl 2 infusion in anesthetized normal and...8-14 1. LUNG STUDIES a) The salutary effects of positive end-expiratory pressure (PEEP) in experimentally-induced Pseudomonas pneumonia...salutary effects of positive end-expiratory pressure (PEEP) in experimentally induced Pseudomonas pneumonia." Anesthesia and Analgesia 58:2C8-215, 1979. 37

  1. Development of an E-H2O2/TiO2 photoelectrocatalytic oxidation system for water and wastewater treatment.

    PubMed

    Li, X Z; Liu, H S

    2005-06-15

    In this study, an innovative E-H2O2/TiO2 (E-H2O2 = electrogenerated hydrogen peroxide) photoelectrocatalytic (PEC) oxidation system was successfully developed for water and wastewater treatment. A TiO2/Ti mesh electrode was applied in this photoreactor as the anode to conduct PEC oxidation, and a reticulated vitreous carbon (RVC) electrode was used as the cathode to electrogenerate hydrogen peroxide simultaneously. The TiO2/Ti mesh electrode was prepared with a modified anodic oxidation process in a quadrielectrolyte (H2SO4-H3PO4-H2O2-HF) solution. The crystal structure, surface morphology, and film thickness of the TiO2/Ti mesh electrode were characterized by X-ray diffraction and scanning electron microscopy. The analytical results showed that a honeycomb-type anatase film with a thickness of 5 microm was formed. Photocatalytic oxidation (PC) and PEC oxidation of 2,4,6-trichlorophenol (TCP) in an aqueous solution were performed under various experimental conditions. Experimental results showed that the TiO2/Ti electrode, anodized in the H2SO4-H3PO4-H2O2-HF solution, had higher photocatalytic activity than the TiO2/Ti electrode anodized in the H2SO4 solution. It was found that the maximum applied potential would be around 2.5 V, corresponding to an optimum applied current density of 50 microA cm(-2) under UV-A illumination. The experiments confirmed that the E-H2O2 on the RVC electrode can significantly enhance the PEC oxidation of TCP in aqueous solution. The rate of TCP degradation in such an E-H2O2-assisted TiO2 PEC reaction was 5.0 times that of the TiO2 PC reaction and 2.3 times that of the TiO2 PEC reaction. The variation of pH during the E-H2O2-assisted TiO2 PEC reaction, affected by individual reactions, was also investigated. It was found that pH was well maintained during the TCP degradation in such an E-H2O2/TiO2 reaction system. This is beneficial to TCP degradation in an aqueous solution.

  2. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon.

    PubMed

    Soulard, P; Tremblay, B

    2015-12-14

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed.

  3. Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag and their application to the recycling of Ni-Co-Fe-based end-of-life superalloys via remelting

    NASA Astrophysics Data System (ADS)

    Lu, Xin; Miki, Takahiro; Nagasaka, Tetsuya

    2017-01-01

    To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni-Co-Fe-based end-of-life (EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO-Al2O3-SiO2 slag. The activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B = (%CaO)/(%SiO2) = 1, where B is the basicity. We observed that controlling the slag composition at approximately B = 1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.

  4. UV and VUV photolysis vs. UV/H2O2 and VUV/H2O2, treatment for removal of clofibric acid from aqueous solution.

    PubMed

    Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

    2011-07-01

    Clofibric acid (CA), a metabolite of lipid regulators, was investigated in ultra-pure water and sewage treatment plant (STP) effluent at 10 degrees C under UV, vacuum UV (VUV), UV/H2O2 and VUV/H2O2 processes. The influences of NO3-, HCO3- and humic acid (HA) on CA photolysis in all processes were examined. The results showed that all the experimental data well fitted the pseudo-first-order kinetic model, and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated accordingly. Direct photolysis of CA through UV irradiation was the main process, compared with the indirect oxidation of CA due to the slight generation of hydroxyl radicals dissociated from water molecules under UV irradiation below 200 nm monochromatic wavelength emission. In contrast, indirect oxidation was the main CA degradation mechanism in UV/H2O2 and VUV/H2O2, and VUV/H2O2 was the most effective process for CA degradation. The addition of 20 mg L(-1) HA could significantly inhibit CA degradation, whereas, except for UV irradiation, the inhibitive effects of NO3- and HCO3- (1.0 x 10(-3) and 0.1 mol L(-1), respectively) on CA degradation were observed in all processes, and their adverse effects were more significant in UV/H2O2 and VUV/H2O2 processes, particularly at the high NO3- and HCO3- concentrations. The degradation rate decreased 1.8-4.9-fold when these processes were applied to a real STP effluent owing to the presence of complex constituents. Of the four processes, VUV/H2O2 was the most effective, and the CA removal efficiency reached over 99% after 40 min in contrast to 80 min in both the UV/H2O2 and VUV processes and 240 min in the UV process.

  5. H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways.

    PubMed

    Aceituno, Mónica; Stalikas, Constantine D; Lunar, Loreto; Rubio, Soledad; Pérez-Bendito, Dolores

    2002-08-01

    The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.

  6. Transcriptome Analysis of H2O2-Treated Wheat Seedlings Reveals a H2O2-Responsive Fatty Acid Desaturase Gene Participating in Powdery Mildew Resistance

    PubMed Central

    Tang, Lichuan; Zhao, Guangyao; Zhu, Mingzhu; Chu, Jinfang; Sun, Xiaohong; Wei, Bo; Zhang, Xiangqi; Jia, Jizeng; Mao, Long

    2011-01-01

    Hydrogen peroxide (H2O2) plays important roles in plant biotic and abiotic stress responses. However, the effect of H2O2 stress on the bread wheat transcriptome is still lacking. To investigate the cellular and metabolic responses triggered by H2O2, we performed an mRNA tag analysis of wheat seedlings under 10 mM H2O2 treatment for 6 hour in one powdery mildew (PM) resistant (PmA) and two susceptible (Cha and Han) lines. In total, 6,156, 6,875 and 3,276 transcripts were found to be differentially expressed in PmA, Han and Cha respectively. Among them, 260 genes exhibited consistent expression patterns in all three wheat lines and may represent a subset of basal H2O2 responsive genes that were associated with cell defense, signal transduction, photosynthesis, carbohydrate metabolism, lipid metabolism, redox homeostasis, and transport. Among genes specific to PmA, ‘transport’ activity was significantly enriched in Gene Ontology analysis. MapMan classification showed that, while both up- and down- regulations were observed for auxin, abscisic acid, and brassinolides signaling genes, the jasmonic acid and ethylene signaling pathway genes were all up-regulated, suggesting H2O2-enhanced JA/Et functions in PmA. To further study whether any of these genes were involved in wheat PM response, 19 H2O2-responsive putative defense related genes were assayed in wheat seedlings infected with Blumeria graminis f. sp. tritici (Bgt). Eight of these genes were found to be co-regulated by H2O2 and Bgt, among which a fatty acid desaturase gene TaFAD was then confirmed by virus induced gene silencing (VIGS) to be required for the PM resistance. Together, our data presents the first global picture of the wheat transcriptome under H2O2 stress and uncovers potential links between H2O2 and Bgt responses, hence providing important candidate genes for the PM resistance in wheat. PMID:22174904

  7. Mechanical ventilation management during extracorporeal membrane oxygenation for acute respiratory distress syndrome: a retrospective international multicenter study.

    PubMed

    Schmidt, Matthieu; Stewart, Claire; Bailey, Michael; Nieszkowska, Ania; Kelly, Joshua; Murphy, Lorna; Pilcher, David; Cooper, D James; Scheinkestel, Carlos; Pellegrino, Vincent; Forrest, Paul; Combes, Alain; Hodgson, Carol

    2015-03-01

    To describe mechanical ventilation settings in adult patients treated for an acute respiratory distress syndrome with extracorporeal membrane oxygenation and assess the potential impact of mechanical ventilation settings on ICU mortality. Retrospective observational study. Three international high-volume extracorporeal membrane oxygenation centers. A total of 168 patients treated with extracorporeal membrane oxygenation for severe acute respiratory distress syndrome from January 2007 to January 2013. We analyzed the association between mechanical ventilation settings (i.e. plateau pressure, tidal volume, and positive end-expiratory pressure) on ICU mortality using multivariable logistic regression model and Cox-proportional hazards model. We obtained detailed demographic, clinical, daily mechanical ventilation settings and ICU outcome data. One hundred sixty-eight patients (41 ± 14 years old; PaO2/FIO2 67 ± 19 mm Hg) fulfilled our inclusion criteria. Median duration of extracorporeal membrane oxygenation and ICU stay were 10 days (6-18 d) and 28 days (16-42 d), respectively. Lower positive end-expiratory pressure levels and significantly lower plateau pressures during extracorporeal membrane oxygenation were used in the French center than in both Australian centers (23.9 ± 1.4 vs 27.6 ± 3.7 and 27.8 ± 3.6; p < 0.0001). Overall ICU mortality was 29%. Lower positive end-expiratory pressure levels (until day 7) and lower delivered tidal volume after 3 days on extracorporeal membrane oxygenation were associated with significantly higher mortality (p < 0.05). In multivariate analysis, higher positive end-expiratory pressure levels during the first 3 days of extracorporeal membrane oxygenation support were associated with lower mortality (odds ratio, 0.75; 95% CI, 0.64-0.88; p = 0.0006). Other independent predictors of ICU mortality included time between ICU admission and extracorporeal membrane oxygenation initiation, plateau pressure greater than 30 cm H2O before

  8. Kinetics of Al + H2O reaction: theoretical study.

    PubMed

    Sharipov, Alexander; Titova, Nataliya; Starik, Alexander

    2011-05-05

    Quantum chemical calculations were carried out to study the reaction of Al atom in the ground electronic state with H(2)O molecule. Examination of the potential energy surface revealed that the Al + H(2)O → AlO + H(2) reaction must be treated as a complex process involving two steps: Al + H(2)O → AlOH + H and AlOH + H → AlO + H(2). Activation barriers for these elementary reaction channels were calculated at B3LYP/6-311+G(3df,2p), CBS-QB3, and G3 levels of theory, and appropriate rate constants were estimated by using a canonical variational theory. Theoretical analysis exhibited that the rate constant for the Al + H(2)O → products reaction measured by McClean et al. must be associated with the Al + H(2)O → AlOH + H reaction path only. The process of direct HAlOH formation was found to be negligible at a pressure smaller than 100 atm.

  9. Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

    NASA Technical Reports Server (NTRS)

    Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

    2004-01-01

    The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

  10. Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Harstad, Kenneth; Okong'o, Nora

    2003-01-01

    This report presents a study of numerical simulations of mixing layers developing between opposing flows of paired fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence. The simulations were performed for two different fluid pairs O2/H2 and C7H16/N2 at similar reduced initial pressures (reduced pressure is defined as pressure divided by critical pressure). Thermodynamically, O2/H2 behaves more nearly like an ideal mixture and has greater solubility, relative to C7H16/N2, which departs strongly from ideality. Because of a specified smaller initial density stratification, the C7H16/N2 layers exhibited greater levels of growth, global molecular mixing, and turbulence. However, smaller density gradients at the transitional state for the O2/H2 system were interpreted as indicating that locally, this system exhibits enhanced mixing as a consequence of its greater solubility and closer approach to ideality. These thermodynamic features were shown to affect entropy dissipation, which was found to be larger for O2/H2 and concentrated in high-density-gradient-magnitude regions that are distortions of the initial density-stratification boundary. In C7H16/N2, the regions of largest dissipation were found to lie in high-density-gradient-magnitude regions that result from mixing of the two fluids.

  11. Effects of variation in background mixing ratios of N2, O2, and Ar on the measurement of δ18O-H2O and δ2H-H2O values by cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Jennifer E.; Rella, Chris W.

    2017-08-01

    Cavity ring-down spectrometers have generally been designed to operate under conditions in which the background gas has a constant composition. However, there are a number of observational and experimental situations of interest in which the background gas has a variable composition. In this study, we examine the effect of background gas composition on a cavity ring-down spectrometer that measures δ18O-H2O and δ2H-H2O values based on the amplitude of water isotopologue absorption features around 7184 cm-1 (L2120-i, Picarro, Inc.). For background mixtures balanced with N2, the apparent δ18O values deviate from true values by -0.50 ± 0.001 ‰ O2 %-1 and -0.57 ± 0.001 ‰ Ar %-1, and apparent δ2H values deviate from true values by 0.26 ± 0.004 ‰ O2 %-1 and 0.42 ± 0.004 ‰ Ar %-1. The artifacts are the result of broadening, narrowing, and shifting of both the target absorption lines and strong neighboring lines. While the background-induced isotopic artifacts can largely be corrected with simple empirical or semi-mechanistic models, neither type of model is capable of completely correcting the isotopic artifacts to within the inherent instrument precision. The development of strategies for dynamically detecting and accommodating background variation in N2, O2, and/or Ar would facilitate the application of cavity ring-down spectrometers to a new class of observations and experiments.

  12. Ab initio and transition state theory study of the OH + HO2H2O + O2(3Σg-)/O2(1Δg) reactions: yield and role of O2(1Δg) in H2O2 decomposition and in combustion of H2.

    PubMed

    Monge-Palacios, M; Sarathy, S Mani

    2018-02-07

    Reactions of hydroxyl (OH) and hydroperoxyl (HO 2 ) are important for governing the reactivity of combustion systems. We performed post-CCSD(T) ab initio calculations at the W3X-L//CCSD = FC/cc-pVTZ level to explore the triplet ground-state and singlet excited-state potential energy surfaces of the OH + HO 2H 2 O + O 2 ( 3 Σ g - )/O 2 ( 1 Δ g ) reactions. Using microcanonical and multistructural canonical transition state theories, we calculated the rate constant for the triplet and singlet channels over the temperature range 200-2500 K, represented by k(T) = 3.08 × 10 12 T 0.07  exp(1151/RT) + 8.00 × 10 12 T 0.32  exp(-6896/RT) and k(T) = 2.14 × 10 6 T 1.65  exp(-2180/RT) in cm 3 mol -1 s -1 , respectively. The branching ratios show that the yield of singlet excited oxygen is small (<0.5% below 1000 K). To ascertain the importance of singlet oxygen channel, our new kinetic information was implemented into the kinetic model for hydrogen combustion recently updated by Konnov (Combust. Flame, 2015, 162, 3755-3772). The updated kinetic model was used to perform H 2 O 2 thermal decomposition simulations for comparison against shock tube experiments performed by Hong et al. (Proc. Combust. Inst., 2013, 34, 565-571), and to estimate flame speeds and ignition delay times in H 2 mixtures. The simulation predicted a larger amount of O 2 ( 1 Δ g ) in H 2 O 2 decomposition than that predicted by Konnov's original model. These differences in the O 2 ( 1 Δ g ) yield are due to the use of a higher ab initio level and a more sophisticated methodology to compute the rate constant than those used in previous studies, thereby predicting a significantly larger rate constant. No effect was observed on the rate of the H 2 O 2 decomposition and on the flame speeds and ignition delay times of different H 2 -oxidizer mixtures. However, if the oxidizer is seeded with O 3 , small differences appear in the flame speed. Given that O 2 ( 1 Δ g ) is much more reactive than O

  13. A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

    PubMed

    Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

    2013-03-01

    The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

  14. Borate mineral assemblages in the system Na2OCaOMgOB2O3H2O

    USGS Publications Warehouse

    Christ, C.L.; Truesdell, A.H.; Erd, Richard C.

    1967-01-01

    he significant known hydrated borate mineral assemblages (principally of the western United States) in the system Na2OCaOz.sbnd;MgOB2O3H2O are expressible in three ternary composition diagrams. Phase rule interpretation of the diagrams is consistent with observation, if the activity of H2O is generally considered to be determined by the geologic environment. The absence of conflicting tie-lines on a diagram indicates that the several mineral assemblages of the diagram were formed under relatively narrow ranges of temperature and pressure. The known structural as well as empirical formulas for the minerals are listed, and the more recent (since 1960) crystal structure findings are discussed briefly. Schematic Gibbs free energy-composition diagrams based on known solubility-temperature relations in the systems Na2B4O7-H2O and Na2B4O7-NaCl-H2O, are highly useful in the interpretation and prediction of the stability relations in these systems; in particular these diagrams indicate clearly that tincalconite, although geologically important, is everywhere a metastable phase. Crystal-chemical considerations indicate that the same thermodynamic and kinetic behavior observed in the Na2B4O7-H2O system will hold in the Ca2B6O11-H2O system. This conclusion is confirmed by the petrologic evidence. The chemical relations among the mineral assemblages of a ternary diagram are expressed by a schematic "activity-activity" diagram. These activity-activity diagrams permit the tracing-out of the paragenetic sequences as a function of changing cation and H2O activities. ?? 1967.

  15. Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

    PubMed Central

    Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

    2011-01-01

    The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

  16. [Cerebral blood flow assessment of preterm infants during respiratory therapy with the expiratory flow increase technique].

    PubMed

    Bassani, Mariana Almada; Caldas, Jamil Pedro Siqueira; Netto, Abimael Aranha; Marba, Sérgio Tadeu Martins

    2016-06-01

    To assess the impact of respiratory therapy with the expiratory flow increase technique on cerebral hemodynamics of premature newborns. This is an intervention study, which included 40 preterm infants (≤34 weeks) aged 8-15 days of life, clinically stable in ambient air or oxygen catheter use. Children with heart defects, diagnosis of brain lesion and/or those using vasoactive drugs were excluded. Ultrasonographic assessments with transcranial Doppler flowmetry were performed before, during and after the increase in expiratory flow session, which lasted 5minutes. Cerebral blood flow velocity and resistance and pulsatility indices in the pericallosal artery were assessed. Respiratory physical therapy did not significantly alter flow velocity at the systolic peak (p=0.50), the end diastolic flow velocity (p=0.17), the mean flow velocity (p=0.07), the resistance index (p=0.41) and the pulsatility index (p=0.67) over time. The expiratory flow increase technique did not affect cerebral blood flow in clinically-stable preterm infants. Copyright © 2015 Sociedade de Pediatria de São Paulo. Publicado por Elsevier Editora Ltda. All rights reserved.

  17. H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

    NASA Technical Reports Server (NTRS)

    Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

    2004-01-01

    The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

  18. A V(IV) Hydroxyhydrogenomonophosphate with an Intersecting Tunnel Structure: HK 4[V 10O 10(H 2O) 2(OH) 4(PO 4) 7]·9H 2O

    NASA Astrophysics Data System (ADS)

    Berrah, F.; Guesdon, A.; Leclaire, A.; Borel, M. M.; Provost, J.; Raveau, B.

    1999-12-01

    A V(IV) hydroxyhydrogenomonophosphate HK4[V10O10(H2O)2(OH)4(PO4)7]·9H2O has been obtained, using hydrothermal conditions. Its structure, closely related to that of (CH3)2NH2K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O, differs from the latter by its I41/a space group (instead of P43). This difference corresponds to a "disordering" of the vanadium atoms, with respect to the dimethyl ammonium phase. It is shown that this disorder, which appears in the form of "V5O22" units distributed at random, does not affect the oxygen framework. The analysis of this complex structure shows that it can be described from the stacking along c of [V8P7O38(OH)4(H2O)2]∞ layers interconnected through layers of isolated VO6 octahedra. In this structure, built up of VO6, VO5OH, and VO4(OH)(H2O) octahedra, of VO4OH pyramids, and of PO4 tetrahedra, large "toffee" tunnels and smaller ones with a tulip-shape section are running along a (or b). The first ones are stuffed with H2O molecules forming aquo tubes, where protons are likely "delocalized," whereas the second ones are occupied by K+ cations.

  19. A theoretical study of the positive and dipositive ions of M(NH3)n and M(H2O)n for M = Mg, Ca, or Sr

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Sodupe, Mariona; Partridge, Harry

    1992-01-01

    The structure and binding energies are determined for many of the M(H2O)n(+) and M(H2O)n(2+) species, for n = 1-3 and M = Mg, Ca, or Sr. The trends are explained in terms of metal sp or sd-sigma hybridization and core polarization. The M(NH3)n(+) systems, with M = Mg or Sr, are also studied. For the positive ions, the low-lying excited states are also studied and compared with experiment. The calculations suggest an alternative interpretation of the SrNH3(+) spectrum.

  20. Synthesis, DFT calculations of structure, vibrational and thermal decomposition studies of the metal complex Pb[Mn(C3H2O4)2(H2O)2].

    PubMed

    Gil, Diego M; Carbonio, Raúl E; Gómez, María Inés

    2015-04-15

    The metallo-organic complex Pb[Mn(C3H2O4)2(H2O)2] was synthesized and characterized by IR and Raman spectroscopy and powder X-ray diffraction methods. The cell parameters for the complex were determined from powder X-ray diffraction using the autoindexing program TREOR, and refined by the Le Bail method with the Fullprof program. A hexagonal unit cell was determined with a=b=13.8366(7)Å, c=9.1454(1)Å, γ=120°. The DFT calculated geometry of the complex anion [Mn(C3H2O4)2(H2O)2](2-) is very close to the experimental data reported for similar systems. The IR and Raman spectra and the thermal analysis of the complex indicate that only one type of water molecules is present in the structure. The thermal decomposition of Pb[Mn(C3H2O4)2(H2O)2] at 700 °C in air produces PbO and Pb2MnO4 as final products. The crystal structure of the mixed oxide is very similar to that reported for Pb3O4. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Removal of pharmaceutically active compounds from synthetic and real aqueous mixtures and simultaneous disinfection by supported TiO2/UV-A, H2O2/UV-A, and TiO2/H2O2/UV-A processes.

    PubMed

    Bosio, Morgana; Satyro, Suéllen; Bassin, João Paulo; Saggioro, Enrico; Dezotti, Márcia

    2018-05-01

    Pharmaceutically active compounds are carried into aquatic bodies along with domestic sewage, industrial and agricultural wastewater discharges. Psychotropic drugs, which can be toxic to the biota, have been detected in natural waters in different parts of the world. Conventional water treatments, such as activated sludge, do not properly remove these recalcitrant substances, so the development of processes able to eliminate these compounds becomes very important. Advanced oxidation processes are considered clean technologies, capable of achieving high rates of organic compounds degradation, and can be an efficient alternative to conventional treatments. In this study, the degradation of alprazolam, clonazepam, diazepam, lorazepam, and carbamazepine was evaluated through TiO 2 /UV-A, H 2 O 2 /UV-A, and TiO 2 /H 2 O 2 /UV-A, using sunlight and artificial irradiation. While using TiO 2 in suspension, best results were found at [TiO 2 ] = 0.1 g L -1 . H 2 O 2 /UV-A displayed better results under acidic conditions, achieving from 60 to 80% of removal. When WWTP was used, degradation decreased around 50% for both processes, TiO 2 /UV-A and H 2 O 2 /UV-A, indicating a strong matrix effect. The combination of both processes was shown to be an adequate approach, since removal increased up to 90%. H 2 O 2 /UV-A was used for disinfecting the aqueous matrices, while mineralization was obtained by TiO 2 -photocatalysis.

  2. Improved oxygenation during standing performance of deep breathing exercises with positive expiratory pressure after cardiac surgery: A randomized controlled trial.

    PubMed

    Pettersson, Henrik; Faager, Gun; Westerdahl, Elisabeth

    2015-09-01

    Breathing exercises after cardiac surgery are often performed in a sitting position. It is unknown whether oxygenation would be better in the standing position. The aim of this study was to evaluate oxygenation and subjective breathing ability during sitting vs standing performance of deep breathing exercises on the second day after cardiac surgery. Patients undergoing coronary artery bypass grafting (n = 189) were randomized to sitting (controls) or standing. Both groups performed 3 × 10 deep breaths with a positive expiratory pressure device. Peripheral oxygen saturation was measured before, directly after, and 15 min after the intervention. Subjective breathing ability, blood pressure, heart rate, and pain were assessed. Oxygenation improved significantly in the standing group compared with controls directly after the breathing exercises (p < 0.001) and after 15 min rest (p = 0.027). The standing group reported better deep breathing ability compared with controls (p = 0.004). A slightly increased heart rate was found in the standing group (p = 0.047). After cardiac surgery, breathing exercises with positive expiratory pressure, performed in a standing position, significantly improved oxygenation and subjective breathing ability compared with sitting performance. Performance of breathing exercises in the standing position is feasible and could be a valuable treatment for patients with postoperative hypoxaemia.

  3. Herschel/HIFI observations of CO, H2O and NH3 in Monoceros R2

    NASA Astrophysics Data System (ADS)

    Pilleri, P.; Fuente, A.; Cernicharo, J.; Ossenkopf, V.; Berné, O.; Gerin, M.; Pety, J.; Goicoechea, J. R.; Rizzo, J. R.; Montillaud, J.; González-García, M.; Joblin, C.; Le Bourlot, J.; Le Petit, F.; Kramer, C.

    2012-08-01

    Context. Mon R2, at a distance of 830 pc, is the only ultracompact H ii region (UCH ii) where the associated photon-dominated region (PDR) can be resolved with Herschel. Owing to its brightness and proximity, it is one of the best-suited sources for investigating the chemistry and physics of highly UV-irradiated PDRs. Aims: Our goal is to estimate the abundance of H2O and NH3 in this region and investigate their origin. Methods: We present new observations ([C ii], 12CO, 13CO, C18O, o-H2O, p-H2O, o-H_218O and o-NH3) obtained with the HIFI instrument onboard Herschel and the IRAM-30 m telescope. We investigated the physical conditions in which these lines arise by analyzing their velocity structure and spatial variations. Using a large velocity gradient approach, we modeled the line intensities and derived an average abundance of H2O and NH3 across the region. Finally, we modeled the line profiles with a non-local radiative transfer model and compared these results with the abundance predicted by the Meudon PDR code. Results: The variations of the line profiles and intensities indicate complex geometrical and kinematical patterns. In several tracers ([C ii], CO 9 → 8 and H2O) the line profiles vary significantly with position and have broader line widths toward the H ii region. The H2O lines present strong self-absorption at the ambient velocity and emission in high-velocity wings toward the H ii region. The emission in the o-H_218O ground state line reaches its maximum value around the H ii region, has smaller linewidths and peaks at the velocity of the ambient cloud. Its spatial distribution shows that the o-H_218O emission arises in the PDR surrounding the H ii region. By modeling the o-H_218O emission and assuming the standard [16O] / [18O] = 500, we derive a mean abundance of o-H2O of ~10-8 relative to H2. The ortho-H2O abundance, however, is larger (~1 × 10-7) in the high-velocity wings detected toward the H ii region. Possible explanations for this larger

  4. H2O2 dynamics in the malaria parasite Plasmodium falciparum

    PubMed Central

    Rahbari, Mahsa; Bogeski, Ivan

    2017-01-01

    Hydrogen peroxide is an important antimicrobial agent but is also crucially involved in redox signaling and pathogen-host cell interactions. As a basis for systematically investigating intracellular H2O2 dynamics and regulation in living malaria parasites, we established the genetically encoded fluorescent H2O2 sensors roGFP2-Orp1 and HyPer-3 in Plasmodium falciparum. Both ratiometric redox probes as well as the pH control SypHer were expressed in the cytosol of blood-stage parasites. Both redox sensors showed reproducible sensitivity towards H2O2 in the lower micromolar range in vitro and in the parasites. Due to the pH sensitivity of HyPer-3, we used parasites expressing roGFP2-Orp1 for evaluation of short-, medium-, and long-term effects of antimalarial drugs on H2O2 levels and detoxification in Plasmodium. None of the quinolines or artemisinins tested had detectable direct effects on the H2O2 homeostasis at pharmacologically relevant concentrations. However, pre-treatment of the cells with antimalarial drugs or heat shock led to a higher tolerance towards exogenous H2O2. The systematic evaluation and comparison of the two genetically encoded cytosolic H2O2 probes in malaria parasites provides a basis for studying parasite-host cell interactions or drug effects with spatio-temporal resolution while preserving cell integrity. PMID:28369083

  5. Rehabilitation of Swallowing and Cough Functions Following Stroke: An Expiratory Muscle Strength Training Trial.

    PubMed

    Hegland, Karen Wheeler; Davenport, Paul W; Brandimore, Alexandra E; Singletary, Floris F; Troche, Michelle S

    2016-08-01

    To determine the effect of expiratory muscle strength training (EMST) on both cough and swallow function in stroke patients. Prospective pre-post intervention trial with 1 participant group. Two outpatient rehabilitation clinics. Adults (N=14) with a history of ischemic stroke in the preceding 3 to 24 months. EMST. The training program was completed at home and consisted of 25 repetitions per day, 5 days per week, for 5 weeks. Baseline and posttraining measures were maximum expiratory pressure, voluntary cough airflows, reflex cough challenge to 200μmol/L of capsaicin, sensory perception of urge to cough, and fluoroscopic swallow evaluation. Repeated measures and 1-way analyses of variance were used to determine significant differences pre- and posttraining. Maximum expiratory pressure increased in all participants by an average of 30cmH2O posttraining. At baseline, all participants demonstrated a blunted reflex cough response to 200μmol/L of capsaicin. After 5 weeks of training, measures of urge to cough and cough effectiveness increased for reflex cough; however, voluntary cough effectiveness did not increase. Swallow function was minimally impaired at baseline, and there were no significant changes in the measures of swallow function posttraining. EMST improves expiratory muscle strength, reflex cough strength, and urge to cough. Voluntary cough and swallow measures were not significantly different posttraining. It may be that stroke patients benefit from the training for upregulation of reflex cough and thus improved airway protection. Copyright © 2016 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

  6. Defining the chemical role of H2O in mantle melts: Effect of melt composition and H2O content on the activity of SiO2

    NASA Astrophysics Data System (ADS)

    Moore, G.; Roggensack, K.

    2007-12-01

    Quantifying the influence of volatiles (H2O, CO2) on the chemistry of mantle melts is a critical aspect of understanding the petrogenesis of arc magmas. A significant amount of experimental work done on the effect of H2O on the solidii of various mantle compositions, as well as on multiple saturation points of various primitive melts, has shown that H2O stabilizes olivine with respect to orthopyroxene. Or, in other words, at constant activity of SiO2, the presence of H2O decreases the activity coefficient of SiO2 in the melt, potentially leading to mantle melts that have suprisingly high SiO2 contents (Carmichael, 2002). Quantification and modelling of this behavior in hydrous silicate melts in equilibrium with the mantle have proven problematic, due mainly to a relatively small set of experiments that allow this type of thermodynamic analysis, and because of the experimental and analytical difficulties of dealing with hydrous high P-T samples (e.g. quench to a glass, rapid melt-solid reaction on quench, electron beam sensitivity of resulting glass, volatile content determination, etc). A further complication in the existing data includes co-variance of important experimental parameters (e.g. T and H2O content), making robust statistical regression analysis difficult and potentially misleading. We present here results of high P-T experiments conducted at a single pressure and temperature (1.0 GPa, 1200 deg C) that have the specific goal of quantifying the effect of H2O, as well as other melt components, on the activity coefficient of SiO2 in mantle melts. Using a "sandwich" type experiment, basaltic melts are saturated with an olivine plus orthopyroxene mineral assemblage with varying H2O and CO2 contents. The resulting samples have their bulk solid phase and glass compositions determined using EPMA, and the volatile content of the glass is determined by FTIR. The activity of SiO2 is then calculated using the olivine and orthopyroxene compositions. This value is

  7. Table 137. H2 16O (H16OH): Line position and intensity for rotational transitions (060)-(060) in the range 757-934 cm-1

    NASA Astrophysics Data System (ADS)

    Guelachvili, G.; Picqué, N.

    This document is part of Subvolume C 'Non-linear Triatomic Molecules', Part 1 'H2O (HOH)', Part α'H2 16O (H16OH)' of Volume 20 'Molecular Constants Mostly from Infrared Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.

  8. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

    PubMed

    Webster, Chris R; Mahaffy, Paul R; Flesch, Gregory J; Niles, Paul B; Jones, John H; Leshin, Laurie A; Atreya, Sushil K; Stern, Jennifer C; Christensen, Lance E; Owen, Tobias; Franz, Heather; Pepin, Robert O; Steele, Andrew; Achilles, Cherie; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Robert; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bell, James; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Gilles; Berger, Jeff; Berman, Daniel; Bish, David; Blake, David F; Blanco Avalos, Juan J; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Bristow, Thomas; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Chipera, Steve; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Crisp, Joy; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; DesMarais, David; Dietrich, William; Dingler, Robert; Donny, Christophe; Downs, Bob; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M Darby; Edgar, Lauren; Edgett, Kenneth; Edwards, Christopher; Edwards, Laurence; Ehlmann, Bethany; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Farmer, Jack; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Grotzinger, John; Guillemot, Philippe; Guo, Jingnan; Gupta, Sanjeev; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hurowitz, Joel; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Lepinette Malvitte, Alain; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F Javier; Mauchien, Patrick; Maurice, Sylvestre; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McLennan, Scott; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Milliken, Ralph; Ming, Douglas; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Morookian, John Michael; Morris, Richard; Morrison, Shaunna; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Newsom, Horton; Nikiforov, Sergey; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Rampe, Elizabeth; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Rice, Melissa; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sarrazin, Philippe; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spanovich, Nicole; Spray, John; Squyres, Steven; Stack, Katie; Stalport, Fabien; Stein, Thomas; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Stolper, Ed; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sumner, Dawn; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Treiman, Allan; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Vaniman, David; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Joshua; Williams, Rebecca; Williams, Richard B; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yen, Albert; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

    2013-07-19

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

  9. Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

    NASA Astrophysics Data System (ADS)

    Teolis, B. D.; Plainaki, C.; Cassidy, T. A.; Raut, U.

    2017-10-01

    O2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self-consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10-7 to 5 × 10-3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long-standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an 30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low-energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1-6) × 10-3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

  10. The model of nano-scale copper particle removal from silicon surface in high pressure CO2 + H2O and CO2 + H2O + IPA cleaning solutions.

    PubMed

    Tan, Xin; Chai, Jiajue; Zhang, Xiaogang; Chen, Jiawei

    2011-12-01

    This study focuses on the description of the static forces in CO2-H2O and CO2-H2O-IPA cleaning solutions with a separate fluid phase entrapped between nano-scale copper particles and a silicon surface. Calculations demonstrate that increasing the pressure of the cleaning system decreases net adhesion force (NAF) between the particle and silicon. The NAF of a particle for in CO2-H2O-IPA system is less than that in CO2-H2O system, suggesting that the particles enter into bulk layer more easily as the CO2-H2O cleaning system is added IPA.

  11. Low levels of iron enhance UV/H2O2 efficiency at neutral pH.

    PubMed

    Ulliman, Sydney L; McKay, Garrett; Rosario-Ortiz, Fernando L; Linden, Karl G

    2018-03-01

    While the presence of iron is generally not seen as favorable for UV-based treatment systems due to lamp fouling and decreased UV transmittance, we show that low levels of iron can lead to improvements in the abatement of chemicals in the UV-hydrogen peroxide advanced oxidation process. The oxidation potential of an iron-assisted UV/H 2 O 2 (UV 254  + H 2 O 2  + iron) process was evaluated at neutral pH using iron levels below USEPA secondary drinking water standards (<0.3 mg/L). Para-chlorobenzoic acid (pCBA) was used as a hydroxyl radical (HO) probe to quantify HO steady state concentrations. Compounds degraded by different mechanisms including, carbamazepine (CBZ, HO oxidation) and N-nitrosodimethylamine (NDMA, direct photolysis), were used to investigate the effect of iron on compound degradation for UV/H 2 O 2 systems. The effects of iron species (Fe 2+ and Fe 3+ ), iron concentration (0-0.3 mg/L), H 2 O 2 concentration (0-10 mg/L) and background water matrix (low-carbon tap (LCT) and well water) on HO production and compound removal were examined. Iron-assisted UV/H 2 O 2 efficiency was most influenced by the target chemical and the water matrix. Added iron to UV/H 2 O 2 was shown to increase the steady-state HO concentration by approximately 25% in all well water scenarios. While CBZ removal was unchanged by iron addition, 0.3 mg/L iron improved NDMA removal rates in both LCT and well water matrices by 15.1% and 4.6% respectively. Furthermore, the combination of UV/Fe without H 2 O 2 was also shown to enhance NDMA removal when compared to UV photolysis alone indicating the presence of degradation pathways other than HO oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Synthesis, structure, optical, photoluminescence and magnetic properties of K2[Co(C2O4)2(H2O)2]·4H2O

    NASA Astrophysics Data System (ADS)

    Narsimhulu, M.; Hussain, K. A.

    2018-06-01

    The synthesis, crystal structure, optical, photoluminescence and magnetic behaviour of potassium bis(oxalato)cobaltate(II)tertrahydrate{K2[Co(C2O4)2(H2O)2]·4H2O} are described. The compound was grown at room temperature from mixture of aqueous solutions by slow evaporation method. The X-ray crystallographic data showed that the compound belongs to the monoclinic crystal system with P21/n space group and Z = 4. The UV-visible diffuse absorbance spectra exhibited bands at 253, 285 and 541 nm in the visible and ultraviolet regions. The optical band gap of the compound was estimated as 3.4 eV. At room temperature, an intense photoluminescence was observed from this material around 392 nm when it excited at 254 nm. The variable temperature dc magnetic susceptibility measurements exposed paramagnetic behaviour at high temperatures and antiferromagnetic ordering at low temperatures.

  13. UV-activated ZnO films on a flexible substrate for room temperature O2 and H2O sensing.

    PubMed

    Jacobs, Christopher B; Maksov, Artem B; Muckley, Eric S; Collins, Liam; Mahjouri-Samani, Masoud; Ievlev, Anton; Rouleau, Christopher M; Moon, Ji-Won; Graham, David E; Sumpter, Bobby G; Ivanov, Ilia N

    2017-07-20

    We demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2 O. We propose that the distinctive responses to O 2 and H 2 O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2 O adsorption energy on ZnO surfaces were performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). These simulations suggest that the adsorption mechanisms differ for O 2 and H 2 O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2 O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2 O at low temperature.

  14. A potential energy surface for the process H2 + H2O yielding H + H + H2O - Ab initio calculations and analytical representation

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1991-01-01

    Extensive ab initio calculations on the ground state potential energy surface of H2 + H2O were performed using a large contracted Gaussian basis set and a high level of correlation treatment. An analytical representation of the potential energy surface was then obtained which reproduces the calculated energies with an overall root-mean-square error of only 0.64 mEh. The analytic representation explicitly includes all nine internal degrees of freedom and is also well behaved as the H2 dissociates; it thus can be used to study collision-induced dissociation or recombination of H2. The strategy used to minimize the number of energy calculations is discussed, as well as other advantages of the present method for determining the analytical representation.

  15. Influences of H2O mass fraction and chemical kinetics mechanism on the turbulent diffusion combustion of H2-O2 in supersonic flows

    NASA Astrophysics Data System (ADS)

    Huang, Wei; Wang, Zhen-guo; Li, Shi-bin; Liu, Wei-dong

    2012-07-01

    Hydrogen is one of the most promising fuels for the airbreathing hypersonic propulsion system, and it attracts an increasing attention of the researchers worldwide. In this study, a typical hydrogen-fueled supersonic combustor was investigated numerically, and the predicted results were compared with the available experimental data in the open literature. Two different chemical reaction mechanisms were employed to evaluate their effects on the combustion of H2-O2, namely the two-step and the seven-step mechanisms, and the vitiation effect was analyzed by varying the H2O mass fraction. The obtained results show that the predicted mole fraction profiles for different components show very good agreement with the available experimental data under the supersonic mixing and combustion conditions, and the chemical reaction mechanism has only a slight impact on the overall performance of the turbulent diffusion combustion. The simple mechanism of H2-O2 can be employed to evaluate the performance of the combustor in order to reduce the computational cost. The H2O flow vitiation makes a great difference to the combustion of H2-O2, and there is an optimal H2O mass fraction existing to enhance the intensity of the turbulent combustion. In the range considered in this paper, its optimal value is 0.15. The initiated location of the reaction appears far away from the bottom wall with the increase of the H2O mass fraction, and the H2O flow vitiation quickens the transition from subsonic to supersonic mode at the exit of the combustor.

  16. Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

    NASA Technical Reports Server (NTRS)

    Brown, L. R.; Toth, R. A.

    1985-01-01

    The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

  17. Ro-vibrational spectrum of H2O-Ne in the ν2 H2O bending region: A combined ab initio and experimental investigation

    NASA Astrophysics Data System (ADS)

    Liu, Xunchen; Hou, Dan; Thomas, Javix; Li, Hui; Xu, Yunjie

    2016-12-01

    High resolution ro-vibrational transitions of the H2O-Ne complex in the ν2 bending region of H2O at 6 μm have been measured using a rapid scan infrared spectrometer based on an external cavity quantum cascade laser and an astigmatic multipass optical cell. To aid the spectral assignment, a four-dimension potential energy surface of H2O-Ne which depends on the intramolecular bending coordinate of the H2O monomer and the three intermolecular vibrational coordinates has been constructed and the rovibrational transitions have been calculated. Three ortho and two para H2O-20Ne bands have been identified from the experimental spectra. Some weaker transitions belonging to H2O-22Ne have also been identified experimentally. Spectroscopic fits have been performed for both the experimental and theoretical transition frequencies using a simple pseudo-diatomic Hamiltonian including both Coriolis coupling and Fermi resonance terms. The experimental and theoretical spectroscopic constants thus obtained have been compared. Further improvements needed in the potential energy surface and the related spectral simulation have been discussed.

  18. Interfacial contributions of H2O2 decomposition-induced reaction current on mesoporous Pt/TiO2 systems

    NASA Astrophysics Data System (ADS)

    Ray, Nathan J.; Styrov, Vladislav V.; Karpov, Eduard G.

    2017-12-01

    We report on conversion of energy released due to chemical reactions into current for the decomposition of aqueous hydrogen peroxide solution on single phases Pt and TiO2, in addition to Pt and TiO2 simultaneously. We observe that H2O2 decomposition-induced current on TiO2 drastically overshadows the current generated by H2O2 decomposition on Pt. Photo-effects avoided, H2O2 decomposition was found to yield a conversion efficiency of 10-3 electrons generated per H2O2 molecule. Further understanding of chemical reaction-induced current shows promise as a metric with which the surface reaction may be monitored and could be greatly extended into the field of analytical chemistry.

  19. Epigallocatechin gallate (EGCG) prevents H2O2-induced oxidative stress in primary rat retinal pigment epithelial cells.

    PubMed

    Cia, David; Vergnaud-Gauduchon, Juliette; Jacquemot, Nathalie; Doly, Michel

    2014-09-01

    To determine whether the green tea polyphenol epigallocatechin gallate (EGCG) could prevent H(2)O(2)-induced oxidative stress in primary rat retinal pigment epithelial cells. Primary cultures of retinal pigment epithelium (RPE) cells were established from Long-Evans newborn rats. RPE cells were pretreated with various concentrations of EGCG for 24 h before being exposed to hydrogen peroxide (H(2)O(2)) for 2h to induce oxidative stress. Cell metabolic activity was measured using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Cell death was quantified by flow cytometry using propidium iodide (PI). Treatment of RPE cells with EGCG alone does not affect the cell viability up to 50 µM. Exposure of RPE cells to 600 µM H(2)O(2) caused a significant decrease in cell viability; whereas pretreatment with 10, 25, and 50 µM EGCG significantly reduced this decrease in a dose-dependent manner. The proportion of PI-positive cells increased significantly in cultures treated with H(2)O(2) alone; whereas pretreatment of RPE cells with 50 µM EGCG significantly reduced H(2)O(2)-induced RPE cell death. Our study shows that EGCG pretreatment can protect primary rat RPE cells from H(2)O(2)-induced death. This suggests potential effect of EGCG in the prevention of retinal diseases associated with H(2)O(2)-induced oxidative stress.

  20. Hydrothermal synthesis and structural characterization of an organic–inorganic hybrid sandwich-type tungstoantimonate [Cu(en){sub 2}(H{sub 2}O)]{sub 4}[Cu(en){sub 2}(H{sub 2}O){sub 2}][Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]·6H{sub 2}O

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

    Liu, Yingjie; College of Medicine, Henan University, Kaifeng, Henan 475004; Cao, Jing

    An organic–inorganic hybrid sandwich-type tungstoantimonate [Cu(en){sub 2}(H{sub 2}O)]{sub 4}[Cu(en){sub 2}(H{sub 2}O){sub 2}][Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]·6H{sub 2}O (1) has been synthesized by reaction of Sb{sub 2}O{sub 3}, Na{sub 2}WO{sub 4}·2H{sub 2}O, CuCl{sub 22H{sub 2}O with en (en=ethanediamine) under hydrothermal conditions and structurally characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry, IR spectrum and single-crystal X-ray diffraction. 1 displays a centric dimeric structure formed by two equivalent trivacant Keggin [α-SbW{sub 9}O{sub 33}]{sup 9−} subunits sandwiching a hexagonal (Cu{sub 2}Na{sub 4}) cluster. Moreover, those related hexagonal hexa-metal cluster sandwiched tungstoantimonates have been also summarized and compared. The variable-temperature magneticmore » measurements of 1 exhibit the weak ferromagnetic exchange interactions within the hexagonal (Cu{sub 2}Na{sub 4}) cluster mediated by the oxygen bridges. - Graphical abstract: An organic–inorganic hybrid (Cu{sub 2}Na{sub 4}) sandwiched tungstoantimonate [Cu(en){sub 2}(H{sub 2}O)]{sub 4}[Cu (en){sub 2}(H{sub 2}O){sub 2}][Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]·6H{sub 2}O was synthesized and magnetic properties was investigated. Display Omitted - Highlights: • Organic–inorganic hybrid sandwich-type tungstoantimonate. • (Cu{sub 2}Na{sub 4} sandwiched) tungstoantimonate [Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]{sup 10−}. • Ferromagnetic tungstoantimonate.« less

  1. Quantum Mechanical Determination of Potential Energy Surfaces for TiO and H2O

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.

    1996-01-01

    We discuss current ab initio methods for determining potential energy surfaces, in relation to the TiO and H2O molecules, both of which make important contributions to the opacity of oxygen-rich stars. For the TiO molecule we discuss the determination of the radiative lifetimes of the excited states and band oscillator strengths for both the triplet and singlet band systems. While the theoretical radiative lifetimes for TiO agree well with recent measurements, the band oscillator strengths differ significantly from those currently employed in opacity calculations. For the H2O molecule we discuss the current results for the potential energy and dipole moment ground state surfaces generated at NASA Ames. We show that it is necessary to account for such effects as core-valence Correlation energy to generate a PES of near spectroscopic accuracy. We also describe how we solve the ro-vibrational problem to obtain the line positions and intensities that are needed for opacity sampling.

  2. Double enzymatic cascade reactions within FeSe-Pt@SiO2 nanospheres: synthesis and application toward colorimetric biosensing of H2O2 and glucose.

    PubMed

    Qiao, Fengmin; Wang, Zhenzhen; Xu, Ke; Ai, Shiyun

    2015-10-07

    A facile process was developed for the synthesis of FeSe-Pt@SiO2 nanospheres based on the hydrothermal treatment of FeCl3·6H2O, selenium and NaBH4 in ethanolamine solvent, followed by reducing HPtCl4 with NaBH4 in the presence of FeSe particles to obtain FeSe coated with Pt NPs (FeSe-Pt), ending with a surfactant assembled sol-gel process to obtain FeSe-Pt@SiO2. The morphology and composition of FeSe-Pt@SiO2 were characterized by transmission electron microscopy, high resolution TEM, X-ray diffraction and Fourier transform infrared spectroscopy. Structural analyses revealed that FeSe-Pt@SiO2 nanospheres were of regular spherical shape with smooth surfaces due to the SiO2 shells, compared with FeSe particles with 150 nm lateral diameter. The prepared FeSe-Pt@SiO2 nanospheres possessed both intrinsic glucose oxidase (GOx-) and peroxidase-mimic activities, and we engineered an artificial enzymatic cascade system with high activity and stability based on this nanostructure. The good catalytic performance of the composites could be attributed to the synergy between the functions of FeSe particles and Pt NPs. Significantly, the FeSe-Pt@SiO2 nanospheres as robust nanoreactors can catalyze a self-organized cascade reaction, which includes oxidation of glucose by oxygen to yield gluconic acid and H2O2, and then oxidation of 3,3,5,5-tetramethylbenzidine (TMB) by H2O2 to produce a colour change. Colorimetric detection of H2O2 and glucose using the FeSe-Pt@SiO2 nanospheres was conducted with high detection sensitivities, 0.227 nM and 1.136 nM, respectively, demonstrating the feasibility of practical sensing applications. It is therefore believed that our findings in this study could open up the possibility of utilizing FeSe-Pt@SiO2 nanospheres as enzymatic mimics in diagnostic and biotechnology fields.

  3. Oxyhydroxide of metallic nanowires in a molecular H2O and H2O2 environment and their effects on mechanical properties.

    PubMed

    Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van

    2018-06-14

    To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.

  4. Non-invasive positive pressure ventilation during sleep at 3800 m: Relationship to acute mountain sickness and sleeping oxyhaemoglobin saturation.

    PubMed

    Johnson, Pamela L; Popa, Daniel A; Prisk, G Kim; Edwards, Natalie; Sullivan, Colin E

    2010-02-01

    Overnight oxyhaemoglobin desaturation is related to AMS. AMS can be debilitating and may require descent. Positive pressure ventilation during sleep at high altitude may prevent AMS and therefore be useful in people travelling to high altitude, who are known to suffer from AMS. Ascent to high altitude results in hypobaric hypoxia and some individuals will develop acute mountain sickness (AMS), which has been shown to be associated with low oxyhaemoglobin saturation during sleep. Previous research has shown that positive end-expiratory pressure by use of expiratory valves in a face mask while awake results in a reduction in AMS symptoms and higher oxyhaemoglobin saturation. We aimed to determine whether positive pressure ventilation would prevent AMS by increasing oxygenation during sleep. We compared sleeping oxyhaemoglobin saturation and the incidence and severity of AMS in seven subjects sleeping for two consecutive nights at 3800 m above sea level using either non-invasive positive pressure ventilation that delivered positive inspiratory and expiratory airway pressure via a face mask, or sleeping without assisted ventilation. The presence and severity of AMS were assessed by administration of the Lake Louise questionnaire. We found significant increases in the mean and minimum sleeping oxyhaemoglobin saturation and decreases in AMS symptoms in subjects who used positive pressure ventilation during sleep. Mean and minimum sleeping SaO2 was lower in subjects who developed AMS after the night spent without positive pressure ventilation. The use of positive pressure ventilation during sleep at 3800 m significantly increased the sleeping oxygen saturation; we suggest that the marked reduction in symptoms of AMS is due to this higher sleeping SaO2. We agree with the findings from previous studies that the development of AMS is associated with a lower sleeping oxygen saturation.

  5. UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

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

    Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.

    Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

  6. UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

    DOE PAGES

    Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.; ...

    2017-07-20

    Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

  7. H2/O2 three-body rates at high temperatures

    NASA Technical Reports Server (NTRS)

    Marinelli, William J.; Kessler, William J.; Carleton, Karen L.

    1991-01-01

    Hydrogen atoms are produced in the presence of excess O2, and the first-order decay are studied as a function of temperature and pressure in order to obtain the rate coefficient for the three-body reaction between H-atoms and O2. Attention is focused on the kinetic scheme employed as well as the reaction cell and photolysis and probe laser system. A two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical-thickness or O2-absorption problems. Results confirm measurements reported previously for the H + O2 + N2 reaction at 300 K and extend these measurements to higher temperatures. Preliminary data indicate non-Arrehenius-type behavior of this reaction rate coefficient as a function of temperature. Measurements of the rate coefficient for H + O2 + Ar reaction at 300 K give a rate coefficient of 2.1 +/- 0.1 x 10 to the -32nd cm exp 6/molecule sec.

  8. Assessment of Factors Related to Auto-PEEP.

    PubMed

    Natalini, Giuseppe; Tuzzo, Daniele; Rosano, Antonio; Testa, Marco; Grazioli, Michele; Pennestrì, Vincenzo; Amodeo, Guido; Marsilia, Paolo F; Tinnirello, Andrea; Berruto, Francesco; Fiorillo, Marialinda; Filippini, Matteo; Peratoner, Alberto; Minelli, Cosetta; Bernardini, Achille

    2016-02-01

    Previous physiological studies have identified factors that are involved in auto-PEEP generation. In our study, we examined how much auto-PEEP is generated from factors that are involved in its development. One hundred eighty-six subjects undergoing controlled mechanical ventilation with persistent expiratory flow at the beginning of each inspiration were enrolled in the study. Volume-controlled continuous mandatory ventilation with PEEP of 0 cm H2O was applied while maintaining the ventilator setting as chosen by the attending physician. End-expiratory and end-inspiratory airway occlusion maneuvers were performed to calculate respiratory mechanics, and tidal flow limitation was assessed by a maneuver of manual compression of the abdomen. The variable with the strongest effect on auto-PEEP was flow limitation, which was associated with an increase of 2.4 cm H2O in auto-PEEP values. Moreover, auto-PEEP values were directly related to resistance of the respiratory system and body mass index and inversely related to expiratory time/time constant. Variables that were associated with the breathing pattern (tidal volume, frequency minute ventilation, and expiratory time) did not show any relationship with auto-PEEP values. The risk of auto-PEEP ≥5 cm H2O was increased by flow limitation (adjusted odds ratio 17; 95% CI: 6-56.2), expiratory time/time constant ratio <1.85 (12.6; 4.7-39.6), respiratory system resistance >15 cm H2O/L s (3; 1.3-6.9), age >65 y (2.8; 1.2-6.5), and body mass index >26 kg/m(2) (2.6; 1.1-6.1). Flow limitation, expiratory time/time constant, resistance of the respiratory system, and obesity are the most important variables that affect auto-PEEP values. Frequency expiratory time, tidal volume, and minute ventilation were not independently associated with auto-PEEP. Therapeutic strategies aimed at reducing auto-PEEP and its adverse effects should be primarily oriented to the variables that mainly affect auto-PEEP values. Copyright © 2016 by

  9. Complexes in the Photocatalytic Reaction of CO2 and H2O: Theoretical Studies

    PubMed Central

    Luo, Dongmei; Zhang, Ning; Hong, Sanguo; Wu, Huanwen; Liu, Zhihua

    2010-01-01

    Complexes (H2O/CO2, e–(H2O/CO2) and h+–(H2O/CO2)) in the reaction system of CO2 photoreduction with H2O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H2O/CO2 captured photo-induced electron and hole produced e–(H2O/CO2) and h+–(H2O/CO2), respectively. The results revealed that CO2 and H2O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO2 and H2O, which might be attributed to the synergistic effect and which could not be captured experimentally. PMID:21152274

  10. Cutin monomers and surface wax constituents elicit H2O2 in conditioned cucumber hypocotyl segments and enhance the activity of other H2O2 elicitors

    PubMed

    Fauth; Schweizer; Buchala; Markstadter; Riederer; Kato; Kauss

    1998-08-01

    Hypocotyls from etiolated cucumber (Cucumis sativus L.) seedlings were gently abraded at their epidermal surface and cut segments were conditioned to develop competence for H2O2 elicitation. Alkaline hydrolysates of cutin from cucumber, tomato, and apple elicited H2O2 in such conditioned segments. The most active constituent of cucumber cutin was identified as dodecan-1-ol, a novel cutin monomer capable of forming hydrophobic terminal chains. Additionally, the cutin hydrolysates enhanced the activity of a fungal H2O2 elicitor, similar to cucumber surface wax, which contained newly identified alkan-1,3-diols. The specificity of elicitor and enhancement activity was further elaborated using some pure model compounds. Certain saturated hydroxy fatty acids were potent H2O2 elicitors as well as enhancers. Some unsaturated epoxy and hydroxy fatty acids were also excellent H2O2 elicitors but inhibited the fungal elicitor activity. Short-chain alkanols exhibited good elicitor and enhancer activity, whereas longer-chain alkan-1-ols were barely active. The enhancement effect was also observed for H2O2 elicitation by ergosterol and chitosan. The physiological significance of these observations might be that once the cuticle is degraded by fungal cutinase, the cutin monomers may act as H2O2 elicitors. Corrosion of cutin may also bring surface wax constituents in contact with protoplasts and enhance elicitation.

  11. Energetics of CO2 and H2O adsorption on zinc oxide.

    PubMed

    Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

    2014-08-05

    Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

  12. Mesospheric H2O Concentrations Retrieved from SABER/TIMED Measurements

    NASA Technical Reports Server (NTRS)

    Feofilov, A. G.; Marshall, B. T.; Garcia-Comas, M.; Kutepov, A. A.; Lopez-Puertas, M.; Manuilova, R. O.; Yankovsky, V.A.; Goldberg, R. A.; Gordley, L. L.; Petelin, S.; hide

    2008-01-01

    The SABER instrument on board the TIMED Satellite is a limb scanning infrared radiometer designed to measure temperature and minor constituent vertical profiles and energetics parameters in the mesosphere and lower thermosphere (MLT). The H2O concentrations are retrieved from 6.3 micron band radiances. The populations of H2O(v2) vibrational levels are in non-Local Thermodynamic Equilibrium (non-LTE) above approximately 55 km altitude and the interpretation of 6.3 micron radiance requires utilizing non-LTE H2O model that includes various energy exchange processes in the system of H2O vibrational levels coupled with O2, N2, and CO2 vibrational levels. We incorporated these processes including kinetics of O2/O3 photolysis products to our research non-LTE H2O model and applied it for the development and optimization of SABER operational model. The latter has been validated using simultaneous SCISAT1/ACE occultation measurements. This helped us to estimate CO2(020)-O2(X,v=I), O2(X,v=I)- H2O(010), and O2(X,v=1) O rates at mesopause temperatures that is critical for an adequate interpretation of non-LTE H2O radiances in the MLT. The first distributions of seasonal and meridional H2O concentrations retrieved from SABER 6.3 micron radiances applying an updated non-LTE H2O model are demonstrated and discussed.

  13. Mass-independent fractionation of oxygen isotopes during H2O2 formation by gas-phase discharge from water vapour

    NASA Astrophysics Data System (ADS)

    Velivetskaya, Tatiana A.; Ignatiev, Alexander V.; Budnitskiy, Sergey Y.; Yakovenko, Victoria V.; Vysotskiy, Sergey V.

    2016-11-01

    Hydrogen peroxide is an important atmospheric component involved in various gas-phase and aqueous-phase transformation processes in the Earth's atmosphere. A study of mass-independent 17O anomalies in H2O2 can provide additional insights into the chemistry of the modern atmosphere and, possibly, of the ancient atmosphere. Here, we report the results of laboratory experiments to study the fractionation of three oxygen isotopes (16O, 17O, and 18O) during H2O2 formation from products of water vapour dissociation. The experiments were carried out by passing an electrical discharge through a gaseous mixture of helium and water at atmospheric pressure. The effect of the presence of O2 in the gas mixture on the isotopic composition of H2O2 was also investigated. All of the experiments showed that H2O2 produced under two different conditions (with or without O2 added in the gas mixtures) was mass-independently fractionated (MIF). We found a positive MIF signal (∼1.4‰) in the no-O2 added experiments, and this signal increased to ∼2.5‰ once O2 was added (1.6% mixing ratio). We suggest that if O2 concentrations are very low, the hydroxyl radical recombination reaction is the dominant pathway for H2O2 formation and is the source of MIF in H2O2. Although H2O2 formation via a hydroxyl radical recombination process is limited in the modern atmosphere, it would be possible in the Archean atmosphere when O2 was a trace constituent, and H2O2 would be mass-independently fractionated. The anomalous 17O excess, which was observed in H2O2 produced by spark discharge experiments, may provide useful information about the radical chemistry of the ancient atmosphere and the role of H2O2 in maintaining and controlling the atmospheric composition.

  14. Quasiparticle interfacial level alignment of highly hybridized frontier levels: H2O on TiO2(110).

    PubMed

    Migani, Annapaola; Mowbray, Duncan J; Zhao, Jin; Petek, Hrvoje

    2015-01-13

    Knowledge of the frontier levels' alignment prior to photoirradiation is necessary to achieve a complete quantitative description of H2O photocatalysis on TiO2(110). Although H2O on rutile TiO2(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H2O occupied levels is still lacking. For experiment, this is due to the H2O levels being obscured by hybridization with TiO2(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H2O-TiO2(110) interface. Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) G0W0, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H2O on TiO2(110). We perform this separation as a function of H2O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO2(110) surface, the H2O 3a1 and 1b1 levels are broadened into several peaks between 5 and 1 eV below the TiO2(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H2O adsorbed intact and dissociated on stoichiometric TiO2(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H2O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QPGW (scQPGW1) to obtain the ionization potential of the H2O-TiO2(110) interface.

  15. CO Diffusion into Amorphous H2O Ices

    NASA Astrophysics Data System (ADS)

    Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

    2015-03-01

    The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

  16. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  17. Voltammetric Determination of Cocaine in Confiscated Samples Using a Carbon Paste Electrode Modified with Different [UO2(X-MeOsalen)(H2O)] · H2O Complexes

    PubMed Central

    de Oliveira, Laura Siqueira; dos Santos Poles, Ana Paula; Balbino, Marco Antonio; Teles de Menezes, Matheus Manoel; de Andrade, José Fernando; Dockal, Edward Ralph; Tristão, Heloísa Maria; de Oliveira, Marcelo Firmino

    2013-01-01

    A fast and non-destructive voltammetric method to detect cocaine in confiscated samples based on carbon paste electrode modified with methoxy-substituted N,N'-ethylene-bis(salcylideneiminato)uranyl(VI)complexes, [UO2(X-MeOSalen)(H2O)].H2O, where X corresponds to the positions 3, 4 or 5 of the methoxy group on the aromatic ring, is described. The electrochemical behavior of the modified electrode and the electrochemical detection of cocaine were investigated using cyclic voltammetry. Using 0.1 mol·L−1 KCl as supporting-electrolyte, a concentration-dependent, well-defined peak current for cocaine at 0.62 V, with an amperometric sensitivity of 6.25 × 104 μA·mol·L−1 for cocaine concentrations ranging between 1.0 × 10−7 and 1.3 × 10−6 mol·L−1 was obtained. Chemical interference studies using lidocaine and procaine were performed. The position of the methoxy group affects the results, with the 3-methoxy derivative being the most sensitive. PMID:23771156

  18. Generation of H2, O2, and H2O2 from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization

    NASA Astrophysics Data System (ADS)

    Chin, S. L.; Lagacé, S.

    1996-02-01

    An intense femtosecond Ti-sapphire laser pulse was focused into water, leading to self-focusing. Apart from generating a white light (supercontinuum), the intense laser field in the self-focusing regions of the laser pulse dissociated the water molecules, giving rise to hydrogen and oxygen gas as well as hydrogen peroxide. Our analysis shows that the formation of free radicals O, H, and OH preceded the formation of the stable products of H2, O2, and H2O2. Because O radicals and H2O2 are strong oxydizing agents, one can take advantage of this phenomenon to design a laser scheme for sterilization in medical and biological applications.

  19. Pd-catalytic in situ generation of H2O2 from H2 and O2 produced by water electrolysis for the efficient electro-fenton degradation of rhodamine B.

    PubMed

    Yuan, Songhu; Fan, Ye; Zhang, Yucheng; Tong, Man; Liao, Peng

    2011-10-01

    A novel electro-Fenton process was developed for wastewater treatment using a modified divided electrolytic system in which H2O2 was generated in situ from electro-generated H2 and O2 in the presence of Pd/C catalyst. Appropriate pH conditions were obtained by the excessive H+ produced at the anode. The performance of the novel process was assessed by Rhodamine B (RhB) degradation in an aqueous solution. Experimental results showed that the accumulation of H2O2 occurred when the pH decreased and time elapsed. The maximum concentration of H2O2 reached 53.1 mg/L within 120 min at pH 2 and a current of 100 mA. Upon the formation of the Fenton reagent by the addition of Fe2+, RhB degraded completely within 30 min at pH 2 with a pseudo first order rate constant of 0.109 ± 0.009 min(-1). An insignificant decline in H2O2 generation and RhB degradation was found after six repetitions. RhB degradation was achieved by the chemisorption of H2O2 on the Pd/C surface, which subsequently decomposed into •OH upon catalysis by Pd0 and Fe2+. The catalytic decomposition of H2O2 to •OH by Fe2+ was more powerful than that by Pd0, which was responsible for the high efficiency of this novel electro-Fenton process.

  20. Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

    PubMed

    Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G

    2013-05-23

    Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

  1. Quasiparticle Interfacial Level Alignment of Highly Hybridized Frontier Levels: H2O on TiO2(110)

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

    Migani, Annapaola; Mowbray, Duncan J.; Zhao, Jin

    Knowledge of the frontier levels’ alignment prior to photoirradiation is necessary to achieve a complete quantitative description of H2O photocatalysis on TiO2(110). Although H2O on rutile TiO2(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H2O occupied levels is still lacking. For experiment, this is due to the H2O levels being obscured by hybridization with TiO2(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H2O–TiO2(110) interface. Using the projected density of states (DOS)more » from state-of-the-art quasiparticle (QP) G0W0, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H2O on TiO2(110). We perform this separation as a function of H2O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO2(110) surface, the H2O 3a1 and 1b1 levels are broadened into several peaks between 5 and 1 eV below the TiO2(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H2O adsorbed intact and dissociated on stoichiometric TiO2(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H2O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QPGW (scQPGW1) to obtain the ionization potential of the H2O–TiO2(110) interface.« less

  2. Rationale and study design of PROVHILO - a worldwide multicenter randomized controlled trial on protective ventilation during general anesthesia for open abdominal surgery.

    PubMed

    Hemmes, Sabrine N T; Severgnini, Paolo; Jaber, Samir; Canet, Jaume; Wrigge, Hermann; Hiesmayr, Michael; Tschernko, Edda M; Hollmann, Markus W; Binnekade, Jan M; Hedenstierna, Göran; Putensen, Christian; de Abreu, Marcelo Gama; Pelosi, Paolo; Schultz, Marcus J

    2011-05-06

    Post-operative pulmonary complications add to the morbidity and mortality of surgical patients, in particular after general anesthesia >2 hours for abdominal surgery. Whether a protective mechanical ventilation strategy with higher levels of positive end-expiratory pressure (PEEP) and repeated recruitment maneuvers; the "open lung strategy", protects against post-operative pulmonary complications is uncertain. The present study aims at comparing a protective mechanical ventilation strategy with a conventional mechanical ventilation strategy during general anesthesia for abdominal non-laparoscopic surgery. The PROtective Ventilation using HIgh versus LOw positive end-expiratory pressure ("PROVHILO") trial is a worldwide investigator-initiated multicenter randomized controlled two-arm study. Nine hundred patients scheduled for non-laparoscopic abdominal surgery at high or intermediate risk for post-operative pulmonary complications are randomized to mechanical ventilation with the level of PEEP at 12 cmH(2)O with recruitment maneuvers (the lung-protective strategy) or mechanical ventilation with the level of PEEP at maximum 2 cmH(2)O without recruitment maneuvers (the conventional strategy). The primary endpoint is any post-operative pulmonary complication. The PROVHILO trial is the first randomized controlled trial powered to investigate whether an open lung mechanical ventilation strategy in short-term mechanical ventilation prevents against postoperative pulmonary complications. ISRCTN: ISRCTN70332574.

  3. Anionic ordering and thermal properties of FeF3·3H2O.

    PubMed

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; Wattiaux, Alain; Demourgues, Alain; Salanne, Mathieu; Groult, Henri; Dambournet, Damien

    2015-10-05

    Iron fluoride trihydrate can be used to prepare iron hydroxyfluoride with the hexagonal-tungsten-bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F(-) and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.

  4. The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

    DOE PAGES

    Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

    2016-04-16

    Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

  5. The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

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

    Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

    Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

  6. Photodesorption of H2O, HDO, and D2O ice and its impact on fractionation

    NASA Astrophysics Data System (ADS)

    Arasa, Carina; Koning, Jesper; Kroes, Geert-Jan; Walsh, Catherine; van Dishoeck, Ewine F.

    2015-03-01

    The HDO/H2O ratio measured in interstellar gas is often used to draw conclusions on the formation and evolution of water in star-forming regions and, by comparison with cometary data, on the origin of water on Earth. In cold cores and in the outer regions of protoplanetary disks, an important source of gas-phase water comes from photodesorption of water ice. This research note presents fitting formulae for implementation in astrochemical models using previously computed photodesorption efficiencies for all water ice isotopologues obtained with classical molecular dynamics simulations. The results are used to investigate to what extent the gas-phase HDO/H2O ratio reflects that present in the ice or whether fractionation can occur during the photodesorption process. Probabilities for the top four monolayers are presented for photodesorption of X (X = H, D) atoms, OX radicals, and X2O and HDO molecules following photodissociation of H2O, D2O, and HDO in H2O amorphous ice at ice temperatures from 10-100 K. Significant isotope effects are found for all possible products: (1) H atom photodesorption probabilities from H2O ice are larger than those for D atom photodesorption from D2O ice by a factor of 1.1; the ratio of H and D photodesorbed upon HDO photodissociation is a factor of 2. This process will enrich the ice in deuterium atoms over time; (2) the OD/OH photodesorption ratio upon D2O and H2O photodissociation is on average a factor of 2, but the OD/OH photodesorption ratio upon HDO photodissociation is almost constant at unity for all ice temperatures; (3) D atoms are more effective in kicking out neighbouring water molecules than H atoms. However, the ratio of the photodesorbed HDO and H2O molecules is equal to the HDO/H2O ratio in the ice, therefore, there is no isotope fractionation when HDO and H2O photodesorb from the ice. Nevertheless, the enrichment of the ice in D atoms due to photodesorption can over time lead to an enhanced HDO/H2O ratio in the ice, and

  7. Researches on Tie Rod Ends Lubricated by Grease with TiO2 and ZrO2 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Wozniak, Marek; Siczek, Krzysztof; Kubiak, Przemysław; Jozwiak, Piotr; Siczek, Krystian

    2018-05-01

    The nanoparticles of some materials can be used successfully to improve tribological properties through decreasing both wear and friction borne out of contact between the contact surfaces of elements in different devices, particularly vehicles. Nanoparticles of TiO2 and ZrO2 were chosen as additives to the lithium grease lubricating the contact surfaces in tie rod ends. The object of study was the steel ball – the component of the tie rod end – mating with the polymer insert and lubricated with the pure lithium grease or containing the addition of pure TiO2, pure ZrO2 nanoparticles, with a 1%wt. Studies on friction were carried out using the tester allowing cyclical rotational motion and different loading of contact. Wear was investigated by driving a car, whose tie rod ends were analysed, on a fixed ‘eight’-shape track and with a fixed velocity pattern. The aim of the study was to obtain the values and waveforms of friction moment and wear versus cycles, loading and composition of lubricating grease. The waveforms of friction coefficient were obtained using the FEM model of the analysed contact zone. Based on the obtained waveforms, recommendations for the composition of additives for lithium grease were made.

  8. Experimental studies on cycling stable characteristics of inorganic phase change material CaCl2·6H2O-MgCl2·6H2O modified with SrCl2·6H2O and CMC

    NASA Astrophysics Data System (ADS)

    He, Meizhi; Yang, Luwei; Zhang, Zhentao

    2018-01-01

    By means of mass ratio method, binary eutectic hydrated salts inorganic phase change thermal energy storage system CaCl2·6H2O-20wt% MgCl2·6H2O was prepared, and through adding nucleating agent 1wt% SrCl2·6H2O and thickening agent 0.5wt% carboxy methyl cellulose (CMC), inoganic phase change material (PCM) modified was obtained. With recording cooling-melting curves simultaneously, this PCM was frozen and melted for 100 cycles under programmable temperature control. After per 10 cycles, the PCM was charaterized by differential scanning calorimeter (DSC), X-ray diffraction (XRD) and density meter, then analysing variation characteristics of phase change temperature, supercooling degree, superheat degree, latent heat, crystal structure and density with the increase of cycle index. The results showed that the average values of average phase change temperature for cooling and heating process were 25.70°C and 27.39°C respectively with small changes. The average values of average supercooling and superheat degree were 0.59°C and 0.49°C respectively, and the maximum value was 1.10°C. The average value and standard deviation of latent heat of fusion were 120.62 J/g and 1.90 J/g respectively. Non-molten white solid sediments resulted from phase separation were tachyhydrite (CaMg2Cl6·12H2O), which was characterized by XRD. Measuring density of the PCM after per 10 cycles, and the results suggested that the total mass of tachyhydrite was limited. In summary, such modified inoganic PCM CaCl2·6H2O-20wt% MgCl2·6H2O-1wt% SrCl2·6H2O-0.5wt% CMC could stay excellent circulation stability within 100 cycles, and providing reference value in practical use.

  9. Degradation of crystal violet by an FeGAC/H2O2 process.

    PubMed

    Chen, Chiing-Chang; Chen, Wen-Ching; Chiou, Mei-Rung; Chen, Sheng-Wei; Chen, Yao Yin; Fan, Huan-Jung

    2011-11-30

    Because of the growing concern over highly contaminated crystal violet (CV) wastewater, an FeGAC/H(2)O(2) process was employed in this research to treat CV-contaminated wastewater. The experimental results indicated that the presence of iron oxide-coated granular activated carbon (FeGAC) greatly improved the oxidative ability of H(2)O(2) for the removal of CV. For instance, the removal efficiencies of H(2)O(2), GAC, FeGAC, GAC/H(2)O(2) and FeGAC/H(2)O(2) processes were 10%, 44%, 40%, 43% and 71%, respectively, at test conditions of pH 3 and 7.4mM H(2)O(2). FeGAC/H(2)O(2) combined both the advantages of FeGAC and H(2)O(2). FeGAC had a good CV adsorption ability and could effectively catalyze the hydrogen peroxide oxidation reaction. Factors (including pH, FeGAC dosage and H(2)O(2) dosage) affecting the removal of CV by FeGAC/H(2)O(2) were investigated in this research as well. In addition, the reaction intermediates were separated and identified using HPLC-ESI-MS. The N-demethylation step might be the main reaction pathway for the removal of CV. The reaction mechanisms for the process proposed in this research might be useful for future application of this technology to the removal of triphenylmethane (TPM) dyes. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Synthesis, crystal structure and thermal study of the hybrid nickel sulfate: C6N2H16[Ni(H2O)6(SO4)2].2H2O

    NASA Astrophysics Data System (ADS)

    Ngopoh, F. A. I.; Hamdi, N.; Chaouch, S.; Lachkar, M.; da Silva, I.; El Bali, B.

    2018-03-01

    A new inorganic-organic hybrid open framework nickel sulfate C6N2H16[Ni(H2O)6(SO4)2].2H2O has been synthesized by slow evaporation in aqueous solution using trans-1,4-diaminocyclohexane as structure-directing agent. It was characterized by single-crystal X-ray diffraction, infrared spectroscopy and analyzed by TGA-DSC. The compound crystallizes in the monoclinic space group P21/n, with the unit cell parameters of a = 6.2586 Å, b = 12.3009 Å, c = 13.2451 Å, β = 98,047°, Z = 4. Its crystal structure consists of isolated polyhedrons [Ni(H2O)6]2+ and [SO4]2- and free water which connects through hydrogen bonds. This association results in the porous framework where the protonated organic molecule trans-1,4-diaminocyclohexane is located as a counter ion. The IR spectra Shows the bands corresponding to the sulfate anion, water molecule and diprotonated trans-1-4-diaminocyclohexane. Thermal study indicates the loss of water molecules and the degradation of trans-1-4-diaminocyclohexane.

  11. An apparatus for the preparation of [15O]-H2O for rapid repetitive PET studies

    NASA Astrophysics Data System (ADS)

    Dahl, J. R.; Chaly, T. C.; Matacchieri, R. A.; Yee, A.; Dhawan, V.; Horowitz, S.; Jespersen, K.; Margouleff, D.; Eidelberg, D.

    1999-06-01

    The use of [15O]-H2O to follow changes in cerebral blood flow using PET has become frequent and widespread, requiring an apparatus easily operated by personnel unfamiliar with the physics and chemistry involved. Oxygen-15 is prepared by the 14N(d,n)15O nuclear reaction using a target of UHP nitrogen with 1% UHP hydrogen added, contained in a target chamber similar to that reported for the preparation of [18F]-F2. Nucleogenic 15O reacts with hydrogen in the target gas to produce [15O]-H2O. Some of the N target reacts with hydrogen to produce NH3, which must be removed. At the end of bombardment (minimum 6 min.) the target gas is released through a small amount of parenteral water which then flows through approximately 50 mg Dowex 50W-X8 resin (100-200 mesh) to remove the NH3. Sufficient 23.4% NaCl solution is added to produce an isotonic solution. The isotonic solution is sterilized by filtration through a 0.22 micron filter into an injection syringe which is sent via pneumatic transport to the PET imaging room. The apparatus, which uses a programmable logic controller and four switches to allow the operator to select standby, refill, collect activity, or deliver dose operations of the production process, provides doses of [15O]-H2O up to 35 mCi/dose at intervals as frequent as seven minutes with minimal radiation exposure to the operators.

  12. An Accurate Potential Energy Surface for H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

  13. Detection of pH and Enzyme-Free H2O2 Sensing Mechanism by Using GdO x Membrane in Electrolyte-Insulator-Semiconductor Structure.

    PubMed

    Kumar, Pankaj; Maikap, Siddheswar; Qiu, Jian-Tai; Jana, Surajit; Roy, Anisha; Singh, Kanishk; Cheng, Hsin-Ming; Chang, Mu-Tung; Mahapatra, Rajat; Chiu, Hsien-Chin; Yang, Jer-Ren

    2016-12-01

    A 15-nm-thick GdO x membrane in an electrolyte-insulator-semiconductor (EIS) structure shows a higher pH sensitivity of 54.2 mV/pH and enzyme-free hydrogen peroxide (H2O2) detection than those of the bare SiO2 and 3-nm-thick GdO x membranes for the first time. Polycrystalline grain and higher Gd content of the thicker GdO x films are confirmed by transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS), respectively. In a thicker GdO x membrane, polycrystalline grain has lower energy gap and Gd(2+) oxidation states lead to change Gd(3+) states in the presence of H2O2, which are confirmed by electron energy loss spectroscopy (EELS). The oxidation/reduction (redox) properties of thicker GdO x membrane with higher Gd content are responsible for detecting H2O2 whereas both bare SiO2 and thinner GdO x membranes do not show sensing. A low detection limit of 1 μM is obtained due to strong catalytic activity of Gd. The reference voltage shift increases with increase of the H2O2 concentration from 1 to 200 μM owing to more generation of Gd(3+) ions, and the H2O2 sensing mechanism has been explained as well.

  14. The Frequency Detuning Correction and the Asymmetry of Line Shapes: The Far Wings of H2O-H2O

    NASA Technical Reports Server (NTRS)

    Ma, Q.; Tipping, R. H.; Hansen, James E. (Technical Monitor)

    2002-01-01

    A far-wing line shape theory which satisfies the detailed balance principle is applied to the H2O-H2O system. Within this formalism, two line shapes are introduced, corresponding to band-averages over the positive and negative resonance lines, respectively. Using the coordinate representation, the two line shapes can be obtained by evaluating 11-dimensional integrations whose integrands are a product of two factors. One depends on the interaction between the two molecules and is easy to evaluate. The other contains the density matrix of the system and is expressed as a product of two 3-dimensional distributions associated with the density matrices of the absorber and the perturber molecule, respectively. If most of the populated states are included in the averaging process, to obtain these distributions requires extensive computer CPU time, but only have to be computed once for a given temperature. The 11-dimensional integrations are evaluated using the Monte Carlo method, and in order to reduce the variance, the integration variables are chosen such that the sensitivity of the integrands on them is clearly distinguished.

  15. Papain-templated Cu nanoclusters: assaying and exhibiting dramatic antibacterial activity cooperating with H2O2

    NASA Astrophysics Data System (ADS)

    Miao, Hong; Zhong, Dan; Zhou, Zinan; Yang, Xiaoming

    2015-11-01

    Herein, papain-functionalized Cu nanoclusters (CuNCs@Papain) were originally synthesized in aqueous solution together with a quantum yield of 14.3%, and showed obviously red fluorescence at 620 nm. Meanwhile, their corresponding fluorescence mechanism was fully elucidated by fluorescence spectroscopy, HR-TEM, FTIR spectroscopy, and XPS. Subsequently, the as-prepared CuNCs were employed as probes for detecting H2O2. Using CuNCs as probes, H2O2 was determined in the range from 1 μM to 50 μM based on a linear decrease of fluorescence intensity as well as a detection limit of 0.2 μM with a signal-to-noise ratio of 3. More significantly, it has been proved that CuNCs could convert H2O2 to &z.rad;OH, which exhibited dramatic antibacterial activity. Both in vitro and in vivo experiments were performed to validate their antibacterial activity against Gram-positive/negative bacteria and actual wound infection, suggesting their potential for serving as one type of promising antibacterial material.Herein, papain-functionalized Cu nanoclusters (CuNCs@Papain) were originally synthesized in aqueous solution together with a quantum yield of 14.3%, and showed obviously red fluorescence at 620 nm. Meanwhile, their corresponding fluorescence mechanism was fully elucidated by fluorescence spectroscopy, HR-TEM, FTIR spectroscopy, and XPS. Subsequently, the as-prepared CuNCs were employed as probes for detecting H2O2. Using CuNCs as probes, H2O2 was determined in the range from 1 μM to 50 μM based on a linear decrease of fluorescence intensity as well as a detection limit of 0.2 μM with a signal-to-noise ratio of 3. More significantly, it has been proved that CuNCs could convert H2O2 to &z.rad;OH, which exhibited dramatic antibacterial activity. Both in vitro and in vivo experiments were performed to validate their antibacterial activity against Gram-positive/negative bacteria and actual wound infection, suggesting their potential for serving as one type of promising

  16. Active sites and mechanisms for H2O2 decomposition over Pd catalysts

    PubMed Central

    Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

    2016-01-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  17. Carbon dioxide clearance in rabbits during expiratory phase intratracheal pulmonary ventilation.

    PubMed

    Meyappan, Raju T; Raszynski, Andre; Bohorquez, Jorge; Totapally, Balagangadhar R; Koul, Pulin B; Norozian, Faraz M; Valcourt, Karl; Torbati, Dan

    2007-01-01

    The purpose of this study was to compare the efficacy of CO2 removal during conventional mechanical ventilation (CMV) with and without expiratory phase intratracheal pulmonary ventilation (expiratory ITPV or Exp-ITPV); and to compare CO2 clearance during Exp-ITPV, in pressure-controlled ventilation (PCV) and in volume-controlled ventilation (VCV) modes. Seven anesthetized rabbits were tracheotomized and intubated using a 4 mm endotracheal tube. Venous and arterial lines were established. The rabbits were paralyzed, mechanically ventilated, and ventilation parameters were adjusted to achieve baseline arterial hypercapnia. Animals were then ventilated during 30-minute trials of CMV and Exp-ITPV, in both PCV and VCV modes. A custom-built, microprocessor-controlled solenoid valve was used to limit ITPV gas flow to the expiratory phase. Proximal and carinal airway pressures and hemodynamic variables were continuously recorded, and arterial blood gases were analyzed at the end of each trial. Exp-ITPV, as compared with CMV, reduced arterial PCO2 by 12% and 21% in PCV and VCV modes, respectively (p < 0.02 and p < 0.001; one-sided paired t test), without significant changes in other cardiorespiratory variables. In conclusion, Exp-ITPV is more effective than CMV in clearing CO2 through a small endotracheal tube. Exp-ITPV is also more effective in VCV mode than PCV mode.

  18. Are H and O Being Lost From the Mars Atmosphere in the H2O Stoichiometric Ratio of 2:1?

    NASA Astrophysics Data System (ADS)

    Jakosky, B. M.; Chaffin, M.; Deighan, J.; Brain, D.; Halekas, J. S.

    2017-12-01

    Loss of gas from the Mars upper atmosphere to space has been a significant process in the evolution of the Mars atmosphere through time. H is derived from photodissociation of H2O, and is lost by Jeans (thermal) escape. O comes from photodissociation of either H2O or CO2, and is lost by non-thermal processes including dissociative recombination, ion pickup, or sputtering by pick-up ions impacting the atmosphere (in order of importance today). McElroy (1972) proposed that H and O are lost in the ratio of 2:1 that comes from photodissociation of H2O; any imbalance would result in build-up of the lesser-escaping atom that increases its loss rate until the rates were in balance. For the Mars year observed by MAVEN, the large seasonal variation in H loss rate makes this hypothesis difficult to evaluate; however, current best estimates of loss rates suggest that they could be in balance, given the observational uncertainties and seasonal variations (both of which are significant). Even if they are in balance over longer timescales, they still might not be during the "MAVEN" year due to: (i) complications resulting from the interplay between multiple loss processes for O beyond only photochemical loss as considered by McElroy, (ii) interannual and longer-term variations in the lower-atmosphere dust and water cycles that can change the escape rate, (iii) the variation in loss rate expected throughout the 11-year solar cycle, (iv) changes in lower-atmosphere forcing due to the changing orbital elements, or (v) loss of C, H, or O to the crust via reaction with surface minerals. The higher (and unequal) loss rates for all species early in history are likely to have kept H and O from being in balance over the 4-billion-year timescale.

  19. 5-AIQ inhibits H2O2-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes.

    PubMed

    Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun; Jang, Yong Chang; Yi, Kyu Yang; Chung, Hun-Jong; Park, Jong Seok; Kim, Bokyung; Feng, Zhong-Ping; Shin, Hwa-Sup

    2013-04-01

    Poly(adenosine 5'-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H2O2-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxide dismutase and catalase accompanied the protective effect of 5-AIQ on H2O2-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H2O2-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H2O2-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. A Novel Dimeric Ni-Substituted beta-Keggin Silicotungstate: Structure and Magnetic Properties of K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O.

    PubMed

    Kortz, Ulrich; Jeannin, Yves P.; Tézé, André; Hervé, Gilbert; Isber, Samih

    1999-08-09

    The novel dimeric polyoxometalate [{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)](12)(-) (1) has been synthesized and characterized by IR spectroscopy, polarography, elemental analysis, thermogravimetric analysis, and magnetic measurements. An X-ray single-crystal analysis was carried out on K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O, which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.701(4) Å, b = 24.448(11) Å, c = 13.995(5) Å, beta = 99.62(3) degrees, and Z = 4. The anion consists of two [beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)] Keggin moieties linked via two OH bridging groups, leading to a planar Ni(2)(OH)(2) unit. The two half-units are related by an inversion center and each contain one Ni atom in the rotated triad. The formation of the new anion involves insertion, isomerization, and dimerization. Magnetic measurements show that the central Ni(4) unit exhibits ferromagnetic (J' = 4.14 cm(-)(1)) as well as weak antiferromagnetic (J = -0.65 cm(-)(1)) Ni-Ni exchange interactions.

  1. The reaction of O(1 D) with H2O and the reaction of OH with C3H6

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Heicklen, J.

    1972-01-01

    The N2O was photolyzed at 2139 A to produce O(1 D) atoms in the presence of H2O and CO. The O(1 D) atoms react with H2O to produce HO radicals, as measured by CO2 production from the reaction of OH with CO. The relative rate constant for O(1 D) removal by H2O compared to that by N2O is 2.1. In the presence of C3H6, the OH can be removed by reaction with either CO or C3H6.

  2. Pulmonary function in men after oxygen breathing at 3.0 ATA for 3.5 h

    NASA Technical Reports Server (NTRS)

    Clark, J. M.; Jackson, R. M.; Lambertsen, C. J.; Gelfand, R.; Hiller, W. D. B.; Unger, M.

    1991-01-01

    A complete description of pulmonary measurements obtained after continuous O2 exposure of 13 healthy men at 3.0 ATA for 3.5 h is presented. Measurements included flow-volume loops, spirometry, and airway resistance(n = 12); CO diffusing capacity (n = 11); closing volumes (n= 6); and air vs. HeO2 forced vital capacity maneuvers (n = 5). The average difference in maximum mid expiratory flows at 50 percent vital capacity on air and HeO2 was found to be significantly reduced postexposure by 18 percent. Raw and CO diffusing capacity were not changed postexposure. It is concluded that the relatively large change in forced expiratory flow at 25-75 percent of vital capacity compared with the mean forced expiratory volume in 1 s, the reduction in density dependence of flow, and the normal Raw postexposure are all consistent with flow limitation in peripheral airways as a major cause of the observed reduction in expiratory flow.

  3. [Effects of recruitment maneuver in prone position on hemodynamics in patients with severe pulmonary infection].

    PubMed

    Fan, Yuan-hua; Liu, Yuan-fei; Zhu, Hua-yong; Zhang, Min

    2012-02-01

    To evaluate effects of recruitment maneuver in prone position on hemodynamics in patients with severe pulmonary infection, based on the protective pulmonary ventilation strategy. Ninety-seven cases with severe pulmonary infection admitted to intensive care unit (ICU) of Ganzhou City People's Hospital undergoing mechanical ventilation were involved. Volume controlled ventilation mode with small tidal volume (8 ml/kg) and positive end-expiratory pressure (PEEP) of 6 cm H(2)O [1 cm H(2)O = 0.098 kPa] was conducted. Each patient underwent recruitment maneuver in supine position and then in prone position [PEEP 20 cm H(2)O+pressure control (PC) 20 cm H(2)O]. Heart rate (HR), mean arterial pressure (MAP), pulse oxygen saturation [SpO(2)] and blood gas analysis data were recorded before and after recruitment maneuver in either position. A double-lumen venous catheter was inserted into internal jugular vein or subclavian vein, and a pulse index contour cardiac output (PiCCO) catheter was introduced into femoral artery. Cardiac index (CI), stroke volume index (SVI), systemic vascular resistance index (SVRI), intra-thoracic blood volume index (ITBVI), extra vascular lung water index (EVLWI), global end-diastolic volume index (GEDVI), global ejection fraction (GEF), stroke volume variation (SVV) and central vein pressure (CVP) were monitored. (1) Compared with data before recruitment maneuver, there were no significant differences in HR and MAP after supine position and prone position recruitment maneuver, but significant differences in SpO(2) were found between before and after recruitment maneuver when patients' position was changed (supine position: 0.954 ± 0.032 vs. 0.917 ± 0.025, P < 0.05; prone position: 0.982 ± 0.028 vs. 0.936 ± 0.039, P < 0.05). SpO(2) was higher in prone position recruitment maneuver (P < 0.05). (2) Compared with data before recruitment maneuver, CI [L×min(-1)×m(-2)], SVI (ml/m(2)), GEDVI (ml/m(2)) and GEF were decreased significantly during

  4. Transfer of a proton between H2 and O2.

    PubMed

    Kluge, Lars; Gärtner, Sabrina; Brünken, Sandra; Asvany, Oskar; Gerlich, Dieter; Schlemmer, Stephan

    2012-11-13

    The proton affinities of hydrogen and oxygen are very similar. Therefore, it has been discussed that the proton transfer from the omnipresent H(3)(+) to molecular oxygen in the near thermoneutral reaction H(3)(+) + O(2) <--> O(2)H(+) + H(2) effectively binds the interstellar oxygen in O(2)H(+). In this work, the proton transfer reaction has been investigated in a low-temperature 22-pole ion trap from almost room temperature (280 K) down to the lowest possible temperature limited by freeze out of oxygen gas (about 40 K at a low pressure). The Arrhenius behaviour of the rate coefficient for the forward reaction shows that it is subject to an activation energy of E(A)/k=113 K. Thus, the forward reaction can proceed only in higher temperature molecular clouds. Applying laser-induced reactions to the given reaction (in the backward direction), a preliminary search for spectroscopic signatures of O(2)H(+) in the infrared was unsuccessful, whereas the forward reaction has been successfully used to probe the population of the lowest ortho and para levels of H(3)(+).

  5. 3-Methyl-7-(2-thienyl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione: pi-stacked bilayers built from N-H...O, C-H...O and C-H...pi hydrogen bonds.

    PubMed

    Trilleras, Jorge; Quiroga, Jairo; Cobo, Justo; Glidewell, Christopher

    2009-06-01

    In the title compound, C(12)H(9)N(3)O(2)S, the thienyl substituent is disordered over two sets of sites with occupancies of 0.749 (3) and 0.251 (3). A combination of N-H...O, C-H...O and C-H...pi hydrogen bonds links the molecules into bilayers and these bilayers are themselves linked into a continuous structure by pi-pi stacking interactions.

  6. H2O2 modulates the energetic metabolism of the cloud microbiome

    NASA Astrophysics Data System (ADS)

    Wirgot, Nolwenn; Vinatier, Virginie; Deguillaume, Laurent; Sancelme, Martine; Delort, Anne-Marie

    2017-12-01

    Chemical reactions in clouds lead to oxidation processes driven by radicals (mainly HO⚫, NO3⚫, or HO2⚫) or strong oxidants such as H2O2, O3, nitrate, and nitrite. Among those species, hydrogen peroxide plays a central role in the cloud chemistry by driving its oxidant capacity. In cloud droplets, H2O2 is transformed by microorganisms which are metabolically active. Biological activity can therefore impact the cloud oxidant capacity. The present article aims at highlighting the interactions between H2O2 and microorganisms within the cloud system. First, experiments were performed with selected strains studied as a reference isolated from clouds in microcosms designed to mimic the cloud chemical composition, including the presence of light and iron. Biotic and abiotic degradation rates of H2O2 were measured and results showed that biodegradation was the most efficient process together with the photo-Fenton process. H2O2 strongly impacted the microbial energetic state as shown by adenosine triphosphate (ATP) measurements in the presence and absence of H2O2. This ATP depletion was not due to the loss of cell viability. Secondly, correlation studies were performed based on real cloud measurements from 37 cloud samples collected at the PUY station (1465 m a.s.l., France). The results support a strong correlation between ATP and H2O2 concentrations and confirm that H2O2 modulates the energetic metabolism of the cloud microbiome. The modulation of microbial metabolism by H2O2 concentration could thus impact cloud chemistry, in particular the biotransformation rates of carbon compounds, and consequently can perturb the way the cloud system is modifying the global atmospheric chemistry.

  7. Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

    NASA Astrophysics Data System (ADS)

    Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

    2018-02-01

    Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.

  8. Magnesium/Lithium-Ion Hybrid Battery with High Reversibility by Employing NaV3O8·1.69H2O Nanobelts as a Positive Electrode.

    PubMed

    Rashad, Muhammad; Li, Xianfeng; Zhang, Huamin

    2018-06-27

    Recently, magnesium-ion batteries (MIBs) have been under remarkable research focus owing to their appealingly high energy density and natural abundance of magnesium. Nevertheless, MIBs exhibit a very limited performance because of sluggish solid-state Mg 2+ ion diffusion and high polarizability, which hinder their progress toward commercialization. Herein, we report a Mg 2+ /Li + hybrid-ion battery (MLIB) with NaV 3 O 8 ·1.69H 2 O (NVO) nanobelts synthesized at room temperature working as the positive electrode. In the hybrid-ion system, Li + intercalates/deintercalates along with a small amount of Mg 2+ adsorption at the NVO cathode, whereas the anode side of the cell is dominated by Mg 2+ deposition/dissolution. As a result, the MLIB exhibits a much higher rate capability (i.e., 446 mA h g -1 at 20 mA g -1 ) than the previously reported MLIBs. MLIB maintains a high specific capacity of 200 mA h g -1 at 80 mA g -1 for 150 cycles, showing excellent stability. Moreover, the effect of different Li-ion concentrations (i.e., 0.5-2.0 M) in the electrolyte and cutoff voltage (ranging from 2 to 2.6 V) on the specific capacities are investigated. The current study highlights a strategy to exploit the Mg 2+ /Li + hybrid electrolyte system with various electrode materials for high-performance MIBs.

  9. Reactions of electronically excited molecular nitrogen with H2 and H2O molecules: theoretical study

    NASA Astrophysics Data System (ADS)

    Pelevkin, Alexey V.; Sharipov, Alexander S.

    2018-05-01

    Comprehensive quantum chemical analysis with the usage of the second-order perturbation multireference XMCQDPT2 approach was carried out to study the processes in the   +  H2 and   +  H2O systems. The energetically favorable reaction pathways have been revealed based on the exploration of potential energy surfaces. It has been shown that the reactions   +  H2 and   +  H2O occur with small activation barriers and, primarily, lead to the formation of N2H  +  H and N2H  +  OH products, respectively. Further, the interaction of these species could give rise to the ground state and H2 (or H2O) products, however, the estimations, based on RRKM theory and dynamic reaction coordinate calculations, exhibited that the   +  H2 and   +  H2O reactions lead to the dissociative quenching predominately. Appropriate rate constants for revealed reaction channels have been estimated by using a canonical variational theory and capture approximation. Corresponding three-parameter Arrhenius expressions for the temperature range T  =  300  ‑  3000 K were reported.

  10. Bacterial Ice Nucleation in Monodisperse D2O and H2O-in-Oil Emulsions.

    PubMed

    Weng, Lindong; Tessier, Shannon N; Smith, Kyle; Edd, Jon F; Stott, Shannon L; Toner, Mehmet

    2016-09-13

    Ice nucleation is of fundamental significance in many areas, including atmospheric science, food technology, and cryobiology. In this study, we investigated the ice-nucleation characteristics of picoliter-sized drops consisting of different D2O and H2O mixtures with and without the ice-nucleating bacteria Pseudomonas syringae. We also studied the effects of commonly used cryoprotectants such as ethylene glycol, propylene glycol, and trehalose on the nucleation characteristics of D2O and H2O mixtures. The results show that the median freezing temperature of the suspension containing 1 mg/mL of a lyophilized preparation of P. syringae is as high as -4.6 °C for 100% D2O, compared to -8.9 °C for 100% H2O. As the D2O concentration increases every 25% (v/v), the profile of the ice-nucleation kinetics of D2O + H2O mixtures containing 1 mg/mL Snomax shifts by about 1 °C, suggesting an ideal mixing behavior of D2O and H2O. Furthermore, all of the cryoprotectants investigated in this study are found to depress the freezing phenomenon. Both the homogeneous and heterogeneous freezing temperatures of these aqueous solutions depend on the water activity and are independent of the nature of the solute. These findings enrich our fundamental knowledge of D2O-related ice nucleation and suggest that the combination of D2O and ice-nucleating agents could be a potential self-ice-nucleating formulation. The implications of self-nucleation include a higher, precisely controlled ice seeding temperature for slow freezing that would significantly improve the viability of many ice-assisted cryopreservation protocols.

  11. Non-Potassic Melts In CMAS-CO2-H2O-K2O Model Peridotite

    NASA Astrophysics Data System (ADS)

    Buisman, I.; Walter, M. J.; Keshav, S.

    2009-12-01

    Volatile mediated model systems have been fundamental in shaping our knowledge about the way we view melting phase relations of peridotite at various depths in the Earth. Volatiles not only affect the melting temperatures, but the resulting liquids are, in some case, dramatically different than those witnessed in melting of dry peridotite. For example, the influence of CO2 and H2O on the melting phase relations of model peridotite shows a remarkable decrease in the solidus temperatures when compared to the dry peridotite (Gudfinnsson and Presnall, 2005). These model systems illustrate a gradational change above the solidus from carbonatites to kimberlites over several hundreds of degrees. Group-II kimberlites are ultrapotassic rocks with high water content where the mineral phlogopite is abundant. To get a better understanding of the melting phase relations related to carbonatitic and kimberlitic magmas, K2O was added to the system CMAS-CO2-H2O. In these systems, fluid and melt can co-exist in P-T space. However, from past studies, it is also known that in hydrous systems, both the fluid and melt will become indistinguishable from one another creating a singularity (second critical endpoint). Starting from the solidus located in six components (Keshav and Gudfinnsson, AGU abstract, 2009), with seven phases, melting phase relations in CMAS-CO2-H2O-K2O involving, fo-opx-cpx-garnet-carbonate-melt-fluid, are divariant. Fluid was recognized with the observation of large cavities seen in exposed capsules. Moreover, the presence of bright, needle-like grains found in large cavities in backscattered images implies the presence of solute in the fluid phase. Significantly, liquids on this divariant region have about 1000 ppm K2O, and so is the case with accompanying cpx. Hence, with this non-interesting amount of K2O in the mentioned phases, fluid must have all the potassium. At 30 kbar/1100C, with fo-opx-cpx-garnet-carbonate-phlogopite-melt-fluid, the melting phase

  12. Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

    NASA Astrophysics Data System (ADS)

    Johannes, Wilhelm

    1980-09-01

    Beginning of melting and subsolidus relationships in the system K2O-CaO-Al2O3-SiO2-H2O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt. The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K2O-CaO-Al2O3-SiO2-H2O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al2O3-SiO2-H2O. The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al2O3-SiO2-H2O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this

  13. 75 FR 10460 - Improving Tracing Procedures for E. coli O157:H7 Positive Raw Beef Product

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-08

    ... Tracing Procedures for E. coli O157:H7 Positive Raw Beef Product AGENCY: Food Safety and Inspection... Agency procedures for identifying suppliers of source material used to produce raw beef product that FSIS... that raw beef is positive for E. coli O157:H7, and whether the Agency takes the appropriate steps to...

  14. Raman spectroscopy of the multianion mineral gartrellite-PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Palmer, Sara J.

    2012-04-01

    The multianion mineral gartrellite PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2 has been studied by a combination of Raman and infrared spectroscopy. The vibrational spectra of two gartrellite samples from Durango and Ashburton Downs were compared. Gartrellite is one of the tsumcorite mineral group based upon arsenate and sulphate anions. Crystal symmetry is either triclinic in the case of an ordered occupation of two cationic sites, triclinic due to ordering of the H bonds in the case of species with 2 water molecules per formula unit, or monoclinic in the other cases. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes. These spectra are related to the structure of gartrellite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO4 anion.

  15. Mars - Remote spectral identification of H2O frost and mineral hydrate

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.; Clark, R. N.; Mccord, T. B.

    1978-01-01

    A reflectance spectrum (0.62-2.6 microns) of Mars (integral disk) is obtained using a newly developed IR spectrometer at the 2.25 m telescope on Mauna Kea, Hawaii. Details of the instrument, observations, and data reduction are presented. Several distinct absorption features are evident that were apparently caused by H2O, but the positions and intensities of the features are quite unusual. In summary, the regolith is probably not as desiccated and dehydrated as the full disk reflectance spectrum and Viking soil analyses would suggest. The surface materials become desiccated and dehydrated as a result of solar UV effects and because of the relative adsorption and desorption rates during the strong diurnal cycling. There may be significant amounts of H2O at depth, and in the Solis Lacus region the H2O reservoir may extend to within a few centimeters of the surface. The Solis Lacus region may therefore be an important target for future Mars landing or sample return mission.

  16. Structure of H2Ti3O7 and its evolution during sodium insertion as anode for Na ion batteries.

    PubMed

    Eguía-Barrio, Aitor; Castillo-Martínez, Elizabeth; Zarrabeitia, Maider; Muñoz-Márquez, Miguel A; Casas-Cabanas, Montse; Rojo, Teófilo

    2015-03-14

    H2Ti3O7 was prepared as a single phase material by ionic exchange from Na2Ti3O7. The complete ionic exchange was confirmed by (1)H and (23)Na solid state Nuclear Magnetic Resonance (NMR). The atomic positions of H2Ti3O7 were obtained from the Rietveld refinement of powder X-ray diffraction (PXRD) and neutron diffraction experimental data, the latter collected at two different wavelengths to precisely determine the hydrogen atomic positions in the structure. All H(+) cations are hydrogen bonded to two adjacent [Ti3O7](2-) layers leading to the gliding of the layers and lattice centring with respect to the parent Na2Ti3O7. In contrast with a previous report where protons were located in two different positions of H2Ti3O7, 3 types of proton positions were found. Two of the three types of proton are bonded to the only oxygen linked to a single titanium atom forming an H-O-H angle close to that of the water molecule. H2Ti3O7 is able to electrochemically insert Na(+). The electrochemical insertion of sodium into H2Ti3O7 starts with a solid solution regime of the C-centred phase. Then, between 0.6 and 1.2 inserted Na(+) the reaction proceeds through a two phase reaction and a plateau at 1.3 V vs. Na(+)/Na is observed in the voltage-composition curve. The second phase resembles the primitive Na2Ti3O7 cell as detected by in situ PXRD. Upon oxidation, from 0.9 to 2.2 V, the PXRD pattern remains mostly unchanged probably due to H(+) removal instead of Na(+), with the capacity quickly fading upon cycling. Conditioning H2Ti3O7 for two cycles at 0.9-2.2 V before cycling in the 0.05-1.6 V range yields similar specific capacity and better retention than the original Na2Ti3O7 in the same voltage range.

  17. GaAs micromachining in the 1 H2SO4:1 H2O2:8 H2O system. From anisotropy to simulation

    NASA Astrophysics Data System (ADS)

    Tellier, C. R.

    2011-02-01

    The bulk micromachining on (010), (110) and (111)A GaAs substrates in the 1 H2SO4:1 H2O2:8 H2O system is investigated. Focus is placed on anisotropy of 3D etching shapes with a special emphasis on convex and concave undercuts which are of prime importance in the wet micromachining of mechanical structures. Etched structures exhibit curved contours and more and less rounded sidewalls showing that the anisotropy is of type 2. This anisotropy can be conveniently described by a kinematic and tensorial model. Hence, a database composed of dissolution constants is further determined from experiments. A self-elaborated simulator which works with the proposed database is used to derive theoretical 3D shapes. Simulated shapes agree well with observed shapes of microstructures. The successful simulations open up two important applications for MEMS: CAD of mask patterns and meshing of simulated shapes for FEM simulation tools.

  18. Anionic ordering and thermal properties of FeF 3·3H 2O

    DOE PAGES

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; ...

    2015-09-17

    In this study, iron fluoride tri-hydrate can be used to prepare iron hydroxyfluoride with the Hexagonal-Tungsten-Bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF 3·3H 2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF 6]n and [FeF 2(H2O) 4] n. The decomposition of FeF 3·3H 2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF 3-x(OH) x with the HTB structure. The releasemore » of H 2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF 3·3H 2O. An average distribution of FeF 4(OH) 2 distorted octahedra in HTB-FeF 3-x(OH) x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F- and H 2O. This study provides a clear understanding of the structure and thermal properties of FeF 3·3H 2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.« less

  19. Two basic bismuth nitrates: [Bi6O6(OH)2](NO3)4 · 2H2O with superior photodegradation activity for rhodamine B and [Bi6O5(OH)3](NO3)5 · 3H2O with ultrahigh adsorption capacity for methyl orange

    NASA Astrophysics Data System (ADS)

    Pang, Jiawei; Han, Qiaofeng; Liu, Weiqi; Shen, Zichen; Wang, Xin; Zhu, Junwu

    2017-11-01

    A novel basic bismuth nitrate, [Bi6O6(OH)2](NO3)4·2H2O (denoted as BiON-4N), was easily obtained at room temperature in the existence of 2-methoxyethanol (CH3OCH2CH2OH; 2ME) with a pH value ranging from 4.5 to 7.0. The morphology of BiON-4N could be easily tailored by changing the variety and amount of bases like urea, hexamethylenetetramine (HMTA), NaOH and NH3·H2O. When the solution pH was decreased lower than 4.5, another basic bismuth nitrate, [Bi6O5(OH)3](NO3)5·3H2O (denoted as BiON-5N), could be synthesized. Among those, BiON-4N nanoparticles obtained with 40 mmol of HMTA exhibited superior photocatalytic activity for rhodamine B (RhB) degradation with an efficiency of 100% within 4 min of UV light irradiation, which was much higher than that of commercial TiO2 (P25). The excellent photocatalytic performance of BiON-4N was mainly attributed to higher surface area (13.1 m2 g-1) in comparison with other basic bismuth nitrates. Furthermore, the as-prepared BiON-5N revealed excellent adsorption performance for the anions like methyl orange (MO) and K2Cr2O7, and especially for MO, the maximum adsorption capacity arrived up to 730 mg g-1, which should be relevant to highly positively charged surface. This work provides a new strategy for developing bismuth-based nanomaterials in the big bismuth family as potential photocatalyst and adsorbent for the removal of dyes and contaminants.

  20. Fluoresence cross section of the H2O(+) A 2A1(0,7,0) produced through photoionization of H2O

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. Robert; Hwang, M. Y.

    1988-01-01

    The cross section for the production of the H2O(+) A 2A1(0,7,0) - X 2B1(0,0,0) fluorescence through photoionization of H2O was measured in the 14.5-20.5 eV region. The maximum quantum yield is 1.4 x 10 to the -3rd at 16.5 eV.

  1. The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

    PubMed

    Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

    2001-12-05

    The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO

  2. Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst.

    PubMed

    Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

    2015-01-01

    Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

  3. Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst

    NASA Astrophysics Data System (ADS)

    Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

    2015-02-01

    Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

  4. Comparison of exogenous surfactant therapy, mechanical ventilation with high end-expiratory pressure and partial liquid ventilation in a model of acute lung injury.

    PubMed

    Hartog, A; Vazquez de Anda, G F; Gommers, D; Kaisers, U; Verbrugge, S J; Schnabel, R; Lachmann, B

    1999-01-01

    We have compared three treatment strategies, that aim to prevent repetitive alveolar collapse, for their effect on gas exchange, lung mechanics, lung injury, protein transfer into the alveoli and surfactant system, in a model of acute lung injury. In adult rats, the lungs were ventilated mechanically with 100% oxygen and a PEEP of 6 cm H2O, and acute lung injury was induced by repeated lung lavage to obtain a PaO2 value < 13 kPa. Animals were then allocated randomly (n = 12 in each group) to receive exogenous surfactant therapy, ventilation with high PEEP (18 cm H2O), partial liquid ventilation or ventilation with low PEEP (8 cm H2O) (ventilated controls). Blood-gas values were measured hourly. At the end of the 4-h study, in six animals per group, pressure-volume curves were constructed and bronchoalveolar lavage (BAL) was performed, whereas in the remaining animals lung injury was assessed. In the ventilated control group, arterial oxygenation did not improve and protein concentration of BAL and conversion of active to non-active surfactant components increased significantly. In the three treatment groups, PaO2 increased rapidly to > 50 kPa and remained stable over the next 4 h. The protein concentration of BAL fluid increased significantly only in the partial liquid ventilation group. Conversion of active to non-active surfactant components increased significantly in the partial liquid ventilation group and in the group ventilated with high PEEP. In the surfactant group and partial liquid ventilation groups, less lung injury was found compared with the ventilated control group and the group ventilated with high PEEP. We conclude that although all three strategies improved PaO2 to > 50 kPa, the impact on protein transfer into the alveoli, surfactant system and lung injury differed markedly.

  5. A neodymium(III)-ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)].H2O.

    PubMed

    Trombe, Jean-Christian; Galy, Jean; Enjalbert, Renée

    2002-10-01

    The title compound, diammonium aqua-mu-carbonato-tri-mu-oxalato-dineodymium(III) hydrate, (NH(4))(2)[Nd(2)(CO(3))(C(2)O(4))(3)(H(2)O)].H(2)O, involving the two ligands oxalate and carbonate, has been prepared hydrothermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (1/2, 1/2, 1/2). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three-dimensional network. The carbonate group acts as a bis-chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis-chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.

  6. Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

    PubMed

    Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

    2017-01-03

    The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

  7. Dwornikite, (Ni,Fe)SO4.H2O, a member of the kieserite group from Minasragra, Peru.

    USGS Publications Warehouse

    Milton, C.; Evans, H.T.; Johnson, R.G.

    1982-01-01

    A new nickel sulphate monohydrate is described from V-sulphide ore from Minasragra; it occurs associated with patronite (VS2) with various sulphates, sulphur and bitumen. Dwornikite forms fine-grained white aggregates mixed with other oxidation products. Indexed X-ray powder data are tabulated; strongest lines 3.342(100) , 4.732(70), 3.024(70), 4.754(50), 3.293(35), 2.491(35) A; a 6.839, b 7.582, c 7.474 A, beta 117.85o; space group C2/c. XRF gave NiO 39.0, FeO 9.3, SO3 42.4, = 90.7; Dcalc. 3.34 g/cm3; mean refr. ind. approx 1.63. Unit-cell data for the synthetic end-member compounds NiSO4.H2O and FeSO4.H2O and new X-ray powder data for retgersite (NiSO4.6H2O) are given. The name is for E. J. Dwornik, mineralogist with the U.S. Geological Survey.-R.A.H.

  8. Preparation, Characterization, and Structure of Two Layered Molybdenum(VI) Phosphates: KMo(H 2O)O 2PO 4 and NH 4Mo(H 2O)O 2PO 4

    NASA Astrophysics Data System (ADS)

    Millini, Roberto; Carati, Angela

    1995-08-01

    New layered Mo(VI) compounds, KMo(H 2O)O 2PO 4 (I) and NH 4Mo(H 2O)O 2PO 4 (II), were synthesized hydrothermally and their structures were determined from single-crystal X-ray analysis. Compounds (I) and (II) are isostructural and crystallize in the monoclinic P2 1/ n space group with a = 12.353(3), b = 8.623(2), c = 5.841(1) Å, β = 102.78(1)°, V = 606.8(2) Å 3, Z = 4, and R = 0.027 ( Rw = 0.030) for compound (I) and a = 12.435(3), b = 8.761(2), c = 6.015(1), β = 103.45(1)°, V = 637.3(2) Å 3, Z = 4, and R = 0.040 ( Rw = 0.041) for compound (II). The structure consists of layers built up of eight- and four-membered rings resulting from the alternation of corner-sharing [MoO 6] octahedra and [PO 4] tetrahedra. The layers stack along the (1¯01) direction by intercalating K and NH 4 ions.

  9. Determinants of expiratory flow limitation in healthy women during exercise.

    PubMed

    Dominelli, Paolo B; Guenette, Jordan A; Wilkie, Sabrina S; Foster, Glen E; Sheel, A William

    2011-09-01

    Expiratory flow limitation (EFL) can occur in healthy young women during exercise. We questioned whether the occurrence and severity of EFL were related to aerobic fitness or anatomical factors. Twenty-two healthy young (<40 yr) women performed a progressive cycle test to exhaustion. The subjects' maximum expiratory flow-volume curve was compiled from several effort-graded vital capacity maneuvers before and after exercise. The maximum expiratory flow-volume curve, along with inspiratory capacity maneuvers, was used to determine lung volumes and expiratory flows and to quantify EFL. To determine relative airway size, we used a ratio sensitive to both airway size and lung volume, called the dysanapsis ratio. The subjects were partitioned into two groups based upon the appearance of >5% EFL. Ten subjects showed EFL during exercise. Forced vital capacities (4.4 ± 0.4 vs 3.7 ± 0.4 L, P < 0.001) and forced expiratory flows for any given lung volume were significantly larger in the non-expiratory flow-limited (NEFL) group. The NEFL group's dysanapsis ratio was significantly larger than that of the EFL group (0.27 ± 0.06 vs 0.21 ± 0.04, respectively, P < 0.05), indicating larger airways in the NEFL group. There was no difference between the NEFL and EFL groups with respect to maximal aerobic capacity (50.8 ± 10.0 vs 46.7 ± 5.9 mL·kg(-1)·min(-1), respectively, P = 0.264). At peak exercise, the NEFL group had a significantly higher end-expiratory lung volume than the EFL group (40.1% ± 4.8% vs 33.7% ± 5.7% FVC, respectively, P < 0.05). We conclude that EFL in women can largely be explained by anatomical factors that influence the capacity to generate flow and volume during exercise rather than fitness per se.

  10. The effect of H2O and CO2 on planetary mantles

    NASA Technical Reports Server (NTRS)

    Wyllie, P. J.

    1978-01-01

    The peridotite-H2O-CO2 system is discussed, and it is shown that even traces of H2O and CO2, in minerals or vapor, lower mantle solidus temperatures through hundreds of degrees in comparison with the volatile-free solidus. The solidus for peridotite-H2O-CO2 is a divariant surface traversed by univariant lines that locate the intersections of subsolidus divariant surfaces for carbonation or hydration reactions occurring in the presence of H2O-CO2 mixtures. Vapor phase compositions are normally buffered to these lines, and near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus. Characteristics on the CO2 side of the maximum and on the H2O side of the maximum are described.

  11. Influence of N-H...O and C-H...O hydrogen bonds on the 17O NMR tensors in crystalline uracil: computational study.

    PubMed

    Ida, Ramsey; De Clerk, Maurice; Wu, Gang

    2006-01-26

    We report a computational study for the 17O NMR tensors (electric field gradient and chemical shielding tensors) in crystalline uracil. We found that N-H...O and C-H...O hydrogen bonds around the uracil molecule in the crystal lattice have quite different influences on the 17O NMR tensors for the two C=O groups. The computed 17O NMR tensors on O4, which is involved in two strong N-H...O hydrogen bonds, show remarkable sensitivity toward the choice of cluster model, whereas the 17O NMR tensors on O2, which is involved in two weak C-H...O hydrogen bonds, show much smaller improvement when the cluster model includes the C-H...O hydrogen bonds. Our results demonstrate that it is important to have accurate hydrogen atom positions in the molecular models used for 17O NMR tensor calculations. In the absence of low-temperature neutron diffraction data, an effective way to generate reliable hydrogen atom positions in the molecular cluster model is to employ partial geometry optimization for hydrogen atom positions using a cluster model that includes all neighboring hydrogen-bonded molecules. Using an optimized seven-molecule model (a total of 84 atoms), we were able to reproduce the experimental 17O NMR tensors to a reasonably good degree of accuracy. However, we also found that the accuracy for the calculated 17O NMR tensors at O2 is not as good as that found for the corresponding tensors at O4. In particular, at the B3LYP/6-311++G(d,p) level of theory, the individual 17O chemical shielding tensor components differ by less than 10 and 30 ppm from the experimental values for O4 and O2, respectively. For the 17O quadrupole coupling constant, the calculated values differ by 0.30 and 0.87 MHz from the experimental values for O4 and O2, respectively.

  12. Evaluation of H2O2 and pH in exhaled breath condensate samples: methodical and physiological aspects.

    PubMed

    Knobloch, Henri; Becher, Gunther; Decker, Manfred; Reinhold, Petra

    2008-05-01

    This veterinary study is aimed at further standardization of H(2)O(2) and pH measurements in exhaled breath condensate (EBC). Data obtained in the study provide valuable information for many mammalian species including humans, and may help to avoid general pitfalls in interpretation of EBC data. EBC was sampled via the 'ECoScreen' in healthy calves (body weight 63-98 kg). Serum samples and condensates of ambient (indoor) air were collected in parallel. In the study on H(2)O(2), concentrations of H(2)O(2) in EBC, blood and ambient air were determined with the biosensor system 'ECoCheck'. In EBC, the concentration of H(2)O(2) was found to be dependent on food intake and increased significantly in the course of the day. Physiologically, lowest H(2)O(2) concentrations at 06:00 varied within the range 138-624 nmol l(-1) EBC or 0.10-0.94 nmol per 100 l exhaled breath and individual concentrations were significantly different indicating a remarkable intersubject variability. Highly reproducible results were seen within each subject (three different days within 4 weeks). No correlation existed between H(2)O(2) concentrations in EBC and blood, and EBC-H(2)O(2) was not influenced by variables of spontaneous breathing. Further results confirmed that standardization of H(2)O(2) measurements in EBC requires (1) the re-calculation of the concentration exhaled per 100 l exhaled breath (because the analyzed concentration in the liquid condensate underlies multiple methodological sources of variability given by the collection process), and (2) subtracting the concentration of inspired indoor H(2)O(2). In the study on pH use of the ISFET electrode (Sentron, the Netherlands) and a blood gas analyzer ABL 550 (Radiometer, Denmark) led to comparable results for EBC-pH (r=0.89, R(2)=79.3%, pH data in non-degassed EBC samples varied between 5.3 and 6.5, and were not significantly different between subjects, but were significantly higher in the evening compared

  13. Noble metal-free RGO/TiO2 composite nanofiber with enhanced photocatalytic H2-production performance

    NASA Astrophysics Data System (ADS)

    Xu, Difa; Li, Lingling; He, Rongan; Qi, Lifang; Zhang, Liuyang; Cheng, Bei

    2018-03-01

    1D reduced graphene oxide (RGO)/TiO2 nanocomposite fibers were fabricated by a facile two-step method. These samples demonstrated high photocatalytic H2-production activity from methanol aqueous solution, even without the aid of noble metal. When the ratio of RGO is 0.25 wt%, the highest H2-production rate was achieved. It increased by 10 fold than bare TiO2, reaching 149 μmol h-1 g-1 with quantum efficiency (QE) of 0.75%. The reasons were as follows. Firstly, the RGO nanosheets acted as electron acceptors. Secondly, some shallow trap states at the surface or interface of TiO2 were created by the reduction of GO during calcination. Thirdly, the redox potential position of graphene/graphene- was suitable. Fourthly, RGO could efficiently promote the separation of photogenerated electron-hole pairs and significantly enhance the photocatalytic H2-production activity. This interpretation was corroborated by transient photocurrent response. The aforementioned marvelous results provided a probable solution to replace noble metals (such as Pt) by graphene as an effective cocatalyst.

  14. The responses of the four main substitution mechanisms of H in olivine to H2O activity at 1050 °C and 3 GPa

    NASA Astrophysics Data System (ADS)

    Tollan, Peter M. E.; Smith, Rachel; O'Neill, Hugh St. C.; Hermann, Jörg

    2017-12-01

    The water solubility in olivine ({C}_{{H}_2O}) has been investigated at 1050 °C and 3 GPa as a function of water activity ({a}_{{H}_2O}) at subsolidus conditions in the piston-cylinder apparatus, with {a}_{{H}_2O} varied using H2O-NaCl fluids. Four sets of experiments were conducted to constrain the effect of {a}_{{H}_2O} on the four main substitution mechanisms. The experiments were designed to grow olivine in situ and thus achieve global equilibrium (G-type), as opposed to hydroxylating olivine with a pre-existing point-defect structure and impurity content (M-type). Olivine grains from the experiments were analysed with polarised and unpolarised FTIR spectroscopy, and where necessary, the spectra have been deconvoluted to quantify the contribution of each substitution mechanism. Olivine buffered with magnesiowüstite produced absorbance bands at high wavenumbers ranging from 3566 to 3612 cm-1. About 50% of the total absorbance was found parallel to the a-axis, 30% parallel to the b-axis and 20% parallel to the c-axis. The total absorbance and hence water concentration in olivine follows the relationship of {C}_{{H}_2O}∝ {a_{{H}_2O}}^2 , indicating that the investigated defect must involve four H atoms substituting for one Si atom (labelled as [Si]). Forsterite buffered with enstatite produced an absorbance band exclusively aligned parallel the c-axis at 3160 cm-1. The band position, polarisation and observed {C}_{{H}_2O}∝ {a}_{{H}_2O} are consistent with two H substituting for one Mg (labelled as [Mg]). Ti-doped, enstatite-buffered olivine displays absorption bands, and polarisation typical of Ti-clinohumite point defects where two H on the Si-site are charge-balanced by one Ti on a Mg-site (labelled as [Ti]). This is further supported by {C}_{{H}_2O}∝ {a}_{{H}_2O} and a 1:1 relationship of molar H2O and TiO2 in these experiments. Sc-doped, enstatite-buffered experiments display a main absorption band at 3355 cm-1 with {C}_{{H}_2O}∝ {a_{{H}_2O}}^{0

  15. Solar kerosene from H2O and CO2

    NASA Astrophysics Data System (ADS)

    Furler, P.; Marxer, D.; Scheffe, J.; Reinalda, D.; Geerlings, H.; Falter, C.; Batteiger, V.; Sizmann, A.; Steinfeld, A.

    2017-06-01

    The entire production chain for renewable kerosene obtained directly from sunlight, H2O, and CO2 is experimentally demonstrated. The key component of the production process is a high-temperature solar reactor containing a reticulated porous ceramic (RPC) structure made of ceria, which enables the splitting of H2O and CO2 via a 2-step thermochemical redox cycle. In the 1st reduction step, ceria is endo-thermally reduced using concentrated solar radiation as the energy source of process heat. In the 2nd oxidation step, nonstoichiometric ceria reacts with H2O and CO2 to form H2 and CO - syngas - which is finally converted into kerosene by the Fischer-Tropsch process. The RPC featured dual-scale porosity for enhanced heat and mass transfer: mm-size pores for volumetric radiation absorption during the reduction step and μm-size pores within its struts for fast kinetics during the oxidation step. We report on the engineering design of the solar reactor and the experimental demonstration of over 290 consecutive redox cycles for producing high-quality syngas suitable for the processing of liquid hydrocarbon fuels.

  16. Activation of Nrf2 by H2O2: de novo synthesis versus nuclear translocation.

    PubMed

    Covas, Gonçalo; Marinho, H Susana; Cyrne, Luísa; Antunes, Fernando

    2013-01-01

    The most common mechanism described for the activation of the transcription factor Nrf2 is based on the inhibition of its degradation in the cytosol followed by its translocation to the nucleus. Recently, Nrf2 de novo synthesis was proposed as an additional mechanism for the rapid upregulation of Nrf2 by hydrogen peroxide (H2O2). Here, we describe a detailed protocol, including solutions, pilot experiments, and experimental setups, which allows exploring the role of H2O2, delivered either as a bolus or as a steady state, in endogenous Nrf2 translocation and synthesis. We also show experimental data, illustrating that H2O2 effects on Nrf2 activation in HeLa cells are strongly dependent both on the H2O2 concentration and on the method of H2O2 delivery. The de novo synthesis of Nrf2 is triggered within 5min of exposure to low concentrations of H2O2, preceding Nrf2 translocation to the nucleus which is slower. Evidence of de novo synthesis of Nrf2 is observed only for low H2O2 steady-state concentrations, a condition that is prevalent in vivo. This study illustrates the applicability of the steady-state delivery of H2O2 to uncover subtle regulatory effects elicited by H2O2 in narrow concentration and time ranges. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Effect of Expiratory Resistive Loading in Expiratory Muscle Strength Training on Orbicularis Oris Muscle Activity

    PubMed Central

    Yanagisawa, Yukio; Matsuo, Yoshimi; Shuntoh, Hisato; Horiuchi, Noriaki

    2014-01-01

    [Purpose] The purpose of this study was to elucidate the effect of expiratory resistive loading on orbicularis oris muscle activity. [Subjects] Subjects were 23 healthy individuals (11 males, mean age 25.5±4.3 years; 12 females, mean age 25.0±3.0 years). [Methods] Surface electromyography was performed to measure the activity of the orbicularis oris muscle during maximum lip closure and resistive loading at different expiratory pressures. Measurement was performed at 10%, 30%, 50%, and 100% of maximum expiratory pressure (MEP) for all subjects. The t-test was used to compare muscle activity between maximum lip closure and 100% MEP, and analysis of variance followed by multiple comparisons was used to compare the muscle activities observed at different expiratory pressures. [Results] No significant difference in muscle activity was observed between maximum lip closure and 100% MEP. Analysis of variance with multiple comparisons revealed significant differences among the different expiratory pressures. [Conclusion] Orbicularis oris muscle activity increased with increasing expiratory resistive loading. PMID:24648644

  18. NASA Lewis H2-O2 MHD program

    NASA Technical Reports Server (NTRS)

    Smith, M.; Nichols, L. D.; Seikel, G. R.

    1974-01-01

    Performance and power costs of H2-O2 combustion powered steam-MHD central power systems are estimated. Hydrogen gas is assumed to be transmitted by pipe from a remote coal gasifier into the city and converted to electricity in a steam MHD plant having an integral gaseous oxygen plant. These steam MHD systems appear to offer an attractive alternative to both in-city clean fueled conventional steam power plants and to remote coal fired power plants with underground electric transmission into the city. Status and plans are outlined for an experimental evaluation of H2-O2 combustion-driven MHD power generators at NASA Lewis Research Center.

  19. Experimental determination of liquidus H2O contents of haplogranite at deep-crustal conditions

    NASA Astrophysics Data System (ADS)

    Makhluf, A. R.; Newton, R. C.; Manning, C. E.

    2017-09-01

    the haplogranite system. For lower H2O (<5.8 wt%) and higher temperature, our results plot on the high end of the extrapolated water contents at liquidus minima when compared to the previous estimates. As a consequence, amounts of metaluminous granites that can be produced from lower crustal biotite-amphibole gneisses by dehydration melting are more restricted than previously thought.

  20. Morphology-defined interaction of copper phthalocyanine with O 2/H 2O

    DOE PAGES

    Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; ...

    2016-11-01

    Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but its interaction with ambient gas/vapor may lead to changes in electronic properties of the material which subsequently limits the lifetime of OPV devices. CuPc films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O 2 and H 2O vapor. Mass loading by O 2 wasmore » enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200° C CuPc -> transition which allows higher O 2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O 2/H 2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O 2/H 2O molecules on gold, which is consistent with findings of other studies.« less

  1. Effective potentials for H2O-He and H2O-Ar systems. Isotropic induction-dispersion potentials

    NASA Astrophysics Data System (ADS)

    Starikov, Vitali I.; Petrova, Tatiana M.; Solodov, Alexander M.; Solodov, Alexander A.; Deichuli, Vladimir M.

    2017-05-01

    The vibrational and rotational dependence of the effective isotropic interaction potential of H2O-He and H2O-Ar systems, taken in the form of Lennard-Jones 6-12 potential has been analyzed. The analysis is based on the experimental line broadening (γ) and line shift (δ) coefficients obtained for different vibrational bands of H2O molecule perturbed by He and Ar. The first and second derivatives of the function C(1)(q) for the long-range part of the induction-dispersion potential with respect to the dimensionless normal coordinates q were calculated using literature information for the dipole moment and mean polarizability functions μ(q) and α(q), respectively. These derivatives have been used in the calculations of the quantities which determine the vibrational and rotational dependence of the long-range part of the effective isotropic potential. The optimal set of the derivatives for the function C(1)(q) is proposed. The comparison with the experimental data has been performed.

  2. Unilateral donor lung dysfunction does not preclude successful contralateral single lung transplantation.

    PubMed

    Puskas, J D; Winton, T L; Miller, J D; Scavuzzo, M; Patterson, G A

    1992-05-01

    Single lung transplantation remains limited by a severe shortage of suitable donor lungs. Potential lung donors are often deemed unsuitable because accepted criteria (both lungs clear on the chest roentgenogram, arterial oxygen tension greater than 300 mm Hg with an inspired oxygen fraction of 1.0, a positive end-expiratory pressure of 5 cm H2O, and no purulent secretions) do not distinguish between unilateral and bilateral pulmonary disease. Many adequate single lung grafts may be discarded as a result of contralateral aspiration or pulmonary trauma. We have recently used intraoperative unilateral ventilation and perfusion to assess single lung function in potential donors with contralateral lung disease. In the 11-month period ending October 1, 1990, we performed 18 single lung transplants. In four of these cases (22%), the donor chest roentgenogram or bronchoscopic examination demonstrated significant unilateral lung injury. Donor arterial oxygen tension, (inspired oxygen fraction 1.0; positive end-expiratory pressure 5 cm H2O) was below the accepted level in each case (246 +/- 47 mm Hg, mean +/- standard deviation). Through the sternotomy used for multiple organ harvest, the pulmonary artery to the injured lung was clamped. A double-lumen endotracheal tube or endobronchial balloon occlusion catheter was used to permit ventilation of the uninjured lung alone. A second measurement of arterial oxygen tension (inspired oxygen fraction 1.0; positive end-expiratory pressure 5 cm H2O) revealed excellent unilateral lung function in all four cases (499.5 +/- 43 mm Hg; p less than 0.0004). These single lung grafts (three right, one left) were transplanted uneventfully into four recipients (three with pulmonary fibrosis and one with primary pulmonary hypertension). Lung function early after transplantation was adequate in all patients. Two patients were extubated within 24 hours. There were two late deaths, one caused by rejection and Aspergillus infection and the other

  3. [Zn(phen)(O,N,O)(H2O)] and [Zn(phen)(O,N)(H2O)] with O,N,O is 2,6-dipicolinate and N,O is L-threoninate: synthesis, characterization, and biomedical properties.

    PubMed

    Chin, Lee-Fang; Kong, Siew-Ming; Seng, Hoi-Ling; Tiong, Yee-Lian; Neo, Kian-Eang; Maah, Mohd Jamil; Khoo, Alan Soo-Beng; Ahmad, Munirah; Hor, Tzi-Sum Andy; Lee, Hong-Boon; San, Swee-Lan; Chye, Soi-Moi; Ng, Chew-Hee

    2012-10-01

    Two ternary Zn(II) complexes, with 1,10-phenanthroline (phen) as the main ligand and a carboxylate-containing ligand [dipicolinate (dipico) or L-threoninate (L-Thr)] as the subsidiary ligand, were prepared and characterized by elemental analysis, Fourier transform IR, UV, and fluorescence spectroscopy, X-ray diffraction, molar conductivity, and electrospray ionization mass spectrometry. X-ray structure analysis shows that both [Zn(phen)(dipico)(H(2)O)]·H(2)O (1) and [Zn(phen)(L-Thr)(H(2)O)Cl]·2H(2)O (2) have octahedral geometry about the Zn(II) atom. Both complexes can inhibit topoisomerase I, and have better anticancer activity than cisplatin against nasopharyngeal cancer cell lines, HK1 and HONE-1, with concentrations causing 50 % inhibition of cell proliferation (IC(50)) in the low micromolar range. Complex 2 has the highest therapeutic index for HK1. Both Zn(II) complexes can induce cell death by apoptosis. Changing the subsidiary ligand in the Zn(II) complexes affects the UV-fluorescence spectral properties of the coordinated phen ligand, the binding affinity for some DNA sequences, nucleobase sequence-selective binding, the phase at which cell cycle progression was arrested for treated cancer cells, and their therapeutic index.

  4. Probing the Release and Uptake of Water in α-MnO 2 · xH 2O

    DOE PAGES

    Yang, Zhenzhen; Ford, Denise C.; Park, Joong Sun; ...

    2016-12-27

    Alpha-MnO 2 is of interest as a cathode material for 3 V lithium batteries and as an electrode/electrocatalyst for higher energy, hybrid Li-ion/Li–O 2 systems. It has a structure with large tunnels that contain stabilizing cations such as Ba 2+, K + , NH 4 + , and H3O + (or water, H 2O). When stabilized by H 3O + /H 2O, the protons can be ion-exchanged with lithium to produce a Li 2O-stabilized α-MnO 2 structure. It has been speculated that the electrocatalytic process in Li–O 2 cells may be linked to the removal of lithium and oxygen frommore » the host α-MnO 2 structure during charge, and their reintroduction during discharge. In this investigation, hydrated α-MnO 2 was used, as a first step, to study the release and uptake of oxygen in α-MnO 2. Temperature-resolved in situ synchrotron X-ray diffraction (XRD) revealed a nonlinear, two-stage, volume change profile, which with the aide of X-ray absorption near-edge spectroscopy (XANES), redox titration, and density functional theory (DFT) calculations, is interpreted as the release of water from the α-MnO 2 tunnels. The two stages correspond to H 2O release from intercalated H 2O species at lower temperatures and H 3O + species at higher temperature. Thermogravimetric analysis confirmed the release of oxygen from α-MnO 2 in several stages during heating–including surface water, occluded water, and structural oxygen–and in situ UV resonance Raman spectroscopy corroborated the uptake and release of tunnel water by revealing small shifts in frequencies during the heating and cooling of α-MnO 2. Lastly, DFT calculations revealed the likelihood of disordered water species in binding sites in α-MnO 2 tunnels and a facile diffusion process.« less

  5. Spectroscopic properties of morin in various CH3OH-H2O and CH3CN-H2O mixed solvents.

    PubMed

    Park, Hyoung-Ryun; Im, Seo-Eun; Seo, Jung-Ja; Kim, Bong-Gon; Yoon, Jin Ah; Bark, Ki-Min

    2015-01-01

    The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation. © 2014 The American Society of Photobiology.

  6. The reactions of HO2 with CO and NO and the reaction of O(1D) with H2O

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Heicklen, J.

    1973-01-01

    HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1D) atoms produced from the photolysis of N2O to give HO radicals or H2 to give HO + H. With H2O two HO radicals are produced for each O(1D) removed low pressures (i.e. approximately 20 torr H2O), but the HO yield drops as the pressure is raised. This drop is attributed to the insertion reaction: O(1D) + H2O + M yields H2O2 +M. The HO radicals generated can react with either CO or H2 to produce H atoms which then add to O2 to produce HO2. Two reactions are given for the reactions of the HO radicals, in the absence of NO.

  7. Assembly of flexible CoMoO4@NiMoO4·xH2O and Fe2O3 electrodes for solid-state asymmetric supercapacitors

    PubMed Central

    Wang, Jing; Zhang, Leipeng; Liu, Xusong; Zhang, Xiang; Tian, Yanlong; Liu, Xiaoxu; Zhao, Jiupeng; Li, Yao

    2017-01-01

    In this work, CoMoO4@NiMoO4·xH2O core-shell heterostructure electrode is directly grown on carbon fabric (CF) via a feasible hydrothermal procedure with CoMoO4 nanowires (NWs) as the core and NiMoO4 nanosheets (NSs) as the shell. This core-shell heterostructure could provide fast ion and electron transfer, a large number of active sites, and good strain accommodation. As a result, the CoMoO4@NiMoO4·xH2O electrode yields high-capacitance performance with a high specific capacitance of 1582 F g−1, good cycling stability with the capacitance retention of 97.1% after 3000 cycles and good rate capability. The electrode also shows excellent mechanical flexibility. Also, a flexible Fe2O3 nanorods/CF electrode with enhanced electrochemical performance was prepared. A solid-state asymmetric supercapacitor device is successfully fabricated by using flexible CoMoO4@NiMoO4·xH2O as the positive electrode and Fe2O3 as the negative electrode. The asymmetric supercapacitor with a maximum voltage of 1.6 V demonstrates high specific energy (41.8 Wh kg−1 at 700 W kg−1), high power density (12000 W kg−1 at 26.7 Wh kg−1), and excellent cycle ability with the capacitance retention of 89.3% after 5000 cycles (at the current density of 3A g−1). PMID:28106170

  8. Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling

    NASA Astrophysics Data System (ADS)

    Tang, Jing; Quan, Yingzhou; Zhang, Yueyu; Jiang, Min; Al-Enizi, Abdullah M.; Kong, Biao; An, Tiance; Wang, Wenshuo; Xia, Limin; Gong, Xingao; Zheng, Gengfeng

    2016-03-01

    Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems.Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in

  9. Reactions of hydrated electrons (H2O)n- with carbon dioxide and molecular oxygen: hydration of the CO2- and O2- ions.

    PubMed

    Balaj, O Petru; Siu, Chi-Kit; Balteanu, Iulia; Beyer, Martin K; Bondybey, Vladimir E

    2004-10-04

    The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

  10. Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

    NASA Technical Reports Server (NTRS)

    Kindler, Andrew; Huang, Yuhong

    2010-01-01

    Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

  11. Seven organic salts assembled from hydrogen-bonds of N-H⋯O, O-H⋯O, and C-H⋯O between acidic compounds and bis(benzimidazole)

    NASA Astrophysics Data System (ADS)

    Jin, Shouwen; Liu, Hui; Gao, Xin Jun; Lin, Zhanghui; Chen, Guqing; Wang, Daqi

    2014-10-01

    Seven crystalline organic acid-base adducts derived from 1,4-bis(benzimidazol-2-yl)butane/1,2-bis(2-benzimidazolyl)-1,2-ethanediol and acidic components (picric acid, 2-hydroxy-5-(phenyldiazenyl)benzoic acid, 5-sulfosalicylic acid, oxalic acid, and 1,5-naphthalenedisulfonic acid) were prepared and characterized by the single crystal X-ray diffraction analysis, IR, mp, and elemental analysis. All of the seven compounds are organic salts involving proton transfer from the acidic components to the bis(benzimidazole). For the salt 3, although a competing carboxyl group is present, it has been observed that only the proton at the -SO3H group is deprotonized rather than the H at the COOH. While in the salt 7, both COOH and SO3H were ionized to exhibit a valence number of -2. For 4, the oxalic acid existed as unionized molecule, monoanion, and dianion simultaneously in one compound. All supramolecular architectures of the organic salts 1-7 involve extensive intermolecular N-H⋯O, O-H⋯O, and C-H⋯O hydrogen bonds as well as other noncovalent interactions. Since the potentially hydrogen bonding phenol group is present in the ortho position to the carboxyl group in 2, 3, and 7, it forms the more facile intramolecular O-H⋯O hydrogen bonding. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, all the complexes displayed 3D framework structure.

  12. Experimental Determination of the H2O-undersaturated Peridotite Solidus

    NASA Astrophysics Data System (ADS)

    Sarafian, E. K.; Gaetani, G. A.; Hauri, E.; Sarafian, A.

    2015-12-01

    Knowledge of the H2O-undersaturated lherzolite solidus places important constraints on the process of melt generation beneath oceanic spreading centers. While it is generally accepted that the small concentration of H2O (~50-200 ug/g) dissolved in the oceanic upper mantle has a strong influence on the peridotite solidus, but this effect has not been directly determined through experiments. This is because (1) precisely controlling low concentrations of H2O in high-pressure melting experiments is thought to be difficult, (2) small amounts of melt are difficult to identify, and (3) the size of mineral grains that grow in near-solidus experiments is too small to be analyzed for H2O by either Fourier transform infrared (FTIR) spectroscopy or secondary ion mass spectrometry (SIMS). We have developed an experimental approach for determining the peridotite solidus as a function of H2O content that overcomes these difficulties. Our approach utilizes large (~300 um diameter) spheres of San Carlos olivine to monitor the concentration and behavior of H2O in our experiments.. The spheres are mixed in 5:95 proportions with a synthetic peridotite that has the composition of the depleted MORB mantle of Workman and Hart (2005). Partial melting experiments are conducted in is a piston cylinder device using pre-conditioned Au80Pd20 capsules. During an experiment, the H2O content of the San Carlos olivine spheres diffusively equilibrates with the peridotite matrix. After each experiment, the concentration of H2O dissolved in the olivine spheres is determined by secondary ion mass spectrometry. By analyzing the H2O content of the San Carlos olivine spheres and performing a simple mass balance, we can then calculate the amount of H2O in the capsule. The spheres also provides a means to determine the solidus temperature due to the strong partitioning of H2O into silicate melt compared to olivine, pyroxene, and spinel. When a small amount of melt is present the H2O partitions into the

  13. New insights into the shock tube ignition of H 2/O 2 at low to moderate temperatures using high-speed end-wall imaging

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

    Ninnemann, Erik; Koroglu, Batikan; Pryor, Owen

    In this study, the effects of pre-ignition energy releases on H 2O 2 mixtures were explored in a shock tube with the aid of high-speed imaging and conventional pressure and emission diagnostics. Ignition delay times and time-resolved camera image sequences were taken behind the reflected shockwaves for two hydrogen mixtures. High concentration experiments spanned temperatures between 858 and 1035 K and pressures between 2.74 and 3.91 atm for a 15% H 2\\18% O 2\\Ar mixture. Low concentration data were also taken at temperatures between 960 and 1131 K and pressures between 3.09 and 5.44 atm for a 4% H 2\\2%more » O 2\\Ar mixture. These two model mixtures were chosen as they were the focus of recent shock tube work conducted in the literature. Experiments were performed in both a clean and dirty shock tube facility; however, no deviations in ignition delay times between the two types of tests were apparent. The high-concentration mixture (15%H 2\\18%O 2\\Ar) experienced energy releases in the form of deflagration flames followed by local detonations at temperatures < 1000 K. Measured ignition delay times were compared to predictions by three chemical kinetic mechanisms: GRI-Mech 3.0, AramcoMech 2.0, and Burke's et al. (2012) mechanisms. It was found that when proper thermodynamic assumptions are used, all mechanisms were able to accurately predict the experiments with superior performance from the well-validated AramcoMech 2.0 and Burke et al. mechanisms. Current work provides better guidance in using available literature hydrogen shock tube measurements, which spanned more than 50 years but were conducted without the aid of high-speed visualization of the ignition process, and their modeling using combustion kinetic mechanisms.« less

  14. New insights into the shock tube ignition of H 2/O 2 at low to moderate temperatures using high-speed end-wall imaging

    DOE PAGES

    Ninnemann, Erik; Koroglu, Batikan; Pryor, Owen; ...

    2017-09-21

    In this study, the effects of pre-ignition energy releases on H 2O 2 mixtures were explored in a shock tube with the aid of high-speed imaging and conventional pressure and emission diagnostics. Ignition delay times and time-resolved camera image sequences were taken behind the reflected shockwaves for two hydrogen mixtures. High concentration experiments spanned temperatures between 858 and 1035 K and pressures between 2.74 and 3.91 atm for a 15% H 2\\18% O 2\\Ar mixture. Low concentration data were also taken at temperatures between 960 and 1131 K and pressures between 3.09 and 5.44 atm for a 4% H 2\\2%more » O 2\\Ar mixture. These two model mixtures were chosen as they were the focus of recent shock tube work conducted in the literature. Experiments were performed in both a clean and dirty shock tube facility; however, no deviations in ignition delay times between the two types of tests were apparent. The high-concentration mixture (15%H 2\\18%O 2\\Ar) experienced energy releases in the form of deflagration flames followed by local detonations at temperatures < 1000 K. Measured ignition delay times were compared to predictions by three chemical kinetic mechanisms: GRI-Mech 3.0, AramcoMech 2.0, and Burke's et al. (2012) mechanisms. It was found that when proper thermodynamic assumptions are used, all mechanisms were able to accurately predict the experiments with superior performance from the well-validated AramcoMech 2.0 and Burke et al. mechanisms. Current work provides better guidance in using available literature hydrogen shock tube measurements, which spanned more than 50 years but were conducted without the aid of high-speed visualization of the ignition process, and their modeling using combustion kinetic mechanisms.« less

  15. KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

    PubMed

    Schlueter, John A; Geiser, Urs; Funk, Kylee A

    2008-02-01

    The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

  16. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

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

    Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

    We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

  17. Degradation mechanism of alachlor during direct ozonation and O(3)/H(2)O(2) advanced oxidation process.

    PubMed

    Qiang, Zhimin; Liu, Chao; Dong, Bingzhi; Zhang, Yalei

    2010-01-01

    The degradation of alachlor by direct ozonation and advanced oxidation process O(3)/H(2)O(2) was investigated in this study with focus on identification of degradation byproducts. The second-order reaction rate constant between ozone and alachlor was determined to be 2.5+/-0.1M(-1)s(-1) at pH 7.0 and 20 degrees C. Twelve and eight high-molecular-weight byproducts (with the benzene ring intact) from alachlor degradation were identified during direct ozonation and O(3)/H(2)O(2), respectively. The common degradation byproducts included N-(2,6-diethylphenyl)-methyleneamine, 8-ethyl-3,4-dihydro-quinoline, 8-ethyl-quinoline, 1-chloroacetyl-2-hydro-3-ketone-7-acetyl-indole, 2-chloro-2',6'-diacetyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-acetyl-6'-ethyl-N-(methoxymethyl)-acetanilide, and two hydroxylated alachlor isomers. In direct ozonation, four more byproducts were also identified including 1-chloroacetyl-2,3-dihydro-7-ethyl-indole, 2-chloro-2',6'-ethyl-acetanilide, 2-chloro-2',6'-acetyl-acetanilide and 2-chloro-2'-ethyl-6'-acetyl-N-(methoxymethyl)-acetanilide. Degradation of alachlor by O(3) and O(3)/H(2)O(2) also led to the formation of low-molecular-weight byproducts including formic, acetic, propionic, monochloroacetic and oxalic acids as well as chloride ion (only detected in O(3)/H(2)O(2)). Nitrite and nitrate formation was negligible. Alachlor degradation occurred via oxidation of the arylethyl group, N-dealkylation, cyclization and cleavage of benzene ring. After O(3) or O(3)/H(2)O(2) treatment, the toxicity of alachlor solution examined by the Daphnia magna bioassay was slightly reduced. 2009 Elsevier Ltd. All rights reserved.

  18. Insertion of bentonite with Organometallic [Fe3O(OOC6H5)6(H2O)3(NO3).nH2O] as Adsorbent of Congo Red

    NASA Astrophysics Data System (ADS)

    Said, Muhammad; Paluta Utami, Hasja; Hayati, Ferlina

    2018-01-01

    The adsorption of Congo red using bentonite inserted organometallic has been investigated. The insertion bentonite was characterized using FT-IR Spectrophotometer, XRD and XRF analysis. The FT-IR characterization showed the higher intensity of peak wavenumber at 470.6 cm-1 for Fe3O on the ratio 1:3. While the XRD characterization showed the shift of diffraction angle of 2θ was 5.2° and has a basal spacing of 16.8 Å. In the XRF characterization, the insertion process of organometallic occurred optimally with the percentage of metal oxide reached 71.75 %. The adsorption process of bentonite inserted organometallic compound [Fe3O(OOC6H5)6(H2O)3(NO3)·nH2O] showed the adsorption rate (k) is 0.050 min-1, the largest adsorption capacity (b) at 70°C is 4.48 mol/g, the largest adsorption energy at temperature 30°C which is 6.4 kJ/mol Organometallic compounds. The value of the enthalpy (ΔH) and entropy (ΔS) decreased with increasing concentrations of the Congo red. Effect of pH on the adsorption on at pH 3 shows the biggest of number Congo red absorbed is 19.52 mg/L for insertion of bentonite.

  19. Novel Process of Simultaneous Removal of Nitric Oxide and Sulfur Dioxide Using a Vacuum Ultraviolet (VUV)-Activated O2/H2O/H2O2 System in A Wet VUV-Spraying Reactor.

    PubMed

    Liu, Yangxian; Wang, Qian; Pan, Jianfeng

    2016-12-06

    A novel process for NO and SO 2 simultaneous removal using a vacuum ultraviolet (VUV, with 185 nm wavelength)-activated O 2 /H 2 O/H 2 O 2 system in a wet VUV-spraying reactor was developed. The influence of different process variables on NO and SO 2 removal was evaluated. Active species (O 3 and ·OH) and liquid products (SO 3 2- , NO 2 - , SO 4 2- , and NO 3 - ) were analyzed. The chemistry and routes of NO and SO 2 removal were investigated. The oxidation removal system exhibits excellent simultaneous removal capacity for NO and SO 2 , and a maximum removal of 96.8% for NO and complete SO 2 removal were obtained under optimized conditions. SO 2 reaches 100% removal efficiency under most of test conditions. NO removal is obviously affected by several process variables. Increasing VUV power, H 2 O 2 concentration, solution pH, liquid-to-gas ratio, and O 2 concentration greatly enhances NO removal. Increasing NO and SO 2 concentration obviously reduces NO removal. Temperature has a dual impact on NO removal, which has an optimal temperature of 318 K. Sulfuric acid and nitric acid are the main removal products of NO and SO 2 . NO removals by oxidation of O 3 , O·, and ·OH are the primary routes. NO removals by H 2 O 2 oxidation and VUV photolysis are the complementary routes. A potential scaled-up removal process was also proposed initially.

  20. Systematic Variations in CO2/H2O Ice Abundance Ratios in Nearby Galaxies Found with AKARI Near-infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yamagishi, M.; Kaneda, H.; Ishihara, D.; Oyabu, S.; Onaka, T.; Shimonishi, T.; Suzuki, T.

    2015-07-01

    We report CO2/H2O ice abundance ratios in seven nearby star-forming galaxies based on the AKARI near-infrared (2.5-5.0 μm) spectra. The CO2/H2O ice abundance ratios show clear variations between 0.05 and 0.2 with the averaged value of 0.14 ± 0.01. The previous study on M82 revealed that the CO2/H2O ice abundance ratios strongly correlate with the intensity ratios of the hydrogen recombination Brα line to the polycyclic aromatic hydrocarbon (PAH) 3.3 μm feature. In the present study, however, we find no correlation for the seven galaxies as a whole due to systematic differences in the relation between CO2/H2O ice abundance and Brα/PAH 3.3 μm intensity ratios from galaxy to galaxy. This result suggests that there is another parameter that determines the CO2/H2O ice abundance ratios in a galaxy in addition to the Brα/PAH 3.3 μm ratios. We find that the CO2/H2O ice abundance ratios positively correlate with the specific star formation rates of the galaxies. From these results, we conclude that CO2/H2O ice abundance ratios tend to be high in young star-forming galaxies.

  1. A new Pu(iii) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media.

    PubMed

    Surbella, Robert G; Ducati, Lucas C; Pellegrini, Kristi L; McNamara, Bruce K; Autschbach, Jochen; Schwantes, Jon M; Cahill, Christopher L

    2017-09-28

    Crystals of a hydrated Pu(iii) chloride, (C 5 H 5 NBr) 2 [PuCl 3 (H 2 O) 5 ]·2Cl·2H 2 O, were grown via slow evaporation from acidic aqueous, high chloride media. X-ray diffraction data reveals the neutral [PuCl 3 (H 2 O) 5 ] tecton is assembled via charge assisted hydrogen and halogen bonds donated by 4-bromopyridinium cations and a series of inter-tecton hydrogen bonds.

  2. Does Regional Lung Strain Correlate With Regional Inflammation in Acute Respiratory Distress Syndrome During Nonprotective Ventilation? An Experimental Porcine Study.

    PubMed

    Retamal, Jaime; Hurtado, Daniel; Villarroel, Nicolás; Bruhn, Alejandro; Bugedo, Guillermo; Amato, Marcelo Britto Passos; Costa, Eduardo Leite Vieira; Hedenstierna, Göran; Larsson, Anders; Borges, João Batista

    2018-06-01

    It is known that ventilator-induced lung injury causes increased pulmonary inflammation. It has been suggested that one of the underlying mechanisms may be strain. The aim of this study was to investigate whether lung regional strain correlates with regional inflammation in a porcine model of acute respiratory distress syndrome. Retrospective analysis of CT images and positron emission tomography images using [F]fluoro-2-deoxy-D-glucose. University animal research laboratory. Seven piglets subjected to experimental acute respiratory distress syndrome and five ventilated controls. Acute respiratory distress syndrome was induced by repeated lung lavages, followed by 210 minutes of injurious mechanical ventilation using low positive end-expiratory pressures (mean, 4 cm H2O) and high inspiratory pressures (mean plateau pressure, 45 cm H2O). All animals were subsequently studied with CT scans acquired at end-expiration and end-inspiration, to obtain maps of volumetric strain (inspiratory volume - expiratory volume)/expiratory volume, and dynamic positron emission tomography imaging. Strain maps and positron emission tomography images were divided into 10 isogravitational horizontal regions-of-interest, from which spatial correlation was calculated for each animal. The acute respiratory distress syndrome model resulted in a decrease in respiratory system compliance (20.3 ± 3.4 to 14.0 ± 4.9 mL/cm H2O; p < 0.05) and oxygenation (PaO2/FIO2, 489 ± 80 to 92 ± 59; p < 0.05), whereas the control animals did not exhibit changes. In the acute respiratory distress syndrome group, strain maps showed a heterogeneous distribution with a greater concentration in the intermediate gravitational regions, which was similar to the distribution of [F]fluoro-2-deoxy-D-glucose uptake observed in the positron emission tomography images, resulting in a positive spatial correlation between both variables (median R = 0.71 [0.02-0.84]; p < 0.05 in five of seven animals

  3. Improved hydrogen storage properties of MgH2 catalyzed with TiO2

    NASA Astrophysics Data System (ADS)

    Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

    2018-05-01

    In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

  4. D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Foustoukos, D.; Mysen, B. O.

    2011-12-01

    Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium

  5. Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

    USGS Publications Warehouse

    Majzlan, J.; Navrotsky, A.; McCleskey, R. Blaine; Alpers, Charles N.

    2006-01-01

    Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

  6. Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

    PubMed

    Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

    2001-02-01

    The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

  7. Interstellar H3O(+) and its relation to the O2 and H2O abundances

    NASA Astrophysics Data System (ADS)

    Phillips, T. G.; van Dishoeck, Ewine F.; Keene, Jocelyn

    1992-11-01

    An interstellar medium study of the three reasonably accessible low-lying submillimeter lines of the H3O(+) molecular ion at 396, 364, and 307 GHz is presented. An analysis of the H3O(+) line ratios shows that under high density (about 10 exp 6 - 10 exp 7/cu cm) and high-temperature (greater than about 50 K), the 396 GHz line is about a factor of two stronger than the 364 GHz line, with the 307 GHz line much weaker. For lower densities, the excitation of the 364 GHz line can be very sensitive to dust radiation pumping, and it is shown that this is the case in Sgr B2, resulting in the 364 GHz line being a factor of 2-3 stronger than the 396 GHz line. Under almost all conditions, the 307 GHz line is weak, the exception being for densities greater than about 10 exp 7/cu cm.

  8. Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)22-OH)2(H2O)4 (P2W16O59)2]14-

    NASA Astrophysics Data System (ADS)

    Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

    2003-08-01

    Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)22-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

  9. Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

    PubMed

    Yang, Jingying; Xie, Zuowei

    2015-04-14

    Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

  10. Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth.

    PubMed

    Haqq-Misra, Jacob; Kasting, James F; Lee, Sukyoung

    2011-05-01

    Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05 nM, which corresponds to a partial pressure for O(2) of about 4 × 10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.

  11. Vapor-liquid phase equilibria of potassium chloride-water mixtures: Equation-of-state representation for KCl-H2O and NaCl-H2O

    USGS Publications Warehouse

    Hovey, J.K.; Pitzer, Kenneth S.; Tanger, J.C.; Bischoff, J.L.; Rosenbauer, R.J.

    1990-01-01

    Measurements of isothermal vapor-liquid compositions for KCl-H2O as a function of pressure are reported. An equation of state, which was originally proposed by Pitzer and was improved and used by Tanger and Pitzer to fit the vapor-liquid coexistence surface for NaCl-H2O, has been used for representation of the KCl-H2O system from 300 to 410??C. Improved parameters are also reported for NaCl-H2O from 300 to 500??C. ?? 1990 American Chemical Society.

  12. Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

    PubMed

    De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

    2014-03-28

    New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

  13. Laboratory IR Detection of H2O, CO2 in Ion-Irradiated Ices Relevant to Europa

    NASA Technical Reports Server (NTRS)

    Moore, Marla H.; Hudson, R. L.

    1999-01-01

    Hydrogen peroxide has been identified on Europa (Carlson et al. 1999) based in part on the 3.50 micron absorption feature observed in Galileo NIMS spectra. The observed feature was fitted with laboratory reflectance spectra of H2O + H2O2. Since condensed phase molecules on Europa (H2O, CO2, SO2, and H2O2) are bombarded with a significant flux of energetic particles (H(+), O(n+), S(n+) and e-), we examined the proton irradiation of H2O at 80 K and the conditions for the IR detection of H2O2 near 3.5 microns. Contrary to expectations, H2O2 was not detected if pure H2O ice was irradiated at 80 K. This was an unexpected result since, H2O2 was detected if pure H2O was irradiated at 18 K. We find, however, that if H2O ice contains either O2 or CO2 then H2O2 is detected after irradiation at 80 K (Moore and Hudson, 1999). The source of O2 for the H2O ice on Europa could come from surface interactions with the tenuous oxygen atmosphere, or from the bombardment of the surface by O(n+).

  14. 5-AIQ inhibits H{sub 2}O{sub 2}-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes

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

    Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun

    2013-04-01

    Poly(adenosine 5′-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H{sub 2}O{sub 2}-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxidemore » dismutase and catalase accompanied the protective effect of 5-AIQ on H{sub 2}O{sub 2}-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H{sub 2}O{sub 2}-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H{sub 2}O{sub 2}-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. - Highlights: ► 5-AIQ, a PARP inhibitor, decreased H{sub 2}O{sub 2}-induced H9c2 cell death and apoptosis. ► 5-AIQ upregulated antioxidant Mn-SOD and catalase, while decreasing ROS production. ► 5-AIQ decreased H{sub 2}O{sub 2}-induced increase in cleaved caspase-3 and Bax and decrease in Bcl2. ► 5-AIQ activated Akt and

  15. The Effects of Prone Position Ventilation on Experimental Mild Acute Lung Injury Induced by Intraperitoneal Lipopolysaccharide Injection in Rats.

    PubMed

    Bianchi, Aydra Mendes Almeida; Reboredo, Maycon Moura; Lucinda, Leda Marília Fonseca; Reis, Fernando Fonseca; Silva, Manfrinni Vinícius Alves; Rabelo, Maria Aparecida Esteves; Holanda, Marcelo Alcantara; Oliveira, Júlio César Abreu; Lorente, José Ángel; Pinheiro, Bruno do Valle

    2016-04-01

    The benefits of prone position ventilation are well demonstrated in the severe forms of acute respiratory distress syndrome, but not in the milder forms. We investigated the effects of prone position on arterial blood gases, lung inflammation, and histology in an experimental mild acute lung injury (ALI) model. ALI was induced in Wistar rats by intraperitoneal Escherichia coli lipopolysaccharide (LPS, 5 mg/kg). After 24 h, the animals with PaO2/FIO2 between 200 and 300 mmHg were randomized into 2 groups: prone position (n = 6) and supine position (n = 6). Both groups were compared with a control group (n = 5) that was ventilated in the supine position. All of the groups were ventilated for 1 h with volume-controlled ventilation mode (tidal volume = 6 ml/kg, respiratory rate = 80 breaths/min, positive end-expiratory pressure = 5 cmH2O, inspired oxygen fraction = 1) RESULTS: Significantly higher lung injury scores were observed in the LPS-supine group compared to the LPS-prone and control groups (0.32 ± 0.03; 0.17 ± 0.03 and 0.13 ± 0.04, respectively) (p < 0.001), mainly due to a higher neutrophil infiltration level in the interstitial space and more proteinaceous debris that filled the airspaces. Similar differences were observed when the gravity-dependent lung regions and non-dependent lung regions were analyzed separately (p < 0.05). The BAL neutrophil content was also higher in the LPS-supine group compared to the LPS-prone and control groups (p < 0.05). There were no significant differences in the wet/dry ratio and gas exchange levels. In this experimental extrapulmonary mild ALI model, prone position ventilation for 1 h, when compared with supine position ventilation, was associated with lower lung inflammation and injury.

  16. Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2.

    PubMed

    Su, Hanrui; Yu, Chunyang; Zhou, Yongfeng; Gong, Lidong; Li, Qilin; Alvarez, Pedro J J; Long, Mingce

    2018-05-02

    Tetra-amido macrocyclic ligand (TAML) activator is a functional analog of peroxidase enzymes, which activates hydrogen peroxide (H 2 O 2 ) to form high valence iron-oxo complexes that selectively degrade persistent aromatic organic contaminants (ACs) in water. Here, we develop quantitative structure-activity relationship (QSAR) models based on measured pseudo first-order kinetic rate coefficients (k obs ) of 29 ACs (e.g., phenols and pharmaceuticals) oxidized by TAML/H 2 O 2 at neutral and basic pH values to gain mechanistic insight on the selectivity and pH dependence of TAML/H 2 O 2 systems. These QSAR models infer that electron donating ability (E HOMO ) is the most important AC characteristic for TAML/H 2 O 2 oxidation, pointing to a rate-limiting single-electron transfer (SET) mechanism. Oxidation rates at pH 7 also depend on AC reactive indices such as f min - and qH + , which respectively represent propensity for electrophilic attack and the most positive net atomic charge on hydrogen atoms. At pH 10, TAML/H 2 O 2 is more reactive towards ACs with a lower hydrogen to carbon atoms ratio (#H:C), suggesting the significance of hydrogen atom abstraction. In addition, lnk obs of 14 monosubstituted phenols is negatively correlated with Hammett constants (σ) and exhibits similar sensitivity to substituent effects as horseradish peroxidase. Although accurately predicting degradation rates of specific ACs in complex wastewater matrices could be difficult, these QSAR models are statistically robust and help predict both relative degradability and reaction mechanism for TAML/H 2 O 2 -based treatment processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

  17. Possible sources of H2 to H2O enrichment at evaporation of parent chondritic material

    NASA Technical Reports Server (NTRS)

    Makalkin, A. B.; Dorofeyeva, V. A.; Vityazev, A. V.

    1993-01-01

    One of the results obtained from thermodynamic simulation of recondensation of the source chondritic material is that at 1500-1800 K it's possible to form iron-rich olivine by reaction between enstatite, metallic iron and water vapor in the case of (H2O)/(H2) approximately equal to 0.1. This could be reached if the gas depletion in hydrogen is 200-300 times relative to solar abundance. To get this range of depletion one needs some source material more rich in hydrogen than the carbonaceous CI material which is the richest in volatiles among chondrites. In the case of recondensation at impact heating and evaporation of colliding planetesimals composed of CI material, we obtain insufficiently high value of (H2)/(H2O) ratio. In the present paper we consider some possible source materials and physical conditions necessary to reach gas composition with (H2)/(H2O) approximately 10 at high temperature.

  18. Outbursts of H2O in Comet P/Halley

    NASA Astrophysics Data System (ADS)

    Larson, H. P.; Hu, H.-Y.; Mumma, M. J.; Weaver, H. A.

    1990-07-01

    Comet Halley gas-production monitoring efforts in March 1986 with the NASA Kuiper Airborne Observatory's Fourier transform spectrometer have indicated rapid temporal variations in H2O emissions; a continuous record of an H2O outburst was thus obtained. The event, in which H2O brightness increased by a factor of 2.2 in less than 10 min, is ascribable to an energetic process in the nucleus whose character may have been that of amorphous H2O ice crystallization, chemical explosion, thermal stress, or a compressed gas pocket. The timing and energy of the event appear to require an internal energy source; amorphous ice crystallization is held to be most consistent with compositional and thermal models of cometary nuclei as well as the observations.

  19. Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols.

    PubMed

    Bi, Jianhong; Kong, Lingtao; Huang, Zixiang; Liu, Jinhuai

    2008-06-02

    Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.

  20. Rad6–Bre1-mediated H2B ubiquitination regulates telomere replication by promoting telomere-end resection

    PubMed Central

    Wu, Zhenfang; Liu, Jun; Zhang, Qiong-Di; Lv, De-Kang; Wu, Nian-Feng

    2017-01-01

    Abstract Rad6 and Bre1, ubiquitin-conjugating E2 and E3 enzymes respectively, are responsible for histone H2B lysine 123 mono-ubiquitination (H2Bub1) in Saccharomyces cerevisiae. Previous studies have shown that Rad6 and Bre1 regulate telomere length and recombination. However, the underlying molecular mechanism remains largely unknown. Here we report that H2BK123 mutation results in telomere shortening, while inactivation of Ubp8 and/or Ubp10, deubiquitinases of H2Bub1, leads to telomere lengthening in Rad6–Bre1-dependent manner. In telomerase-deficient cells, inactivation of Rad6–Bre1 pathway retards telomere shortening rate and the onset of senescence, while deletion of UBP8 and/or UBP10 accelerates senescence. Thus, Rad6–Bre1 pathway regulates both telomere length and recombination through its role in H2Bub1. Additionally, inactivation of both Rad6–Bre1–H2Bub1 and Mre11–Rad50–Xrs2 (MRX) pathways causes synthetic growth defects and telomere shortening in telomerase-proficient cells, and significantly accelerates senescence and eliminates type II telomere recombination in telomerase-deficient cells. Furthermore, RAD6 or BRE1 deletion, or H2BK123R mutation decreases the accumulation of ssDNA at telomere ends. These results support the model that Rad6–Bre1–H2Bub1 cooperates with MRX to promote telomere-end resection and thus positively regulates both telomerase- and recombination-dependent telomere replication. This study provides a mechanistic link between histone H2B ubiquitination and telomere replication. PMID:28180293

  1. Photogeneration of H2O2 in Water-Swollen SPEEK/PVA Polymer Films.

    PubMed

    Lockhart, PaviElle; Little, Brian K; Slaten, B L; Mills, G

    2016-06-09

    Efficient reduction of O2 took place via illumination with 350 nm photons of cross-linked films containing a blend of sulfonated poly(ether etherketone) and poly(vinyl alcohol) in contact with air-saturated aqueous solutions. Swelling of the solid macromolecular matrices in H2O enabled O2 diffusion into the films and also continuous extraction of the photogenerated H2O2, which was the basis for a method that allowed quantification of the product. Peroxide formed with similar efficiencies in films containing sulfonated polyketones prepared from different precursors and the initial photochemical process was found to be the rate-determining step. Generation of H2O2 was most proficient in the range of 4.9 ≤ pH ≤ 8 with a quantum yield of 0.2, which was 10 times higher than the efficiencies determined for solutions of the polymer blend. Increases in temperature as well as [O2] in solution were factors that enhanced the H2O2 generation. H2O2 quantum yields as high as 0.6 were achieved in H2O/CH3CN mixtures with low water concentrations, but peroxide no longer formed when film swelling was suppressed. A mechanism involving reduction of O2 by photogenerated α-hydroxy radicals from the polyketone in competition with second-order radical decay processes explains the kinetic features. Higher yields result from the films because cross-links present in them hinder diffusion of the radicals, limiting their decay and enhancing the oxygen reduction pathway.

  2. Empirical electronic polarizabilities: deviations from the additivity rule. I. M2+SO4·nH2O, blödite Na2M2+(SO4)2·4H2O, and kieserite-related minerals with sterically strained structures

    NASA Astrophysics Data System (ADS)

    Gagné, Olivier; Hawthorne, Frank; Shannon, Robert D.; Fischer, Reinhard X.

    2017-09-01

    Empirical electronic polarizabilities allow the prediction of total mineral polarizabilities and mean refractive indices of the vast majority of minerals and synthetic oxides. However, deviations from the valence-sum rule at cations in some minerals are associated with large deviations of observed from calculated total polarizabilities. We have identified several groups of minerals and compounds where deviations from the valence-sum rule at cations lead to polarizability deviations of 2-5%: M(SO4)·nH2O, n = 1-6, blödite-group minerals [Na2M2+(SO4)2·4H2O], and the kieserite-related minerals: isokite, panasqueiraite and tilasite. In these minerals, the environment of the M ions contains both O and H2O: Mg[O4(H2O)2] in kieserite, szmikite, and szomolnokite; Mg[O2(H2O)4] in starkeyite, ilesite, and rozenite, and Mg[(H2O)6] in hexahydrite. In compounds where the ligands are only H2O, deviations from the valence-sum rule at the M(H2O)6 groups are not accompanied by significant polarizability deviations. This is the case for epsomite, MgSO4·7H2O; bieberite, CoSO4·7H2O; goslarite, ZnSO4·7H2O, six silicofluorides, MSiF6·6H2O; eighteen Tutton's salts, M2M'(SO4)2·6H2O, where M = K, Rb, Cs and M' = Mg, Mn, Fe, Co, Ni, Cu, and Zn; and eleven MM'(SO4)2·12H2O alums, where M = Na, K, Rb and Cs, and M' = Al, Cr, Ga and In. This is also the case for the sulfates alunogen, Al2(SO4)3·17H2O and halotrichite, FeAl2(SO4)4·22H2O; three hydrated nitrates; one phosphate; three antimonates and two hydrated perchlorates. A possible explanation for this different behavior is that the bond-valence model treats O and H separately, whereas polarizability calculations treat the polarizability of the entire H2O molecule.

  3. Phonon-mediated nuclear spin relaxation in H2O

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Azami, Shinya; Arakawa, Ichiro

    2017-03-01

    A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5-15 K. Temperature dependence of the rate is discussed in terms of the devised model.

  4. Electrochemical Quantification of Extracellular Local H2O2 Kinetics Originating from Single Cells.

    PubMed

    Bozem, Monika; Knapp, Phillip; Mirčeski, Valentin; Slowik, Ewa J; Bogeski, Ivan; Kappl, Reinhard; Heinemann, Christian; Hoth, Markus

    2017-05-15

    H 2 O 2 is produced by all eukaryotic cells under physiological and pathological conditions. Due to its enormous relevance for cell signaling at low concentrations and antipathogenic function at high concentrations, precise quantification of extracellular local H 2 O 2 concentrations ([H 2 O 2 ]) originating from single cells is required. Using a scanning electrochemical microscope and bare platinum disk ultramicroelectrodes, we established sensitive long-term measurements of extracellular [H 2 O 2 ] kinetics originating from single primary human monocytes (MCs) ex vivo. For the electrochemical techniques square wave voltammetry, cyclic and linear scan voltammetry, and chronoamperometry, detection limits for [H 2 O 2 ] were determined to be 5, 50, and 500 nM, respectively. Following phorbol ester stimulation, local [H 2 O 2 ] 5-8 μm above a single MC increased by 3.4 nM/s within the first 10 min before reaching a plateau. After extracellular addition of H 2 O 2 to an unstimulated MC, the local [H 2 O 2 ] decreased on average by 4.2 nM/s due to degradation processes of the cell. Using the scanning mode of the setup, we found that H 2 O 2 is evenly distributed around the producing cell and can still be detected up to 30 μm away from the cell. The electrochemical single-cell measurements were validated in MC populations using electron spin resonance spectroscopy and the Amplex ® UltraRed assay. Innovation and Conclusion: We demonstrate a highly sensitive, spatially, and temporally resolved electrochemical approach to monitor dynamics of production and degradation processes for H 2 O 2 separately. Local extracellular [H 2 O 2 ] kinetics originating from single cells is quantified in real time. Antioxid. Redox Signal. 00, 000-000.

  5. Visible light induced H2PO(4)(-) removal over CuAlO2 catalyst.

    PubMed

    Benreguia, N; Omeiri, S; Bellal, B; Trari, M

    2011-09-15

    The delafossite CuAlO(2) is successfully used for the visible light driven H(2)PO(4)(-) reduction. It is prepared from the nitrates decomposition in order to increase the ratio of reaction surface per given mass. CuAlO(2) is a narrow band gap semiconductor which exhibits a good chemical stability with a corrosion rate of 1.70 μmol year(-1) at neutral pH. The flat band potential (+0.25 V(SCE)) is determined from the Mott-Schottky characteristic. Hence, the conduction band, positioned at (-1.19 V(SCE)), lies below the H(2)PO(4)(-) level yielding a spontaneous reduction under visible illumination. The photocatalytic process is investigated under mild conditions and 30% conversion occurs in less than ~6h with a quantum efficiency of 0.04% under full light. The concentration decreases by a factor of 39% after a second cycle. The photoactivity follows a first order kinetic with a rate constant of 6.6 × 10(-2)h(-1). The possibility of identifying the reaction products via the intensity-potential characteristics is explored. The decrease of the conversion rate over illumination time is due to the competitive water reduction. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. O2 reduction to H2O by the multicopper oxidases.

    PubMed

    Solomon, Edward I; Augustine, Anthony J; Yoon, Jungjoo

    2008-08-14

    In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in nature.

  7. O2 Reduction to H2O by the Multicopper Oxidases

    PubMed Central

    Solomon, Edward I.; Augustine, Anthony J.; Yoon, Jungjoo

    2010-01-01

    In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c Oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in Nature. PMID:18648693

  8. Degradation of 40 selected pharmaceuticals by UV/H2O2.

    PubMed

    Wols, B A; Hofman-Caris, C H M; Harmsen, D J H; Beerendonk, E F

    2013-10-01

    The occurrence of pharmaceuticals in source waters is increasing. Although UV advanced oxidation is known to be an effective barrier against micropollutants, degradation rates are only available for limited amounts of pharmaceuticals. Therefore, the degradation of a large group of pharmaceuticals has been studied in this research for the UV/H2O2 process under different conditions, including pharmaceuticals of which the degradation by UV/H2O2 was never reported before (e.g., metformin, paroxetine, pindolol, sotalol, venlafaxine, etc.). Monochromatic low pressure (LP) and polychromatic medium pressure (MP) lamps were used for three different water matrices. In order to have well defined hydraulic conditions, all experiments were conducted in a collimated beam apparatus. Degradation rates for the pharmaceuticals were determined. For those compounds used in this research that are also reported in literature, measured degradation results are in good agreement with literature data. Pharmaceutical degradation for only photolysis with LP lamps is small, which is increased by using a MP lamp. Most of the pharmaceuticals are well removed when applying both UV (either LP or MP) and H2O2. However, differences in degradation rates between pharmaceuticals can be large. For example, ketoprofen, prednisolone, pindolol are very well removed by UV/H2O2, whereas metformin, cyclophosphamide, ifosfamide are very little removed by UV/H2O2. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Bobjonesite, V4+ O (SO4) (H2O 3, a new mineral species from Temple Mountain, Emery County, Utah, U.S.A

    USGS Publications Warehouse

    Schindler, M.; Hawthorne, F.C.; Huminicki, D.M.C.; Haynes, P.; Grice, Joel D.; Evans, H.T.

    2003-01-01

    Bobjonesite, V4+ O (SO4) (H2O 3, is a new mineral species from Temple Mountain, Emery County, Utah, U.S.A. It occurs as blue-green crusts and efflorescences in fractures in a fossil (Triassic) tree: individual crystals are ??1 mm and are intimately intergrown. Bobjonesite hydrates very easily, and is unstable in all but the driest atmosphere. Its structure was determined on a crystal of bobjonesite: however, the physical properties, optical properties and X-ray powder-diffraction pattern were recorded on the synthetic equivalent, and an electron-microprobe analysis was not possible. Bobjonesite has a pale blue streak, a vitreous luster and no observable fluorescence under ultraviolet light. It has no cleavage or parting. The Mohs hardness is ???1, and the calculated density is 2.28 g/cm3. Bobjonesite is biaxial positive, with ?? 1.555(2 , ?? 1.561(1), ?? 1.574(2), 2V(obs.) = 72(1)??, 2V(calc.) = 69??; it is non-pleochroic, X = b, Y ??? 19?? (in ?? obtuse). Bobjonesite is monoclinic, space group P21/n, cell dimensions from single-crystal data: a 7.3940(5), b 7.4111(3), c 12.0597(9) A??, ?? 106.55(1)??, V 633.5(1) A??3, Z=4. The strongest seven lines in the X-ray powder-diffraction pattern [d in A??(I)(hkl)] are as follows: 5.795(100)(002), 3.498(90)(112), 3.881(48)(1??03), 5.408(37) (101), 4.571(20)(012), 6.962(11 (1??01) and 6.254(11)(011). The chemical formula was derived from crystal-structure analysis; the end-member formula is V O (SO4) (H2O)3. The crystal structure of bobjonesite was refined to an R index of 3.6% for 1105 observed (Fo> 5??F) reflections measured with an automated four-circle X-ray diffractometer using MoK?? X-radiation. There is one V site occupied by V4+ and surrounded by three O atoms and three (H2O) groups in an octahedral arrangement, with one short vanadyl bond (1.577 A??), four similar equatorial bonds (<2.022 A??), and one longer V-O bond (2.278 A??) trans to the vanadyl bond. The structure consists of isolated [V4+2 O2 (H2O)6 (SO4)2

  10. X-ray irradiation activates K+ channels via H2O2 signaling.

    PubMed

    Gibhardt, Christine S; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

    2015-09-09

    Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels.

  11. Triaqua-1κO,2κ2 O-bis­(2,2′-bipyridine)-1κ2 N,N′;2κ2 N,N′-chlorido-1κCl-μ-terephthalato-1:2κ2 O 1:O 4-dicopper(II) nitrate monohydrate

    PubMed Central

    Liu, Yang; Feng, Yong-Lan; Kuang, Dai-Zhi

    2012-01-01

    In the binuclear title compound, [Cu2(C8H4O4)Cl(C10H8N2)2(H2O)3]NO3·H2O, the two crystallographically independent CuII ions have similar coordination environments. One of the CuII ions has a square-pyramidal arrangement, which is defined by a water mol­ecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2′-bipyridine mol­ecule, one carboxyl­ate O atom from a terephthalate ligand and one O atom from a water mol­ecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water mol­ecule. An O—H⋯O and O—H⋯Cl hydrogen-bonded three-dimensional network is formed between the components. PMID:22719307

  12. Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

    PubMed

    Monegan, Jessie D; Bunge, Scott D

    2009-04-06

    The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

  13. Determination of the ortho to para ratio of H2Cl+ and H2O+ from submillimeter observations.

    PubMed

    Gerin, Maryvonne; de Luca, Massimo; Lis, Dariusz C; Kramer, Carsten; Navarro, Santiago; Neufeld, David; Indriolo, Nick; Godard, Benjamin; Le Petit, Franck; Peng, Ruisheng; Phillips, Thomas G; Roueff, Evelyne

    2013-10-03

    The opening of the submillimeter sky with the Herschel Space Observatory has led to the detection of new interstellar molecular ions, H2O(+), H2Cl(+), and HCl(+), which are important intermediates in the synthesis of water vapor and hydrogen chloride. In this paper, we report new observations of H2O(+) and H2Cl(+) performed with both Herschel and ground-based telescopes, to determine the abundances of their ortho and para forms separately and derive the ortho-to-para ratio. At the achieved signal-to-noise ratio, the observations are consistent with an ortho-to-para ratios of 3 for both H2O(+) and H2Cl(+), in all velocity components detected along the lines-of-sight to the massive star-forming regions W31C and W49N. We discuss the mechanisms that contribute to establishing the observed ortho-to-para ratio and point to the need for a better understanding of chemical reactions, which are important for establishing the H2O(+) and H2Cl(+) ortho-to-para ratios.

  14. Design of plasmonic Ag-TiO2/H3PW12O40 composite film with enhanced sunlight photocatalytic activity towards o-chlorophenol degradation.

    PubMed

    Lu, Nan; Wang, Yaqi; Ning, Shiqi; Zhao, Wenjing; Qian, Min; Ma, Ying; Wang, Jia; Fan, Lingyun; Guan, Jiunian; Yuan, Xing

    2017-12-11

    A series of plasmonic Ag-TiO 2 /H 3 PW 12 O 40 composite films were fabricated and immobilized by validated preparation technique. The chemical composition and phase, optical, SPR effect and pore-structure properties together with the morphology of as-prepared composite film are well-characterized. The multi-synergies of as-prepared composite films were gained by combined action of electron-capture action via H 3 PW 12 O 40 , visible-response induced by Ag, and Schottky-junction formed between TiO 2 -Ag. Under simulated sunlight, the maximal K app of o-chlorophenol (o-CP) reached 0.0075 min -1 which was 3.95-fold larger than that of TiO 2 film, while it was restrained obviously under acid condition. In the photocatalytic degradation process, ·OH and ·O 2 - attacked preferentially ortho and para position of o-CP molecule, and accordingly the specific degradation pathways were speculated. The novel composite film exhibited an excellent applicability due to self-regeneration of H 3 PW 12 O 40 , well-protection of metal Ag° and favorable immobilization.

  15. Vibrational spectra of Mg2KH(XO4)2·15H2O (X = P, As) containing dimer units [H(XO4)2

    NASA Astrophysics Data System (ADS)

    Stefov, V.; Koleva, V.; Najdoski, M.; Abdija, Z.; Cahil, A.; Šoptrajanov, B.

    2017-08-01

    Infrared and Raman spectra of Mg2KH(PO4)2·15H2O and Mg2KH(AsO4)2·15H2O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg2KH(XO4)2·15H2O (X = P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO4)2] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C1 crystallographic symmetry of the XO4 groups. The observation of a singlet Raman band for the ν1(XO4) mode as well as the absence of substantial splitting of the ν3(XO4) modes and IR activation of the ν1(XO4) mode suggest that the dimer units [H(XO4)2] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg2KH(AsO4)2·15H2O, both ν1(AsО4) and ν3(AsО4) modes have practically the same wavenumber around 830 cm- 1. It was also established that the ν4(PО4) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D2O librations. As a whole, the spectral picture of Mg2KH(XO4)2·15H2O (X = P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO4·6H2O (X = P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO4)2] play a relatively small part in the general spectral appearance.

  16. Expiratory timing in obstructive sleep apnoeas.

    PubMed

    Cibella, F; Marrone, O; Sanci, S; Bellia, V; Bonsignore, G

    1990-03-01

    Diaphragmatic electromyogram was recorded during NREM sleep in 4 patients affected by obstructive sleep apnoea (OSA) syndrome in order to evaluate the behaviour of expiratory time (TE) in the course of the obstructive apnoea-ventilation cycle. The two components of TE, i.e. time of post-inspiratory inspiratory activity (TPIIA) and time of expiratory phase 2 (TE2) were separately analysed. TPIIA showed a short duration, with only minor variations, within the apnoea, while its duration was more variable and longer in the interapnoeic periods: the longest TPIIA values were associated with the highest inspiratory volumes in the same breaths. This behaviour seemed regulated according to the need of a more or less effective expiratory flow braking, probably as a result of pulmonary stretch receptors discharge. Conversely TE2 showed a continuous gradual modulation, progressively increasing in the pre-apnoeic period, decreasing during the apnoea and increasing in the post-apnoeic period: these TE2 variations seemed related to oscillations in chemical drive. These data show that TE in the obstructive apnoea-ventilation cycle results from a different modulation in its two components and suggest that both mechanical and chemical influences play a role in its overall duration.

  17. Co3(PO4)2·4H2O

    PubMed Central

    Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

    2008-01-01

    Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

  18. Isotopic separation of D.sub.2 O from H.sub.2 O using ruthenium adsorbent

    DOEpatents

    Thiel, Patricia A.

    1990-04-10

    A method of enrichment of D.sub.2 O in solutions of D.sub.2 O in H.sub.2 O by contacting said solutions in the steam phase with hexagonal crystalline to produce enriched D.sub.2 O. The passages may be repeated to achieve a desired amount of D.sub.2 O.

  19. FoxO proteins restrain osteoclastogenesis and bone resorption by attenuating H2O2 accumulation

    PubMed Central

    Bartell, Shoshana M.; Kim, Ha-Neui; Ambrogini, Elena; Han, Li; Iyer, Srividhya; Serra Ucer, S.; Rabinovitch, Peter; Jilka, Robert L.; Weinstein, Robert S.; Zhao, Haibo; O’Brien, Charles A.; Manolagas, Stavros C.; Almeida, Maria

    2014-01-01

    Besides their cell-damaging effects in the setting of oxidative stress, reactive oxygen species (ROS) play an important role in physiological intracellular signalling by triggering proliferation and survival. FoxO transcription factors counteract ROS generation by upregulating antioxidant enzymes. Here we show that intracellular H2O2 accumulation is a critical and purposeful adaptation for the differentiation and survival of osteoclasts, the bone cells responsible for the resorption of mineralized bone matrix. Using mice with conditional loss or gain of FoxO transcription factor function, or mitochondria-targeted catalase in osteoclasts, we demonstrate this is achieved, at least in part, by downregulating the H2O2-inactivating enzyme catalase. Catalase downregulation results from the repression of the transcriptional activity of FoxO1, 3 and 4 by RANKL, the indispensable signal for the generation of osteoclasts, via an Akt-mediated mechanism. Notably, mitochondria-targeted catalase prevented the loss of bone caused by loss of oestrogens, suggesting that decreasing H2O2 production in mitochondria may represent a rational pharmacotherapeutic approach to diseases with increased bone resorption. PMID:24781012

  20. Effects of sevoflurane on ventilator induced lung injury in a healthy lung experimental model.

    PubMed

    Romero, A; Moreno, A; García, J; Sánchez, C; Santos, M; García, J

    2016-01-01

    Ventilator-induced lung injury (VILI) causes a systemic inflammatory response in tissues, with an increase in IL-1, IL-6 and TNF-α in blood and tissues. Cytoprotective effects of sevoflurane in different experimental models are well known, and this protective effect can also be observed in VILI. The objective of this study was to assess the effects of sevoflurane in VILI. A prospective, randomized, controlled study was designed. Twenty female rats were studied. The animals were mechanically ventilated, without sevoflurane in the control group and sevoflurane 3% in the treated group (SEV group). VILI was induced applying a maximal inspiratory pressure of 35 cmH2O for 20 min without any positive end-expiratory pressure for 20 min (INJURY time). The animals were then ventilated 30 min with a maximal inspiratory pressure of 12 cmH2O and 3 cmH2O positive end-expiratory pressure (time 30 min POST-INJURY), at which time the animals were euthanized and pathological and biomarkers studies were performed. Heart rate, invasive blood pressure, pH, PaO2, and PaCO2 were recorded. The lung wet-to-dry weight ratio was used as an index of lung edema. No differences were found in the blood gas analysis parameters or heart rate between the 2 groups. Blood pressure was statistically higher in the control group, but still within the normal clinical range. The percentage of pulmonary edema and concentrations of TNF-α and IL-6 in lung tissue in the SEV group were lower than in the control group. Sevoflurane attenuates VILI in a previous healthy lung in an experimental subclinical model in rats. Copyright © 2015 Sociedad Española de Anestesiología, Reanimación y Terapéutica del Dolor. Publicado por Elsevier España, S.L.U. All rights reserved.

  1. Density Functional Theory Study of the Reaction between d0 Tungsten Alkylidyne Complexes and H2O: Addition versus Hydrolysis.

    PubMed

    Chen, Ping; Zhang, Linxing; Xue, Zi-Ling; Wu, Yun-Dong; Zhang, Xinhao

    2017-06-19

    The reactions of early-transition-metal complexes with H 2 O have been investigated. An understanding of these elementary steps promotes the design of precursors for the preparation of metal oxide materials or supported heterogeneous catalysts. Density functional theory (DFT) calculations have been conducted to investigate two elementary steps of the reactions between tungsten alkylidyne complexes and H 2 O, i.e., the addition of H 2 O to the W≡C bond and ligand hydrolysis. Four tungsten alkylidyne complexes, W(≡CSiMe 3 )(CH 2 SiMe 3 ) 3 (A-1), W(≡CSiMe 3 )(CH 2 t Bu) 3 (B-1), W(≡C t Bu)(CH 2 t Bu) 3 (C-1), and W(≡C t Bu)(O t Bu) 3 (D-1), have been compared. The DFT studies provide an energy profile of the two competing pathways. An additional H 2 O molecule can serve as a proton shuttle, accelerating the H 2 O addition reaction. The effect of atoms at the α and β positions has also been examined. Because the lone-pair electrons of an O atom at the α position can interact with the orbital of the proton, the barrier of the ligand-hydrolysis reaction for D-1 is dramatically reduced. Both the electronic and steric effects of the silyl group at the β position lower the barriers of both the H 2 O addition and ligand-hydrolysis reactions. These new mechanistic findings may lead to the further development of metal complex precursors.

  2. Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

    PubMed

    Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

    2015-01-07

    Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

  3. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

    1995-01-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  4. Multichannel processes of H2O in the 18 eV region

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. Robert; Judge, D. L.

    1988-01-01

    Measurements were made of: (1) the fluorescence cross sections of OH(A 2Sigma+) fragments; (2) the absolute cross sections producing H atoms in the n = 2, 3, and 4 states; (3) the cross section for producing excited O atoms which has an upper limit of 5 x 10 to the -21 sq cm; and (4) the fluorescence cross section for producing H2(a 3Sigma g +) fragments. It is shown that, in the 16-20 eV region, there are excellent correspondences in the peak positions and spacings among the photoabsorption, photoionization spectra, and fluorescence functions of OH(A) and H(n).

  5. Characterization of hMTr1, a Human Cap1 2′-O-Ribose Methyltransferase*

    PubMed Central

    Bélanger, François; Stepinski, Janusz; Darzynkiewicz, Edward; Pelletier, Jerry

    2010-01-01

    Cellular eukaryotic mRNAs are capped at their 5′ ends with a 7-methylguanosine nucleotide, a structural feature that has been shown to be important for conferring mRNA stability, stimulating mRNA biogenesis (splicing, poly(A) addition, nucleocytoplasmic transport), and increasing translational efficiency. Whereas yeast mRNAs have no additional modifications to the cap, called cap0, higher eukaryotes are methylated at the 2′-O-ribose of the first or the first and second transcribed nucleotides, called cap1 and cap2, respectively. In the present study, we identify the methyltransferase responsible for cap1 formation in human cells, which we call hMTr1 (also known as FTSJD2 and ISG95). We show in vitro that hMTr1 catalyzes specific methylation of the 2′-O-ribose of the first nucleotide of a capped RNA transcript. Using siRNA-mediated knockdown of hMTr1 in HeLa cells, we demonstrate that hMTr1 is responsible for cap1 formation in vivo. PMID:20713356

  6. H2/O2 three-body rates at high temperatures

    NASA Technical Reports Server (NTRS)

    Marinelli, William J.; Kessler, William J.; Piper, Lawrence G.; Rawlins, W. Terry

    1990-01-01

    The extraction of thrust from air breathing hypersonic propulsion systems is critically dependent on the degree to which chemical equilibrium is reached in the combustion process. In the combustion of H2/Air mixtures, slow three-body chemical reactions involving H-atoms, O-atoms, and the OH radical play an important role in energy extraction. A first-generation high temperature and pressure flash-photolysis/laser-induced fluorescence reactor was designed and constructed to measure these important three-body rates. The system employs a high power excimer laser to produce these radicals via the photolysis of stable precursors. A novel two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical thickness or O2 absorption problems. To demonstrate the feasibility of the technique the apparatus in the program is designed to perform preliminary measurements on the H + O2 + M reaction at temperatures from 300 to 835 K.

  7. Spectral and thermal studies of MgI2·8H2O

    NASA Astrophysics Data System (ADS)

    Koleva, Violeta; Stefov, Viktor; Najdoski, Metodija; Ilievski, Zlatko; Cahil, Adnan

    2017-10-01

    In the present contribution special attention is paid to the spectroscopic and thermal characterization of MgI2·8H2O which is the stable hydrated form at room temperature. The infrared spectra of MgI2·8H2O and its deuterated analogues recorded at room and liquid nitrogen temperature are presented and interpreted. In the low-temperature diference infrared spectrum of the slightly deuterated analogue (≈5% D) at least four bands are found out of the expected five (at 2595, 2550, 2538 and 2495 cm-1) as a result of the uncoupled O-D oscillators in the isotopically isolated HOD molecules. Multiple bands are observed in the water bending region and only two bands of the HOH librational modes are found. For more precise and deep description of the processes occurring upon heating of MgI2·8H2O we have applied simultaneous TG/DTA/Mass spectrometry technique identifying the gases evolved during the thermal transformations. We have established that the thermal decomposition of MgI2·8H2O is a complex process that takes place in two main stages. In the first stage (between 120 and 275 °C) the salt undergoes a partial stepwise dehydration to MgI2·2H2O followed by a hydrolytic decomposition with formation of magnesium hydroxyiodide Mg(OH)1.44I0.56 accompanied with simultaneous release of H2O and HI. In the second stage Mg(OH)1.44I0.56 is completely decomposed to MgO with elimination of gaseous H2O, HI, I2 and H2. Infrared spectra of the annealed samples heated between 190 and 270 °C confirmed the formation of magnesium hydroxyiodide.

  8. Phase and Physicochemical Properties Diagrams of Quaternary System Li2B4O7 + Na2B4O7 + Mg2B6O11 + H2O

    NASA Astrophysics Data System (ADS)

    Wang, Shi-qiang; Du, Xue-min; Jing, Yan; Guo, Ya-fei; Deng, Tian-long

    2017-12-01

    The phase and physicochemical properties diagrams of the quaternary system (Li2B4O7 + Na2B4O7 + Mg2B6O11) at 288.15 K and 0.1 MPa were constructed using the solubilities, densities, and refractive indices measured. In the phase diagrams of the system there are one invariant point, three univariant isothermic dissolution curves, and three crystallization regions corresponding to Li2B4O7 · 3H2O, Na2B4O7 · 10H2O, and Mg2B6O11 · 15H2O, respectively. The solution density, refractive index of the quaternary system changes regularly with the increasing of Li2B4O7 concentration. The calculated values of density and refractive index using empirical equations of the quaternary system are in good agreement with the experimental values.

  9. Fe{sub 2}O{sub 3}-Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses as lithium-free nonsilicate pH responsive glasses – Compatibility between pH responsivity and hydrophobicity

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

    Hashimoto, Tadanori, E-mail: hasimoto@chem.mie-u.ac.jp; Hamajima, Mitsuaki; Ohta, Honami

    Highlights: • Fe{sub 2}O{sub 3}-rich FeBiB glasses show high pH sensitivity and short pH response time. • Bi{sub 2}O{sub 3}-rich FeBiB glasses show relatively high contact angle for water. • FeBiB glasses are lithium-free nonsilicate pH responsive ones. • pH responsivity and hydrophobicity are obtained for optimum glass compositions. - Abstract: Lithium silicate-based glasses have widely been used as commercially available pH glass electrodes. It was revealed that Ti{sup 3+}-containing titanophosphate (TiO{sub 2}-P{sub 2}O{sub 5}, TP) glasses are pH responsive as lithium-free nonsilicate glasses for the first time. TP glasses with the compatibility between pH responsivity and self-cleaning property weremore » obtained by the sequential post-annealing (oxidation and reduction) of as-prepared glasses. Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} (BiB) glasses are relatively hydrophobic and are expected to show anti-fouling effect. They are unsuitable for pH responsive glasses, because they have high electrical resistivity. In the present study, xFe{sub 2}O{sub 3}·yBi{sub 2}O{sub 3}·(100 − x − y)B{sub 2}O{sub 3} glasses (xFeyBiB, x = 0–20 mol%, y = 20–80 mol%) glasses were selected as new pH responsive glasses with hydrophobicity, because Fe{sub 2}O{sub 3} is a representative component for causing hopping conduction to the glasses. BiB glass did not show pH responsivity, whereas xFeyBiB glasses showed good pH responsivity. xFeyBiB glasses are lithium-free nonsilicate pH responsive ones as well as TP glasses. The electrical resistivity and pH response time decreased with increasing Fe{sub 2}O{sub 3} content. The pH repeatability for standard solutions increased with increasing Bi{sub 2}O{sub 3} content. Silicate glass (20Fe70BiSi) showed better pH responsivity but lower contact angle than those of borate glass (20Fe70BiB). pH sensitivity increased in order of TP glasses (about 80%), xFeyBiB glasses (about 90%) and commercial pH responsive glass (about 100

  10. Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

    PubMed

    Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

    2018-01-01

    H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

  11. Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures

    PubMed Central

    Wang, Zhong-hua; Gao, Xing-cun; Liu, Cheng-hao; Qi, Han-bing

    2018-01-01

    H2O2 was adopted to oxidize NO in simulated flue gas at 100–500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300–500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption. PMID:29668672

  12. O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

    PubMed

    Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

    2017-10-05

    Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

  13. Microhydration effects on the electronic spectra of protonated polycyclic aromatic hydrocarbons: [naphthalene-(H2O)n = 1,2]H+

    NASA Astrophysics Data System (ADS)

    Alata, Ivan; Broquier, Michel; Dedonder-Lardeux, Claude; Jouvet, Christophe; Kim, Minho; Sohn, Woon Yong; Kim, Sang-su; Kang, Hyuk; Schütz, Markus; Patzer, Alexander; Dopfer, Otto

    2011-02-01

    Vibrational and electronic spectra of protonated naphthalene (NaphH+) microsolvated by one and two water molecules were obtained by photofragmentation spectroscopy. The IR spectrum of the monohydrated species is consistent with a structure with the proton located on the aromatic molecule, NaphH+-H2O. Similar to isolated NaphH+, the first electronic transition of NaphH+-H2O (S1) occurs in the visible range near 500 nm. The doubly hydrated species lacks any absorption in the visible range (420-600 nm) but absorbs in the UV range, similar to neutral Naph. This observation is consistent with a structure, in which the proton is located on the water moiety, Naph-(H2O)2H+. Ab initio calculations for [Naph-(H2O)n]H+ confirm that the excess proton transfers from Naph to the solvent cluster upon attachment of the second water molecule.

  14. Do aerosols influence the diurnal variation of H2O2 in the atmosphere?

    NASA Astrophysics Data System (ADS)

    Liang, H.; Chen, Z.; Wu, Q.; Huang, D.; Zhao, Y.

    2013-12-01

    Hydrogen peroxide (H2O2) and organic peroxides are crucial reactive species that are involved in the cycling of HOx (OH and HO2) radicals and the formation of secondary inorganic and organic aerosols in the atmosphere. Despite the importance of peroxides, their formation and removal mechanisms with the coexistence of aerosols are as yet less well known. From June 10 to July 15 2013, summertime surface measurements for atmospheric peroxides were simultaneously obtained in urban Beijing (UB) and Gucheng (GC). The UB site is located in the northern downtown of Beijing city, while the GC site is a rural site located in the North China Plain and ~100 km southwest of Beijing. In both sites, the major peroxides were determined to be H2O2, methyl hydroperoxide (MHP), peroxyformic acid (PFA) and peroxyacetic acid (PAA). By comparing the concentrations of PFA and PAA in the gas phase and rainwater, for the first time, we estimated the Henry's law constant for PFA as ~210 M atm-1 at 298 K, a quarter of that for PAA. Interestingly, we observed different H2O2 profiles in the two sites as follows: (i) the average concentration of H2O2 in UB was 50% higher than that in GC; (ii) H2O2 in GC reached its peak concentration at around 15:30, whereas the peak concentration in UB appeared at as late as 21:00; and (iii) the daily variation of H2O2 in GC generally kept consistent with that of O3 and organic peroxides while it was not always the case in UB. These differences indicate a hitherto unrecognized storage-release mechanism for H2O2 in UB, that is, an extra sink in the noontime and an extra source in the early evening. The extra source of H2O2 would enhance the aerosol phase OH radical in the early evening by the Fenton reaction. A box model analysis shows that the impacts of aerosols were majorly responsible to this unrecognized mechanism, although NOx, regional transport and planet boundary layer height also contributed a minor part. Aerosols participated in the storage

  15. Synthesis and physicochemical characterization of carbon backbone modified [Gd(TTDA)(H2O)]2- derivatives.

    PubMed

    Chang, Ya-Hui; Chen, Chiao-Yun; Singh, Gyan; Chen, Hsing-Yin; Liu, Gin-Chung; Goan, Yih-Gang; Aime, Silvio; Wang, Yun-Ming

    2011-02-21

    The present study was designed to exploit optimum lipophilicity and high water-exchange rate (k(ex)) on low molecular weight Gd(III) complexes to generate high bound relaxivity (r(1)(b)), upon binding to the lipophilic site of human serum albumin (HSA). Two new carbon backbone modified TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triazadodecanedioic acid) derivatives, CB-TTDA and Bz-CB-TTDA, were synthesized. The complexes [Gd(CB-TTDA)(H(2)O)](2-) and [Gd(Bz-CB-TTDA)(H(2)O)](2-) both display high stability constant (log K(GdL) = 20.28 and 20.09, respectively). Furthermore, CB-TTDA (log K(Gd/Zn) = 4.22) and Bz-CB-TTDA (log K(Gd/Zn) = 4.12) exhibit superior selectivity of Gd(III) against Zn(II) than those of TTDA (log K(Gd/Zn) = 2.93), EPTPA-bz-NO(2) (log K(Gd/Zn) = 3.19), and DTPA (log K(Gd/Zn) = 3.76). However, the stability constant values of [Gd(CB-TTDA)(H(2)O)](2-) and [Gd(Bz-CB-TTDA)(H(2)O)](2-) are lower than that of MS-325. The parameters that affect proton relaxivity have been determined in a combined variable temperature (17)O NMR and NMRD study. The water exchange rates are comparable for the two complexes, 232 × 10(6) s(-1) for [Gd(CB-TTDA)(H(2)O)](2-) and 271 × 10(6) s(-1) for [Gd(Bz-CB-TTDA)(H(2)O)](2-). They are higher than those of [Gd(TTDA)(H(2)O)](2-) (146 × 10(6) s(-1)), [Gd(DTPA)(H(2)O)](2-) (4.1 × 10(6) s(-1)), and MS-325 (6.1 × 10(6) s(-1)). Elevated stability and water exchange rate indicate that the presence of cyclobutyl on the carbon backbone imparts rigidity and steric constraint to [Gd(CB-TTDA)(H(2)O)](2-)and [Gd(Bz-CB-TTDA)(H(2)O)](2-). In addition, the major objective for selecting the cyclobutyl is to tune the lipophilicity of [Gd(Bz-CB-TTDA)(H(2)O)](2-). The binding affinity of [Gd(Bz-CB-TTDA)(H(2)O)](2-) to HSA was evaluated by ultrafiltration study across a membrane with a 30 kDa MW cutoff, and the first three stepwise binding constants were determined by fitting the data to a stoichiometric model. The binding association constants (K

  16. Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

    PubMed

    Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

    2015-01-01

    The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

  17. X-ray irradiation activates K+ channels via H2O2 signaling

    PubMed Central

    Gibhardt, Christine S.; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

    2015-01-01

    Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels. PMID:26350345

  18. Template-free fabrication of hollow N-doped carbon sphere (h-NCS) to synthesize h-NCS@PANI positive material for MoO3//h-NCS@PANI asymmetric supercapacitor

    NASA Astrophysics Data System (ADS)

    Li, Xiaoqin; Xiang, Xinxin; Liu, Yunhua; Xiao, Dan

    2018-06-01

    Asymmetric supercapacitors (ASCs) based on pseudocapacitor electrode materials are vital to improve the electrochemical properties of devices in aqueous electrolytes. This study fabricates hollow N-doped carbon sphere (h-NCS) to produce h-NCS@PANI nanocomposite as positive electrode and α-MoO3 as negative electrode to assemble ASC device. In particular, a facile template-free synthesis method, catalyzed by Cu2+, is used to prepare hollow PANI nanosphere precursor to build h-NCS. The mechanism of the precursor formation is illustrated in detail. After polymerization of PANI on the surface of h-NCS, the capacitance increases to 327 F g-1 at 1 A g-1. Furthermore, a hydrothermal reaction is carried out to produce α-MoO3 negative electrode material. The maximum specific capacitance of 720 F g-1 is achieved at 1 A g-1. The obtained h-NCS@PANI and α-MoO3 are utilized to construct an ASC device. The electrochemical properties of this device are investigated comprehensively. The maximum energy density of 34.1 W h kg-1 and power density of 9350.6 W kg-1 are observed, which provide an insight into the development of ASCs.

  19. CO2-induced pH reduction increases physiological toxicity of nano-TiO2 in the mussel Mytilus coruscus

    PubMed Central

    Hu, Menghong; Lin, Daohui; Shang, Yueyong; Hu, Yi; Lu, Weiqun; Huang, Xizhi; Ning, Ke; Chen, Yimin; Wang, Youji

    2017-01-01

    The increasing usage of nanoparticles has caused their considerable release into the aquatic environment. Meanwhile, anthropogenic CO2 emissions have caused a reduction of seawater pH. However, their combined effects on marine species have not been experimentally evaluated. This study estimated the physiological toxicity of nano-TiO2 in the mussel Mytilus coruscus under high pCO2 (2500–2600 μatm). We found that respiration rate (RR), food absorption efficiency (AE), clearance rate (CR), scope for growth (SFG) and O:N ratio were significantly reduced by nano-TiO2, whereas faecal organic weight rate and ammonia excretion rate (ER) were increased under nano-TiO2 conditions. High pCO2 exerted lower effects on CR, RR, ER and O:N ratio than nano-TiO2. Despite this, significant interactions of CO2-induced pH change and nano-TiO2 were found in RR, ER and O:N ratio. PCA showed close relationships among most test parameters, i.e., RR, CR, AE, SFG and O:N ratio. The normal physiological responses were strongly correlated to a positive SFG with normal pH and no/low nano-TiO2 conditions. Our results indicate that physiological functions of M. coruscus are more severely impaired by the combination of nano-TiO2 and high pCO2. PMID:28054631

  20. CO2-induced pH reduction increases physiological toxicity of nano-TiO2 in the mussel Mytilus coruscus

    NASA Astrophysics Data System (ADS)

    Hu, Menghong; Lin, Daohui; Shang, Yueyong; Hu, Yi; Lu, Weiqun; Huang, Xizhi; Ning, Ke; Chen, Yimin; Wang, Youji

    2017-01-01

    The increasing usage of nanoparticles has caused their considerable release into the aquatic environment. Meanwhile, anthropogenic CO2 emissions have caused a reduction of seawater pH. However, their combined effects on marine species have not been experimentally evaluated. This study estimated the physiological toxicity of nano-TiO2 in the mussel Mytilus coruscus under high pCO2 (2500-2600 μatm). We found that respiration rate (RR), food absorption efficiency (AE), clearance rate (CR), scope for growth (SFG) and O:N ratio were significantly reduced by nano-TiO2, whereas faecal organic weight rate and ammonia excretion rate (ER) were increased under nano-TiO2 conditions. High pCO2 exerted lower effects on CR, RR, ER and O:N ratio than nano-TiO2. Despite this, significant interactions of CO2-induced pH change and nano-TiO2 were found in RR, ER and O:N ratio. PCA showed close relationships among most test parameters, i.e., RR, CR, AE, SFG and O:N ratio. The normal physiological responses were strongly correlated to a positive SFG with normal pH and no/low nano-TiO2 conditions. Our results indicate that physiological functions of M. coruscus are more severely impaired by the combination of nano-TiO2 and high pCO2.

  1. Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

    NASA Astrophysics Data System (ADS)

    Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

    1983-12-01

    Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.

  2. Crystalline and amorphous H2O on Charon

    NASA Astrophysics Data System (ADS)

    Dalle Ore, Cristina M.; Cruikshank, Dale P.; Grundy, Will M.; Ennico, Kimberly; Olkin, Catherine B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.

    2015-11-01

    Charon, the largest satellite of Pluto, is a gray-colored icy world covered mostly in H2O ice, with spectral evidence for NH3, as previously reported (Cook et al. 2007, Astrophys. J. 663, 1406-1419 Merlin, et al. 2010, Icarus, 210, 930; Cook, et al. 2014, AAS/Division for Planetary Sciences Meeting Abstracts, 46, #401.04). Images from the New Horizons spacecraft reveal a surface with terrains of widely different ages and a moderate degree of localized coloration. The presence of H2O ice in its crystalline form (Brown & Calvin 2000 Science 287, 107-109; Buie & Grundy 2000 Icarus 148, 324-339; Merlin et al, 2010) along with NH3 is consistent with a fresh surface.The phase of H2O ice is a key tracer of variations in temperature and physical conditions on the surface of outer Solar System objects. At Charon’s surface temperature H2O is expected to be amorphous, but ground-based observations (e.g., Merlin et al. 2010) show a clearly crystalline signature. From laboratory experiments it is known that amorphous H2O ice becomes crystalline at temperatures of ~130 K. Other mechanisms that can change the phase of the ice from amorphous to crystalline include micro-meteoritic bombardment (Porter et al. 2010, Icarus, 208, 492) or resurfacing processes such as cryovolcanism.New Horizons observed Charon with the LEISA imaging spectrometer, part of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Science Reviews, 140, 129). Making use of high spatial resolution (better than 10 km/px) and spectral resolving power of 240 in the wavelength range 1.25-2.5 µm, and 560 in the range 2.1-2.25 µm, we report on an analysis of the phase of H2O ice on parts of Charon’s surface with a view to investigate the recent history and evolution of this small but intriguing object.This work was supported by NASA’s New Horizons project.

  3. Photochemical Generation of H_{2}NCNX, H_{2}NNCX, H_{2}NC(NX) (x = O, s) in Low-Temperature Matrices

    NASA Astrophysics Data System (ADS)

    Voros, Tamas; Lajgut, Gyozo Gyorgy; Magyarfalvi, Gabor; Tarczay, Gyorgy

    2017-06-01

    The [NH_{2}, C, N, O] and the [NH_{2}, C, N, S] systems were investigated by quantum-chemical computations and matrix-isolation spectroscopic methods. The equilibrium structures of the isomers and their relative energies were determined by CCSD(T) method. This was followed by the computation of the harmonic and anharmonic vibrational wavenumbers, infrared intensities, relative Raman activities and UV excitation energies. These computed data were used to assist the identification of products obtained by UV laser photolysis of 3,4-diaminofurazan, 3,4-diaminothiadiazole and 1,2,4-thiadiazole-3,5-diamine in low-temperature Ar and Kr matrices. Experimentally, first the precursors were studied by matrix-isolation IR and UV spectroscopic methods. Based on these UV spectra, different wavelengths were selected for photolysis. The irradiations, carried out by a tunable UV laser-light source, resulted in the decomposition of the precursors, and in the appearance of new bands in the IR spectra. Some of these bands were assigned to cyanamide (H_{2}NCN) and its isomer, the carbodiimide molecule (HNCNH), generated from H_{2}NCN. By the analysis of the relative absorbance vs. photolysis time curves, the other bands were grouped to three different species both for the O- and the S-containing systems. In the case of the O-containing isomers, these bands were assigned to the H_{2}NNCO:H_{2}NCN, and H_{2}NCNO:H_{2}NCN complexes, and to the ring-structure H_{2}NC(NO) isomer. In a similar way, the complexes of H_{2}NNCS and H_{2}NCNS with the H_{2}NCN, and H_{2}NC(NS) were also identified. 1,2,4-thiadiazole-3,5-diamine was also investigated in similar way like the above mentioned precursors. The results of this study also support the identification of the new S-containing isomers. Except for H_{2}NNCO and H_{2}NCNS, these molecules were not identified previously. It is expected that at least some of these species, like the methyl isocyanate (CH_{3}CNO) isomer, are present and could be

  4. Modeling approaches to describe H2O and CO2 exchange in mare ecosystems

    NASA Astrophysics Data System (ADS)

    Olchev, A.; Novenko, E.; Volkova, E.

    2012-04-01

    The modern climatic conditions is strongly influenced by both internal variability of climatic system, and various external natural and anthropogenic factors (IPCC 2007). Significant increase of concentration of greenhouse gases in the atmosphere and especially the growth of atmospheric CO2 due to human activity are considered as the main factors that are responsible for global warming and climate changes. A significant part of anthropogenic CO2 is absorbed from the atmosphere by land biota and especially by vegetation cover. However, it is still not completely clear what is the role of different land ecosystems and especially forests and mares in global cycles of H2O and CO2 and what is a sensitivity of these ecosystems to climate changes. Within the frameworks of this study the spatial and temporal variability of H2O and CO2 fluxes in different types of mare ecosystems of the forest-steppe zone in European part of Russia was described using modeling approaches and results of field measurements. For this modeling and experimental study the mare ecosystems of Tula region were selected. The Tula region is located mostly in the forest-steppe zone and it is unique area for such studies because almost all existed types of mare ecosystems of Northern Eurasia distinguished by a geomorphological position, water and mineral supply can be found there. Most mares in Tula region have a relatively small size and surrounded by very heterogeneous forests that make not possible an application of the classical measuring and modeling approaches e.g. an eddy covariance technique or one-dimensional H2O and CO2 exchange models for flux estimation in such sites. In our study to describe the radiation, sensible heat, H2O and CO2 exchange between such heterogeneous mare ecosystems and the atmosphere a three-dimensional model Forbog-3D and one-dimensional Mixfor-SVAT were applied. The main concept used in the Forbog-3D and Mixfor-SVAT models is an aggregated description of physical and

  5. Influence of H2O2 on LPG fuel performance evaluation

    NASA Astrophysics Data System (ADS)

    Khan, Muhammad Saad; Ahmed, Iqbal; Mutalib, Mohammad Ibrahim bin Abdul; Nadeem, Saad; Ali, Shahid

    2014-10-01

    The objective of this mode of combustion is to insertion of hydrogen peroxide (H2O2) to the Liquefied Petroleum Gas (LPG) combustion on spark plug ignition engines. The addition of hydrogen peroxide may probably decrease the formation of NOx, COx and unburned hydrocarbons. Hypothetically, Studies have shown that addition of hydrogen peroxide to examine the performance of LPG/H2O2 mixture in numerous volumetric compositions starting from lean LPG until obtaining a better composition can reduce the LPG fuel consumption. The theory behind this idea is that, the addition of H2O2 can cover the lean operation limit, increase the lean burn ability, diminution the burn duration along with controlling the exhaust emission by significantly reducing the greenhouse gaseous.

  6. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    NASA Astrophysics Data System (ADS)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  7. Bleaching of cotton fabric with tetraacetylhydrazine as bleach activator for H2O2.

    PubMed

    Liu, Kai; Zhang, Xuan; Yan, Kelu

    2018-05-15

    Tetraacetylhydrazine (TH) as bleach activator for H 2 O 2 cotton bleaching was synthesized and characterized by 1 H NMR, 13 C NMR and MS spectra. TH has better solubility than that of TAED. The CIE whiteness index (WI), H 2 O 2 decomposition rate and bursting strength were employed to investigate the performance of H 2 O 2 /TH bleaching system. By addition of TH, WI and H 2 O 2 decomposition rate increased significantly at 70 °C. Bleaching temperature, NaHCO 3 concentration and bleaching time were also discussed in detail and the loss of bursting strength is not clear. By using benzenepentacarboxylic acid (BA) as a fluorescent probe for hydroxyl radical detection, the bleaching process of H 2 O 2 /TH system was investigated. Acetylhydrazine and diacetylhydrazine were also utilized to further confirm the process. In addition, bimolecular decomposition was investigated by using 9,10-dimethylanthracene (DMA) as fluorescent probe of 1 O 2 . Based on these experimental results, the bleaching mechanism of H 2 O 2 /TH system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Comparisons of multilayer H2O adsorption onto the (110) surfaces of alpha-TiO2 and SnO2 as calculated with density functional theory.

    PubMed

    Bandura, Andrei V; Kubicki, James D; Sofo, Jorge O

    2008-09-18

    Mono- and bilayer adsorption of H2O molecules on TiO2 and SnO 2 (110) surfaces has been investigated using static planewave density functional theory (PW DFT) simulations. Potential energies and structures were calculated for the associative, mixed, and dissociative adsorption states. The DOS of the bare and hydrated surfaces has been used for the analysis of the difference between the H2O interaction with TiO2 and SnO 2 surfaces. The important role of the bridging oxygen in the H2O dissociation process is discussed. The influence of the second layer of H2O molecules on relaxation of the surface atoms was estimated.

  9. Vibrational spectra of Mg2KH(XO4)2·15H2O (X=P, As) containing dimer units [H(XO4)2].

    PubMed

    Stefov, V; Koleva, V; Najdoski, M; Abdija, Z; Cahil, A; Šoptrajanov, B

    2017-08-05

    Infrared and Raman spectra of Mg 2 KH(PO 4 ) 2 ·15H 2 O and Mg 2 KH(AsO 4 ) 2 ·15H 2 O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO 4 ) 2 ] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO 4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C 1 crystallographic symmetry of the XO 4 groups. The observation of a singlet Raman band for the ν 1 (XO 4 ) mode as well as the absence of substantial splitting of the ν 3 (XO 4 ) modes and IR activation of the ν 1 (XO 4 ) mode suggest that the dimer units [H(XO 4 ) 2 ] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg 2 KH(AsO 4 ) 2 ·15H 2 O, both ν 1 (AsО 4 ) and ν 3 (AsО 4 ) modes have practically the same wavenumber around 830cm -1 . It was also established that the ν 4 (PО 4 ) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D 2 O librations. As a whole, the spectral picture of Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO 4 ·6H 2 O (X=P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO 4 ) 2 ] play a relatively small part in the general spectral appearance. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Association Between Expiratory Central Airway Collapse and Respiratory Outcomes Among Smokers.

    PubMed

    Bhatt, Surya P; Terry, Nina L J; Nath, Hrudaya; Zach, Jordan A; Tschirren, Juerg; Bolding, Mark S; Stinson, Douglas S; Wilson, Carla G; Curran-Everett, Douglas; Lynch, David A; Putcha, Nirupama; Soler, Xavi; Wise, Robert A; Washko, George R; Hoffman, Eric A; Foreman, Marilyn G; Dransfield, Mark T

    2016-02-02

    Central airway collapse greater than 50% of luminal area during exhalation (expiratory central airway collapse [ECAC]) is associated with cigarette smoking and chronic obstructive pulmonary disease (COPD). However, its prevalence and clinical significance are unknown. To determine whether ECAC is associated with respiratory morbidity in smokers independent of underlying lung disease. Analysis of paired inspiratory-expiratory computed tomography images from a large multicenter study (COPDGene) of current and former smokers from 21 clinical centers across the United States. Participants were enrolled from January 2008 to June 2011 and followed up longitudinally until October 2014. Images were initially screened using a quantitative method to detect at least a 30% reduction in minor axis tracheal diameter from inspiration to end-expiration. From this sample of screen-positive scans, cross-sectional area of the trachea was measured manually at 3 predetermined levels (aortic arch, carina, and bronchus intermedius) to confirm ECAC (>50% reduction in cross-sectional area). Expiratory central airway collapse. The primary outcome was baseline respiratory quality of life (St George's Respiratory Questionnaire [SGRQ] scale 0 to 100; 100 represents worst health status; minimum clinically important difference [MCID], 4 units). Secondary outcomes were baseline measures of dyspnea (modified Medical Research Council [mMRC] scale 0 to 4; 4 represents worse dyspnea; MCID, 0.7 units), baseline 6-minute walk distance (MCID, 30 m), and exacerbation frequency (events per 100 person-years) on longitudinal follow-up. The study included 8820 participants with and without COPD (mean age, 59.7 [SD, 6.9] years; 4667 [56.7%] men; 4559 [51.7%] active smokers). The prevalence of ECAC was 5% (443 cases). Patients with ECAC compared with those without ECAC had worse SGRQ scores (30.9 vs 26.5 units; P < .001; absolute difference, 4.4 [95% CI, 2.2-6.6]) and mMRC scale scores (median, 2

  11. Ab Initio Reaction Kinetics of CH 3 O$$\\dot{C}$$(=O) and $$\\dot{C}$$H 2 OC(=O)H Radicals

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

    Tan, Ting; Yang, Xueliang; Ju, Yiguang

    The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3Omore » $$\\dot{C}$$(=O)) and (formyloxy)methyl radical ($$\\dot{C}$$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$$\\dot{C}$$(=O) to $$\\dot{C}$$H3 and CO2 is predicted to be much faster than dissociating to CH3$$\\dot{O}$$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$$\\dot{C}$$(=O) and $$\\dot{C}$$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$$\\dot{O}$$ removal mechanisms under atmospheric conditions, the reaction kinetics of

  12. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  13. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

    PubMed

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-27

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  14. Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

    PubMed

    Cao, Zhiji; Balasubramanian, K

    2009-10-28

    Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

  15. Towards a Quantum Dynamical Study of the H_2O+H_2O Inelastic Collision: Representation of the Potential and Preliminary Results

    NASA Astrophysics Data System (ADS)

    Ndengue, Steve Alexandre; Dawes, Richard

    2017-06-01

    Water, an essential ingredient of life, is prevalent in space and various media. H_2O in the gas phase is the major polyatomic species in the interstellar medium (ISM) and a primary target of current studies of collisional dynamics. In recent years a number of theoretical and experimental studies have been devoted to H_2O-X (with X=He, H_2, D_2, Ar, ?) elastic and inelastic collisions in an effort to understand rotational distributions of H_2O in molecular clouds. Although those studies treated several abundant species, no quantum mechanical calculation has been reported to date for a nonlinear polyatomic collider. We present in this talk the preliminary steps toward this goal, using the H_2O molecule itself as our collider, the very accurate MB-Pol surface to describe the intermolecular interaction and the MultiConfiguration Time Dependent (MCTDH) algorithm to study the dynamics. One main challenge in this effort is the need to express the Potential Energy Surface (PES) in a sum-of-products form optimal for MCTDH calculations. We will describe how this was done and present preliminary results of state-to-state probabilities.

  16. Site-specific vibrational spectral signatures of water molecules in the magic H3O+(H2O)20 and Cs+(H2O)20 clusters

    PubMed Central

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; Johnson, Mark A.; Heine, Nadja; Gewinner, Sandy; Schöllkopf, Wieland; Esser, Tim K.; Fagiani, Matias R.; Knorke, Harald; Asmis, Knut R.

    2014-01-01

    Theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H3O+ and Cs+ ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm−1 range. The magic H3O+(H2O)20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface. PMID:25489068

  17. Site-specific vibrational spectral signatures of water molecules in the magic H 3O +(H 2O) 20 and Cs +(H 2O) 20 clusters

    DOE PAGES

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; ...

    2014-12-08

    Here, theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H 3O + and Cs +more » ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm -1 range. The magic H 3O +(H 2O) 20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface.« less

  18. Hygroscopic La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O: Insight into the evolution of borate fundamental building blocks

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

    Zhao, Biao-Chun, E-mail: zhaobiaochun@sohu.com; Sun, Wei, E-mail: 421221789@qq.com; Ren, Wei-Jian, E-mail: 935428502@qq.com

    2013-10-15

    Borates have exceptionally diverse fundamental building blocks (FBBs), but factors controlling the formation of borate FBBs are poorly understood. The title compound La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O crystallizes in the space group P2{sub 1}/n with a=6.5396(12) Å, b=15.550(3) Å, c=10.6719(19) Å, β=90.44(1)° and Z=4 at 173(2) K. Its structure has been refined from single-crystal X-ray diffraction data to R{sub 1}=0.049 (for 2465) and wR{sub 2}=0.173 (for 2459 I>2σ(I)). This structure analysis and first-principles calculations show that the change of the FBB from 3Δ2□ in the title compound to 2Δ3□ in La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O is accompanied by amore » rotation of the NO{sub 3} group. FTIR, Rietveld and thermal analysis results show that the hygroscopic title compound is partially changed to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O, with the conversion of [BO{sub 3}] to [BO{sub 3}(H{sub 2}O)] by water absorption. - Graphical abstract: The change of fundamental building blocks from La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O is accompanied by a rotation of the NO{sub 3} group . Display Omitted - Highlights: • Synthesis of a new hydrous lanthanum polyborate nitrate. • Single-crystal XRD structure with the 3Δ2⎕ FBB and an oriented NO{sub 3} group. • DFT calculations locate the H positions in three lanthanide polyborate nitrates. • Rietveld, FTIR and DFT results show hygroscopicity changes the FBBs.« less

  19. Conductivity measurements on H 2O-bearing CO 2-rich fluids

    DOE PAGES

    Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; ...

    2014-09-10

    Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H 2O to CO 2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO 2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H 2O concentrationsmore » up to ~1600 ppmw (xH 2O ≈ 3.9 x 10 -3), corresponding to the H 2O solubility limit in liquid CO 2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO 2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

  20. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells.

    PubMed

    Sim, Junyoung; An, Junyeong; Elbeshbishy, Elsayed; Ryu, Hodon; Lee, Hyung-Sool

    2015-11-01

    Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2O2 conversion efficiency was negligible at 0.3-12%. Current density decreased for passive O2 diffusion to the cathode, but H2O2 conversion efficiency increased by 65%. An MEC equipped with a gas diffusion cathode was operated with acetate medium and domestic wastewater, which presented relatively high H2O2 conversion efficiency from 36% to 47%, although cathode overpotential was fluctuated. Due to different current densities, the maximum H2O2 production rate was 141 mg H2O2/L-h in the MEC fed with acetate medium, but it became low at 6 mg H2O2/L-h in the MEC fed with the wastewater. Our study clearly indicates that improving anodic current density and mitigating membrane fouling would be key parameters for large-scale H2O2-MECs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Ilyukhinite (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 • 3H2O, a New Mineral of the Eudialyte Group

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Rastsvetaeva, R. K.; Rozenberg, K. A.; Aksenov, S. M.; Pekov, I. V.; Belakovsky, D. I.; Kristiansen, R.; Van, K. V.

    2017-12-01

    A new eudialyte-group mineral, ilyukhinite, ideally (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 · 3H2O, has been found in peralkaline pegmatite at Mt. Kukisvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. It occurs as brownish orange, with vitreous luster anhedral grains up to 1 mm across in hydrothermally altered peralkaline rock, in association with aegirine, murmanite, albite, microcline, rhabdophane-(Ce), fluorite, sphalerite and molybdenite. The Mohs hardness is 5; cleavage is not observed. D meas 2.67(2), D calc 2.703 g/cm3. Ilyukhinite is optically uniaxial (-): ω = 1.585(2), ɛ = 1.584(2). The IR spectrum is given. The average chemical composition of ilyukhinite (wt %; electron microprobe, ranges given in parentheses; H2O determined by gas chromatography) is as follows: 3.07 (3.63-4.43) Na2O, 0.32 (0.28-0.52) K2O, 10.63 (10.26-10.90) CaO, 3.06 (2.74-3.22) MnO, 1.15 (0.93-1.37) FeO, 0.79 (0.51-0.89) La2O3, 1.21 (0.97-1.44) Ce2O3, 0.41 (0.30-0.56) Nd2O3, 0.90 (0.77-1.12) TiO2, 10.94 (10.15-11.21) ZrO2, 1.40 (0.76-1.68) Nb2O5, 51.24 (49.98-52.28) SiO2, 1.14 (0.89-1.37) SO3, 0.27 (0.19—0.38) Cl, 10.9(5 )H2O,-0.06-O = C1, total is 98.27. The empirical formula is H36.04(Na3.82K0.20)(Ca5.65Ce0.22La0.14Nd0.07)(Mn1.285Fe0.48)(Zr2.645Ti0.34)Nb0.31Si25.41S0.42Cl0.23O86.82. The crystal structure has been solved ( R = 0.046). Ilyukhinite is trigonal, R3 m; a = 14.1695(6) Å, b = 31.026(1) Å, V = 5394.7(7) Å3, Z = 3. The strongest XRD reflections [ d, Å (I, %) ( hkl)] are 11.44 (82) (101), 7.09 (70) (110), 6.02 (44) (021), 4.371 (89) 205), 3.805 (47) (303, 033), 3.376 (41) (131), 2.985 (100) (315, 128), 2.852 (92) (404). Ilyukhinite was named in memory of Vladimir V. Ilyukhin (1934-1982), an outstanding Soviet crystallographer. The type specimen of ilyukhinite has been deposited in the collection of the Natural History Museum, University of Oslo, Norway.

  2. Gravity predominates over ventilatory pattern in the prevention of ventilator-associated pneumonia.

    PubMed

    Li Bassi, Gianluigi; Marti, Joan Daniel; Saucedo, Lina; Rigol, Montserrat; Roca, Ignasi; Cabanas, Maria; Muñoz, Laura; Ranzani, Otavio Tavares; Giunta, Valeria; Luque, Nestor; Esperatti, Mariano; Gabarrus, Albert; Fernandez, Laia; Rinaudo, Mariano; Ferrer, Miguel; Ramirez, Jose; Vila, Jordi; Torres, Antoni

    2014-09-01

    In the semirecumbent position, gravity-dependent dissemination of pathogens has been implicated in the pathogenesis of ventilator-associated pneumonia. We compared the preventive effects of a ventilatory strategy, aimed at decreasing pulmonary aspiration and enhancing mucus clearance versus the Trendelenburg position. Prospective randomized animal study. Animal research facility, University of Barcelona, Spain. Twenty-four Large White-Landrace pigs. Pigs were intubated and on mechanical ventilation for 72 hours. Following surgical preparation, pigs were randomized to be positioned: 1) in semirecumbent/prone position, ventilated with a duty cycle (TITTOT) of 0.33 and without positive end-expiratory pressure (control); 2) as in the control group, positive end-expiratory pressure of 5 cm H2O and TITTOT to achieve a mean expiratory-inspiratory flow bias of 10 L/min (treatment); 3) in Trendelenburg/prone position and ventilated as in the control group (Trendelenburg). Following randomization, Pseudomonas aeruginosa was instilled into the oropharynx. Mucus clearance rate was measured through fluoroscopic tracking of tracheal markers. Microspheres were instilled into the subglottic trachea to assess pulmonary aspiration. Ventilator-associated pneumonia was confirmed by histological/microbiological studies. The mean expiratory-inspiratory flow in the treatment, control, and Trendelenburg groups were 10.7 ± 1.7, 1.8 ± 3.7 and 4.3 ± 2.8 L/min, respectively (p < 0.001). Mucus clearance rate was 11.3 ± 9.9 mm/min in the Trendelenburg group versus 0.1 ± 1.0 in the control and 0.2 ± 1.0 in the treatment groups (p = 0.002). In the control group, we recovered 1.35% ± 1.24% of the instilled microspheres per gram of tracheal secretions, whereas 0.22% ± 0.25% and 0.97% ± 1.44% were recovered in the treatment and Trendelenburg groups, respectively (p = 0.031). Ventilator-associated pneumonia developed in 66.67%, 85.71%, and 0% of the animals in

  3. H-TiO2/C/MnO2 nanocomposite materials for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Di, Jing; Fu, Xincui; Zheng, Huajun; Jia, Yi

    2015-06-01

    Functionalized TiO2 nanotube arrays with decoration of MnO2 nanoparticles (denoted as H-TiO2/C/MnO2) have been synthesized in the application of electrochemical capacitors. To improve both areal and gravimetric capacitance, hydrogen treatment and carbon coating process were conducted on TiO2 nanotube arrays. By scanning electron microscopy and X-ray photoelectron spectroscopy, it is confirmed that the nanostructure is formed by the uniform incorporation of MnO2 nanoparticles growing round the surface of the TiO2 nanotube arrays. Impedance analysis proves that the enhanced capacitive is due to the decrease of charge transfer resistance and diffusion resistance. Electrochemical measurements performed on this H-TiO2/C/MnO2 nanocomposite when used as an electrode material for an electrochemical pseudocapacitor presents quasi-rectangular shaped cyclic voltammetry curves up to 100 mV/s, with a large specific capacitance (SC) of 299.8 F g-1 at the current density of 0.5 A g-1 in 1 M Na2SO4 electrolyte. More importantly, the electrode also exhibits long-term cycling stability, only 13 % of SC loss after 2000 continuous charge-discharge cycles. Based on the concept of integrating active materials on highly ordered nanostructure framework, this method can be widely applied to the synthesis of high-performance electrode materials for energy storage.

  4. Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

    NASA Astrophysics Data System (ADS)

    Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

    2015-10-01

    We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

  5. Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

    NASA Astrophysics Data System (ADS)

    Sun, Shichen; Awadallah, Osama; Cheng, Zhe

    2018-02-01

    It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

  6. Lateral variation of H2O/K2O ratios in Quaternary Magma of the Northeastern Japan arc

    NASA Astrophysics Data System (ADS)

    Miyagi, I.

    2012-12-01

    Water plays a fundamental role in the magma genesis beneath subduction zones. In order to estimate a spatial distribution of the density of water flux in the wedge mantle of the Northeastern Japan arc, this study examines a lateral variation of pre-eruptive bulk rock H2O/K2O contents among volcanoes located both in the frontal and in back arc settings. The analytical targets are the frontal volcanoes Nigorikawa (N42.12 E140.45), Zenikame (N41.74 E140.85), Adachi (N38.22 E140.65), and Nanashigure (N40.07 E141.11), and the back arc ones Hijiori (N38.61 E140.17) and Kanpu (N39.93 E139.88). The bulk magmatic H2O content (TH2O) is calculated from a mass balance of hydrogen isotopic ratios among three phases in a batch of magma; dissolved water in melt, excess H2O vapor, and hydrous phenocrysts such as amphiboles (Miyagi and Matsubaya, 2003). Since the amount of H2O in hydrous phenocryst is negligible, the bulk magmatic H2O content can be written as TH2O = (30 XD CD) / (15 - dT + dMW), where dMW is the measured hydrogen isotopic ratio of hydrous phenocrysts, XD is a melt fraction of magma, CD is a water concentration of the melt, and dT is hydrogen isotopic ratios of a bulk magma (assumed to be -50 per-mil). Both XD and CD are estimated from bulk rock chemistry of the sample using the MELTS program (Ghiorso and Sack, 1995). Hydrogen isotopic fractionation factors are assumed to be -15 and -30 per-mil for vapor and hydrous mineral, and vapor and silicate melt, respectively. There observed a clear difference among the H2O/K2O ratios of bulk magmas from the frontal and back arc volcanoes. For instance higher H2O/K2O wt ratios was observed in the frontal volcanoes (Nigorikawa 5.3, Zenikame 11-12, Adachi 8-10, and Nanashigure 4-18), while lower H2O/K2O wt ratios was observed in the back arc ones (Kanpu 0-2.5 and Hijiori 1.4). The lateral variation of H2O/K2O ratios infer the higher water flux through the frontal side of wedge mantle, which can be a potential cause of the

  7. Image-Based Measurement of H2O2 Reaction-Diffusion in Wounded Zebrafish Larvae.

    PubMed

    Jelcic, Mark; Enyedi, Balázs; Xavier, João B; Niethammer, Philipp

    2017-05-09

    Epithelial injury induces rapid recruitment of antimicrobial leukocytes to the wound site. In zebrafish larvae, activation of the epithelial NADPH oxidase Duox at the wound margin is required early during this response. Before injury, leukocytes are near the vascular region, that is, ∼100-300 μm away from the injury site. How Duox establishes long-range signaling to leukocytes is unclear. We conceived that extracellular hydrogen peroxide (H 2 O 2 ) generated by Duox diffuses through the tissue to directly regulate chemotactic signaling in these cells. But before it can oxidize cellular proteins, H 2 O 2 must get past the antioxidant barriers that protect the cellular proteome. To test whether, or on which length scales this occurs during physiological wound signaling, we developed a computational method based on reaction-diffusion principles that infers H 2 O 2 degradation rates from intravital H 2 O 2 -biosensor imaging data. Our results indicate that at high tissue H 2 O 2 levels the peroxiredoxin-thioredoxin antioxidant chain becomes overwhelmed, and H 2 O 2 degradation stalls or ceases. Although the wound H 2 O 2 gradient reaches deep into the tissue, it likely overcomes antioxidant barriers only within ∼30 μm of the wound margin. Thus, Duox-mediated long-range signaling may require other spatial relay mechanisms besides extracellular H 2 O 2 diffusion. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  8. Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe3)(CO)2H, CpMo(PMe3)2(CO)H, [CpMo(μ-O)(μ-O2CH)]2, and [Cp*Mo(μ-O)(μ-O2CH)]2.

    PubMed

    Neary, Michelle C; Parkin, Gerard

    2017-02-06

    The molecular structures of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H 2 from formic acid, the carbonyl derivatives, Cp R Mo(CO) 3 H, are also observed to form dinuclear formate compounds, namely, [Cp R Mo(μ-O)(μ-O 2 CH)] 2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2 CH)] 2 and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2 CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ 2 δ* 2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

  9. A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

    NASA Astrophysics Data System (ADS)

    Dou, Ming-Yu; Lu, Jing

    2017-12-01

    A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

  10. Characterization of supramolecular (H2O)18 water morphology and water-methanol (H2O)15(CH3OH)3 clusters in a novel phosphorus functionalized trimeric amino acid host.

    PubMed

    Raghuraman, Kannan; Katti, Kavita K; Barbour, Leonard J; Pillarsetty, Nagavarakishore; Barnes, Charles L; Katti, Kattesh V

    2003-06-11

    Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A).

  11. Half-metallicity in the ferrimagnet [MnII(enH)(H2O)][CrIII(CN)6]·H2O: Ab initio study

    NASA Astrophysics Data System (ADS)

    Li, N.; Yao, K. L.; Zhong, G. H.; Ching, W. Y.

    2013-03-01

    The density-functional theory (DFT) within the full potential linearized augmented plane wave (FPLAPW) method is applied to study the two-dimensional achiral soft ferrimagnet [MnII(enH)(H2O)][CrIII(CN)6]·H2O. The phase stability, electronic structure, magnetic and conducting properties are investigated. Our results reveal that the compound has a stable ferrimagnetic ground state in good agreement with the experiment. From the spin density distribution, the spin magnetic moment of the compound is mainly from Cr3+ and Mn2+ ions with small contributions from the oxygen, nitrogen and carbon ions. The calculated electronic band structure predicts the compound to be a half-metal with the spin magnetic moment of 1.000 μB per molecule.

  12. Rheological properties of sewage sludge during enhanced anaerobic digestion with microwave-H2O2 pretreatment.

    PubMed

    Liu, Jibao; Yu, Dawei; Zhang, Jian; Yang, Min; Wang, Yawei; Wei, Yuansong; Tong, Juan

    2016-07-01

    The rheological behavior of sludge is of serious concern in anaerobic digestion. This study investigated the rheological properties of sewage sludge during enhanced anaerobic digestion with microwave-H2O2 pretreatment (MW-H2O2). The results showed that MW-H2O2 pretreatment resulted in the improvement of sludge flowability and weakening of its viscoelastic properties. Further positive effects on the rheological properties of digested sludge during anaerobic digestion were observed. The flowability was improved with a low level of apparent viscosity. The decrease of the consistency index and increase of the flow behavior index indicated that the strength of the inner structures and non-Newtonian flow characteristics of digested sludge weakened. Both the storage modulus (G') and loss modulus (G″) decreased, indicating that the viscoelastic behavior became weak. These effects were possibly attributed to the changes of the digested sludge micro-structures, such as extracellular polymeric substances (EPS). This study concluded that anaerobic digestion for treating sewage sludge combined with pretreatment is a more favorable option than single anaerobic digestion from the perspective of rheology. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Effectiveness evaluation of glyphosate oxidation employing the H(2)O(2)/UVC process: toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles.

    PubMed

    Junges, Celina M; Vidal, Eduardo E; Attademo, Andrés M; Mariani, Melisa L; Cardell, Leandro; Negro, Antonio C; Cassano, Alberto; Peltzer, Paola M; Lajmanovich, Rafael C; Zalazar, Cristina S

    2013-01-01

    The H(2)O(2)/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M(1,) M(2), and M(3) following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H(2)O(2). Subsamples of M(1), M(2), and M(3) were then used to create samples M(1,E), M(2,E) and M(3,E) in which the H(2)O(2) had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M(1,E), which was collected early in the photodegradation process, caused 52% inhibition, while M(3,E), which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M(2), M(3), and in M(1,E), M(2,E) and M(3,E). The lowest percentages of enzymatic inhibition were observed in samples without removal of H(2)O(2): 13.96% (AChE) and 16% (BChE) for M(2), and 24.12% (AChE) and 13.83% (BChE) for M(3). These results show the efficiency of the H(2)O(2)/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M(2) (11 ± 1 mg a.e. L(-1) glyphosate and 11 ± 1 mg L(-1) H(2)O(2)) could be used as a final point for glyphosate treatment with the H(2)O(2)/UV process.

  14. Special hydrogen bonds observed in two monovalent metal carboxylate-phosphinates: {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2H2O}∞

    NASA Astrophysics Data System (ADS)

    Zhao, Cui-Cui; Zhang, Jian-Wei; Zhou, Zhong-Gao; Du, Zi-Yi

    2013-02-01

    The addition of strong base such as sodium hydroxide or potassium hydroxide to the aqueous solution of (2-carboxyethyl)(phenyl)phosphinic acid afforded two novel monovalent metal carboxylate-phosphinates, namely, {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ (1) and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2H2O}∞ (2). They represent the first examples of phosphinate containing short, symmetric or almost symmetric O⋯H⋯O hydrogen bonds.

  15. Effect of Training Frequency on Maximum Expiratory Pressure

    ERIC Educational Resources Information Center

    Anand, Supraja; El-Bashiti, Nour; Sapienza, Christine

    2012-01-01

    Purpose: To determine the effects of expiratory muscle strength training (EMST) frequency on maximum expiratory pressure (MEP). Method: We assigned 12 healthy participants to 2 groups of training frequency (3 days per week and 5 days per week). They completed a 4-week training program on an EMST trainer (Aspire Products, LLC). MEP was the primary…

  16. Comparison of photo-Fenton, O3/H2O2/UV and photocatalytic processes for the treatment of gray water.

    PubMed

    Hassanshahi, Nahid; Karimi-Jashni, Ayoub

    2018-06-21

    This research was carried out to compare and optimize the gray water treatment performance by the photo-Fenton, photocatalysis and ozone/H 2 O 2 /UV processes. Experimental design and optimization were carried out using Central Composite Design of Response Surface Methodology. The results of experiments showed that the most effective and influencing factors in photo-Fenton process were H 2 O 2 /Fe 2+ ratio, in ozone/H 2 O 2 /UV experiment were O 3 concentration, H 2 O 2 concentration, reaction time and pH and in photocatalytic process were TiO 2 concentration, pH and reaction time. The highest COD removal in photo-Fenton, ozone/H 2 O 2 /UV and photocatalytic process were 90%, 92% and 55%, respectively. The results were analyzed by design expert software and for all three processes second-order models were proposed to simulate the COD removal efficiency. In conclusion the ozone/H 2 O 2 /UV process is recommended for the treatment of gray water, since it was able to remove both COD and turbidity by 92% and 93%, respectively. Copyright © 2018 Elsevier Inc. All rights reserved.

  17. Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O

    NASA Astrophysics Data System (ADS)

    Mereiter, Kurt

    2013-04-01

    Albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O, triclinic, space group Pī, a = 13.569(2), b = 13.419(2), c = 11.622(2) Å, α = 115.82(1), β = 107.61(1), γ = 92.84(1)° (structural unit cell, not reduced), V = 1774.6(5) Å3, Z = 2, D c = 2.69 g/cm3 (for 17.5 H2O), is a mineral that was found in small amounts with schröckingerite, NaCa3F[UO2(CO3)3](SO4)ṡ10H2O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca2[UO2(CO3)3]ṡ ~ 11H2O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX = 1.511(2), nY = 1.550(2), nZ = 1.566(2), 2 V = 65(1)° ( λ = 589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO2 and H2O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1 = 0.0206 and wR2 = 0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO2(CO3)3]4- anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF2(Ocarbonate)3(H2O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO6, CaF2O2(H2O)4, CaFO3(H2O)4 and CaO2(H2O)6 coordination polyhedra. The crystal structure is built up from MgCa3F2[UO2(CO3)3]ṡ8H2O layers parallel to (001) which are linked by Ca[UO2(CO3)3]ṡ5H2O moieties into a framework of the composition MgCa4F2[UO2(CO3)3]ṡ13H2O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a

  18. Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

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

    Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

    A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

  19. Cathodic detection of H2O2 based on nanopyramidal gold surface with enhanced electron transfer of myoglobin.

    PubMed

    Xia, Peipei; Liu, Haiqing; Tian, Yang

    2009-04-15

    Direct and reversible electron transfer of myoglobin (Mb), for the first time, is achieved at nanopyramidal gold surface, which was fabricated by one-step electrodeposition, with redox formal potential of 0.21+/-0.01 V (vs. Ag/AgCl) and an apparent heterogeneous electron-transfer rate constant (k(s)) of 1.6+/-0.2 s(-1). Electrochemical investigation indicates that Mb is stably confined on the nanopyramidal gold surface and maintains electrocatalytic activity toward hydrogen peroxide (H(2)O(2)). The facilitated electron transfer combined with the intrinsic catalytical activity of Mb substantially construct the third-generation biosensor for H(2)O(2). The positive redox potential of Mb at the nanostructured gold electrode gives a strong basis for determination of H(2)O(2) with high selectivity. Besides this advantage, the present biosensor also exhibits quick response time, broad linear range, and good sensitivity. The dynamic detection linear range is from 1 microM to 1.4 mM with a detection limit of 0.5 microM at 3sigma. The striking analytical performance of the present biosensor, as well as the biocompatibility of gold nanostructures provided a potential for continuous, on-line detection of H(2)O(2) in the biological system.

  20. CO2 splitting by H2O to CO and O2 under UV light in TiMCM-41silicate sieve

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

    Lin, Wenyong; Han, Hongxian; Frei, Heinz

    2004-04-06

    The 266 nm light-induced reaction of CO{sub 2} and H{sub 2}O gas mixtures (including isotopic modifications {sup 13}CO{sub 2}, C{sup 18}O{sub 2}, and D{sub 2}O) in framework TiMCM-41 silicate sieve was monitored by in-situ FT-IR spectroscopy at room temperature. Carbon monoxide gas was observed as the sole product by infrared, and the growth was found to depend linearly on the photolysis laser power. H{sub 2}O was confirmed as stoichiometric electron donor. The work establishes CO as the single photon, 2-electron transfer product of CO{sub 2} photoreduction by H{sub 2}O at framework Ti centers for the first time. O{sub 2} wasmore » detected as co-product by mass spectrometric analysis of the photolysis gas mixture. These results are explained by single UV photon-induced splitting of CO{sub 2} by H{sub 2}O to CO and surface OH radical.« less