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Effect of high-frequency ventilation on gas exchange and pulmonary vascular resistance in lambs.

We studied the effects of conventional mechanical ventilation (CMV) (15 ml/kg tidal volume delivered at 18-25 breaths/min) and high-frequency oscillatory ventilation (HFOV) (less than or equal to 2 ml/kg delivered at 10 Hz) on pulmonary hemodynamics and gas exchange during ambient air breathing and hypoxic gas breathing in 10 4-day-old lambs. After instrumentation and randomization to either HFOV or CMV the animals breathed first ambient air and then hypoxic gas (inspired O2 fraction = 0.13) for 20 min. The mode of ventilation was then changed, and the normoxic and hypoxic gas challenges were repeated. The multiple inert gas elimination technique was utilized to assess gas exchange. There was a significant increase with HFOV in mean pulmonary arterial pressure (Ppa) (20.1 +/- 4.2 vs. 22 +/- 3.8 Torr, CMV vs. HFOV, P less than 0.05) during ambient air breathing. During hypoxic gas breathing Ppa was also greater with HFOV than with CMV (29.5 +/- 5.7 vs. 34 +/- 3.1 Torr, CMV vs. HFOV, P less than 0.05). HFOV reduced pulmonary blood flow (Qp) during ambient air breathing (0.33 +/- 0.11 vs. 0.28 +/- 0.09 l . kg-1 . min-1, CMV vs. HFOV, P less than 0.05) and during hypoxic gas breathing (0.38 +/- 0.11 vs. 0.29 +/- 0.09 l . kg-1 . min-1, P less than 0.05). There was no significant difference in calculated venous admixture for sulfur hexafluoride or in the index of low ventilation-perfusion lung regions with HFOV compared with CMV.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

Importance of oscillations in alveolar gas concentrations in the analysis of rebreathing data.

Cyclic rebreathing of a soluble inert gas can be used to estimate lung tissue volume (Vt) and pulmonary blood flow (Qc). A recently proposed method for analyzing such cyclic data (Respir. Physiol. 48: 255-279, 1982) mathematically assumes that ventilation is a continuous process. However, neglecting the cyclic nature of ventilation may prevent the accurate estimation of Vt and Qc. We evaluated this possibility by simulating the uptake of soluble inert gases during rebreathing using a cyclic model of gas exchange. Under cyclic uptake conditions alveolar gases follow an oscillating time course, because gas concentrations tend to increase during inspiration and to decrease during expiration. We found that neglecting these alveolar gas oscillations leads to the underestimation of soluble gas uptake by blood, particularly during the early rebreathing breaths. When continuous ventilation is assumed Vt and Qc are overestimated unless rapid rebreathing rates, large tidal volumes, and gases of moderately low solubility are used. Under these conditions the amplitude of the cyclic oscillations is minimized, the alveolar time course more closely resembles that expected from continuous ventilation, and the resulting errors are minimized. Alternatively, when the effect of oscillating alveolar gas concentrations on mass transfer are considered, these estimation errors can be eliminated without restricting rebreathing rate or gas solubility. We conclude that failure to consider the effect of cyclic rebreathing on the time course of alveolar gas concentrations may result in significant errors when evaluating rebreathing data for Vt and Qc.

Lung Volume Measurements↗

High-frequency partial liquid ventilation in respiratory distress syndrome: hemodynamics and gas exchange.

Partial liquid ventilation using conventional ventilatory schemes improves lung function in animal models of respiratory failure. We examined the feasibility of high-frequency partial liquid ventilation in the preterm lamb with respiratory distress syndrome and evaluated its effect on pulmonary and systemic hemodynamics. Seventeen lambs were studied in three groups: high-frequency gas ventilation (Gas group), high-frequency partial liquid ventilation (Liquid group), and high-frequency partial liquid ventilation with hypoxia-hypercarbia (Liquid-Hypoxia group). High-frequency partial liquid ventilation increased oxygenation compared with high-frequency gas ventilation over 5 h (arterial oxygen tension 253 +/- 21.3 vs. 17 +/- 1.8 Torr; P < 0.001). Pulmonary vascular resistance decreased 78% (P < 0.001), pulmonary blood flow increased fivefold (P < 0.001), and aortic pressure was maintained (P < 0.01) in the Liquid group, in contrast to progressive hypoxemia, hypercarbia, and shock in the Gas group. Central venous pressure did not change. The Liquid-Hypoxia group was similar to the Gas group. We conclude that high-frequency partial liquid ventilation improves gas exchange and stabilizes pulmonary and systemic hemodynamics compared with high-frequency gas ventilation. The stabilization appears to be due in large part to improvement in gas exchange.

Animals↗

A method of reconstruction of clinical gas-analyzer signals corrupted by positive-pressure ventilation.

The use of sidestream infrared and paramagnetic clinical gas analyzers is widespread in anesthesiology and respiratory medicine. For most clinical applications, these instruments are entirely satisfactory. However, their ability to measure breath-by-breath volumetric gas fluxes, as required for measurement of airway dead space, oxygen uptake, and so on, is usually inferior to that of the mass spectrometer, and this is thought to be due, in part, to their slower response times. We describe how volumetric gas analysis with the Datex Ultima analyzer, although reasonably accurate for spontaneous ventilation, gives very inaccurate results in conditions of positive-pressure ventilation. We show that this problem is a property of the gas sampling system rather than the technique of gas analysis itself. We examine the source of this error and describe how cyclic changes in airway pressure result in variations in the flow rate of the gas within the sampling catheter. This results in the phenomenon of "time distortion," and the resultant gas concentration signal becomes a nonlinear time series. This corrupted signal cannot be aligned or integrated with the measured flow signal. We describe a method to correct for this effect. With the use of this method, measurements required for breath-by-breath gas-exchange models can be made easily and reliably in the clinical setting.

Algorithms↗

Computer tomographic assessment of perfluorocarbon and gas distribution during partial liquid ventilation for acute respiratory failure.

The average in vivo chest computed tomographic (CT) attenuation number (air = -1,000, soft tissue = 0, perflubron = +2,300 Hounsfield units [HU]) of 10 ventrodorsal-oriented lung segments was calculated to assess the distribution of gas and perflubron in 14 oleic acid lung-injured adult sheep during partial liquid ventilation (PLV, n = 7) or gas ventilation (GV, n = 7). Partial liquid ventilation was associated with a significant decrease in shunt fraction (PLV = 40 +/- 12%, GV = 76 +/- 12%, p = 0.004). Computed tomographic attenuation data during expiration (HUexp) demonstrated minimal gas aeration in GV animals in the dependent (segments 6-10) lung zones (HUexp = -562 +/- 108 for segments 1-5, HUexp = -165 +/- 104 for segments 6-10, p = 0.015). During PLV, perflubron was predominantly distributed to the dependent lung regions (HUexp = 579 +/- 338 for segments 1-5, HUexp = 790 +/- 149 for segments 6-10, p = 0.04). The ratio of the inspiratory to expiratory HU (HUinsp/exp) was greater in dependent than nondependent regions (mean HUinsp/exp segments 1-5 = 0.56, segments 6-10 = 0.81, p = 0.01), indicating that during inspiration relatively more gas than perflubron was distributed to the nondependent lung regions. We conclude that during PLV in this lung injury model, (1) gas exchange is improved when compared with gas ventilation, (2) perflubron is distributed predominantly to the dependent regions of the lung, and (3) although gas is distributed throughout the lung with each inspiration, more gas than perflubron goes to the nondependent lung regions.

Acute Disease↗

Insect gas exchange patterns: a phylogenetic perspective.

Most investigations of insect gas exchange patterns and the hypotheses proposed to account for their evolution have been based either on small-scale, manipulative experiments, or comparisons of a few closely related species. Despite their potential utility, no explicit, phylogeny-based, broad-scale comparative studies of the evolution of gas exchange in insects have been undertaken. This may be due partly to the preponderance of information for the endopterygotes, and its scarcity for the apterygotes and exopterygotes. Here we undertake such a broad-scale study. Information on gas exchange patterns for the large majority of insects examined to date (eight orders, 99 species) is compiled, and new information on 19 exemplar species from a further ten orders, not previously represented in the literature (Archaeognatha, Zygentoma, Ephemeroptera, Odonata, Mantodea, Mantophasmatodea, Phasmatodea, Dermaptera, Neuroptera, Trichoptera), is provided. These data are then used in a formal, phylogeny-based parsimony analysis of the evolution of gas exchange patterns at the order level. Cyclic gas exchange is likely to be the ancestral gas exchange pattern at rest (recognizing that active individuals typically show continuous gas exchange), and discontinuous gas exchange probably originated independently a minimum of five times in the Insecta.

Animals↗

Continuous intra-arterial blood gas monitoring in rats.

Studies on lung injury and its treatment options are often performed on small animals like rats. Because conventional blood gas analyses may not detect rapid changes in gas exchange during respiratory distress syndrome and intermittent blood withdrawal can result in hypo-volaemia and anaemia, we tested the applicability and accuracy of a continuous intravascular blood gas monitor (Paratrend 7+). Anaesthetized and ventilated rats with a body weight of 398 +/-45 g (n =22) had a 20-gauge cannula inserted in both carotid arteries. A photochemical blood gas sensor for continuous measurement (Paratrend 7+) was advanced into the aorta via the left carotid artery. Blood was sampled for intermittent blood gas analysis by means of the right carotid artery. Arterial pO(2) was varied by applying different inspiratory oxygen concentrations, and arterial pCO(2) by applying different respiratory rates. Paired blood gas measurements (n =136) were analysed over a wide range of pO(2) values (5.3-76.8 kPa). We found an acceptable correlation for pO(2) (r(2)=0.98), pCO(2) (r(2)=0.96) and pH (r(2)=0.92). The calculated bias and imprecision for pO(2) was -1.0 +/- 3.3 kPa, for pCO(2) 0.04 +/- 0.28 kPa and for hydrogen ion concentration -0.05 +/-2.2 nmol/l. We conclude that in rats, continuous blood gas monitoring with a photochemical blood gas sensor provides pO(2), pCO(2) and pH measurements with acceptable accuracy.

Animals↗

Improvement of gas exchange, pulmonary function, and lung injury with partial liquid ventilation. A study model in a setting of severe respiratory failure.

STUDY OBJECTIVE: To evaluate gas exchange, pulmonary function, and lung histology during gas ventilation of the perfluorocarbon-filled lung compared with gas ventilation of the gas-filled lung in severe respiratory failure. STUDY DESIGN: Application of gas (GV) or partial liquid (PLV) ventilation in lung-injured sheep. SETTING: A research laboratory at a university medical center. SUBJECTS: Eleven sheep 17.1 +/- 1.8 kg in weight. INTERVENTIONS: Lung injury was induced by intravenous administration of 0.07 mL/kg oleic acid followed by saline pulmonary lavage. When alveolar-arterial oxygen pressure difference (P[A-a]O2) was 600 mm Hg or more and PaO2 was 50 mm Hg or less with fraction of inspired oxygen of 1.0, bijugular venovenous extracorporeal life support (ECLS) was instituted. For the first 30 min on ECLS, all animals were ventilated with gas. Over the ensuing 2.5 h, ventilation with 15 mL/kg gas was continued without intervention in the control group (GV, n = 6) or with the addition of 35 mL/kg of perflubron (PLV, n = 5). MEASUREMENTS AND RESULTS: At 3 h after initiation of ECLS, Qps/Qt was significantly reduced in the PLV animals when compared with the GV animals (PLV = 41 +/- 13%; GV = 93 +/- 4%; p < 0.005). At the same time point, pulmonary compliance was increased in the PLV when compared with the GV group (PLV = 0.61 +/- 0.14 mL/cm H2O/kg; GV = 0.41 +/- 0.02 mL/cm H2O/kg; p < 0.005). The ECLS flow rate required to maintain the PaO2 in the 50 to 80 mm Hg range was substantially and significantly lower in the PLV group when compared with that of the GV group (PLV = 25 +/- 20 mL/kg/min; GV = 87 +/- 15 mL/kg/min; p < 0.001). Light microscopy performed on lung biopsy specimens demonstrated a marked reduction in lung injury in the liquid ventilated (LV) when compared with the GV animals. CONCLUSION: In a model of severe respiratory failure, PLV improves pulmonary gas exchange and pulmonary function and is associated with a reduction in pulmonary pathology.

Acute Disease↗

Effect of body position on gas exchange in patients with idiopathic pulmonary alveolar proteinosis: no benefit of prone positioning.

BACKGROUND: Prone positioning may improve oxygenation in patients with acute lung injury/ARDS. However, the beneficial effect of prone positioning on gas exchange has never been investigated in patients with diffuse pulmonary infiltrates who breathe spontaneously. OBJECTIVE: To evaluate the effect of body position on gas exchange in patients with idiopathic pulmonary alveolar proteinosis (PAP) with special reference to the benefit of prone positioning. DESIGN: A prospective study. SETTING: Tertiary medical center. PATIENTS AND METHODS: Eight patients with PAP were studied on 25 occasions using spirometry, body plethysmography, and single-breath diffusing capacity of the lung for carbon monoxide (Dlco). Arterial blood gas levels were measured in the sitting position and in four lying positions randomly while patients breathed room air. To serve as control subjects, 16 age-matched healthy hospital personnel were studied. To evaluate the impact of oxygen therapy on positional effect in gas exchange, arterial blood gas levels were measured in the supine and prone positions in some PAP patients while breathing 40% oxygen. RESULTS: Normal to varying degrees of restrictive ventilatory defect and gas exchange impairment, as evidenced by Dlco, Pao(2), and alveolar-arterial oxygen pressure difference (P[A-a]O(2)), were found in PAP patients. The ventilatory function parameters correlated positively with Pao(2) and negatively with P(A-a)O(2). The values of Pao(2) and P(A-a)O(2) measured in four lying positions showed no significant difference in both PAP patients and healthy control subjects. Furthermore, the differences in Pao(2) and P(A-a)O(2) between measurements made in the supine and prone positions and the ratio of Pao(2) measured in the prone position/Pao(2) measured in the supine position were comparable between PAP patients and healthy control subjects. Arterial blood gas levels showed no significant difference between measurements made in PAP patients in the supine and prone positions while breathing 40% oxygen. CONCLUSIONS: Positional change did not significantly affect gas exchange, and no benefit of prone positioning was found in both PAP patients and healthy control subjects. Further studies are needed to verify the benefit of prone ventilation in patients with diffuse pulmonary disorders who breathe spontaneously.

Adult↗

Clinical use of continuous arterial blood gas monitoring in the pediatric intensive care unit.

CONTEXT: Continuous arterial blood gas monitoring is a new technology based on the combination of opto-chemical and fiber-optic detectors that can measure pH, PCO2, PO2, and temperature on a continuous basis via a sensor placed in an artery. OBJECTIVE: To evaluate this technology in pediatric patients who would normally require frequent arterial blood gas sampling. DESIGN: A criterion standard study in which the results of arterial blood gas samples measured by the laboratory analyzer were compared with the sensor readings. SETTING: A pediatric intensive care unit of a tertiary referral center. PATIENTS: Children with severe respiratory failure who required frequent arterial blood gas sampling and who had a 20-gauge arterial line in either a radial or femoral site. RESULTS: Twenty-four patients with a mean age of 6.4 years (range 1-21 years) had a sensor placed. Sensors were in place for a mean of 101 +/- 62 hours. Eighteen patients underwent continuous monitoring for at least 24 hours or until no longer clinically necessary. There were 414 pairs of blood gas samples obtained. The bias/precision for pH was 0.005/0.030; for PCO2, -1.8/6.3 mm Hg; and for PO2, 1.2/24 mm Hg. The correlation (r value) between the sensor readings and the blood gases were pH 0. 960, PCO2 0.927, PO2 0.813 (P <.01 for all values). The bias and precision for PO2 levels < 70 mm Hg were 0.057/9.34 mm Hg. There were no complications from sensor placement. Continuous blood gas monitoring allowed immediate recognition of clinical changes. CONCLUSION: The continuous arterial blood gas sensor is capable of clinically accurate blood gas measurements. This technology provides the clinician with immediate data that can allow rapid interventions in unstable patients.

Adolescent↗

Relationship between the transfer rate and the gap in partial pressure of gas molecules at a heterogeneous interface.

The kinetic energy of a gas molecule dissolved in an aqueous solution in the stationary state is inversely proportional to its solubility according to the distribution law of kinetic energy between the gas and liquid phases. From the difference in solubility, it is deduced that the gas molecule undergoes a change in energy in the passage across a heterogeneous interface, which is countered by a difference in energy level, or a gap in partial pressure, between the two sides. In order words, unless there is the gap in partial pressure, which has hitherto been disregarded in solving the diffusion equation, it is impossible to equalize the efflux of gas molecules with the influx. The relationship between the gap in partial pressure and the transfer rate is theoretically derived from the difference in solubility. The transfer rate is evaluated by multiplying the gap size by the transfer coefficient n, which in turn is expressed by an equation containing the unique value, k, for conductivity across the interface. Comparing the theoretical and experimental transfer coefficients obtained across the gas-liquid interface, the k value at which a gas traverses the liquid side per unit difference in partial pressure is estimated to be 6.58 x 10(-3) cm.s-1.Atm-1. Gas solubility in the RBC membrane is estimated to be ca. 22% of that in water, regardless of gas type, for O2, CO, and CO2. The increase in transfer coefficient across the RBC membrane by convection is explained by an additional change in kinetic energy in extracellular fluid attributable to an external force. The reduction in the transfer coefficient in the presence of increased protein is ascribed to an increase in kinetic energy of the membrane at the RBC boundary. The solubility in the membrane is linearly related to added protein concentration.

Animals↗

[Gas gangrene].

In spite of surgical, intensive, and hyperbaric oxygen therapy, the gas gangrene is still one of the most dangerous surgical infections. In recent literature, the average mortality is about 50%. The patients die within a few days because of general intoxication. A review of our own results achieved between 1971 and 1981 shows that 50 out of 73 patients with clostridium infection and all 77 patients in whom a gas gangrene was suspected have survived [ 2 ]. For the prognosis and therapy of the gas gangrene, the classification into stages I to IV according to the severity has proved to be useful. The prognosis depends on the incubation period (the shorter the incubation period the worse the prognosis), on the beginning of the treatment and on the site of a primary or secondary gas gangrene. The more distally the gas gangrene is situated in the extremities, the better is the prognosis with regard to mortality and invalidity. An early diagnosis of the gas gangrene is of primary importance. As early as a gas gangrene is suspected because of typical local findings and clinical symptoms, therapeutic measures are immediately necessary (surgery, intensive treatment and hyperbaric oxygen therapy). A transport of more than six hours with prolonged interruption of the treatment will decrease the chances of success even in a "gas gangrene therapy centre".

Gas Gangrene↗

Mass casualties from acute inhalation of chloramine gas.

Mass exposure to chloramine gas has not been reported. We report two groups of 36 patients (72 total) suffering from acute inhalation of chloramine gas. Chloramine gas is produced from mixing common household cleaning agents containing sodium hypochlorite (bleach) and ammonia. The first mass casualty event occurred when 36 male soldiers were exposed during a "cleaning party" in their barracks. Ten days later, 36 female soldiers were exposed in a similar manner and presented to our emergency department. In each event, commonly available cleaning agents--liquid bleach and ammonia--were mixed together, liberating toxic chloramine gas. Nebulized sodium bicarbonate solution has been suggested for treatment of chlorine gas inhalation, but no report of nebulized sodium bicarbonate for treatment of chloramine gas inhalation injury exists. In our series, 22 patients exposed to chloramine gas were treated with a nebulized solution of 3.75% sodium bicarbonate. This treatment made no significant statistical or clinical difference in outcome. We present the largest case series of patients presenting to an emergency department for treatment of acute inhalation of chloramine gas.

Adult↗

Oxygen respiratory gas analysis by sine-wave measurement: a theoretical model.

A sinusoidal forcing function inert-gas-exchange model (C. E. W. Hahn, A. M. S. Black, S. A. Barton, and I. Scott. J. Appl. Physiol. 75: 1863-1876, 1993) is modified by replacing the inspired inert gas with oxygen, which then behaves mathematically in the gas phase as if it were an inert gas. A simple perturbation theory is developed that relates the ratios of the amplitudes of the inspired, end-expired, and mixed-expired oxygen sine-wave oscillations to the airways' dead space volume and lung alveolar volume. These relationships are independent of oxygen consumption, the gas-exchange ratio, and the mean fractional inspired (FIO2) and expired oxygen partial pressures. The model also predicts that blood flow shunt fraction (Qs/QT) is directly related to the oxygen sine-wave amplitude perturbations transmitted to end-expired air and arterial and mixed-venous blood through two simple equations. When the mean FIO2 is sufficiently high for arterial hemoglobin to be fully saturated, oxygen behaves mathematically in the blood like a low-solubility inert gas, and the amplitudes of the arterial and end-expired sine-wave perturbations are directly related to Qs/QT. This relationship is independent of the mean arterial and mixed-venous oxygen partial pressures and is also free from mixed-venous perturbation effects at high forcing frequencies. When arterial blood is not fully saturated, the theory predicts that QS/QT is directly related to the ratio of the amplitudes of the induced-saturation sinusoids in arterial and mixed-venous blood. The model therefore predicts that 1) on-line calculation of airway dead space and end-expired lung volume can be made by the addition of an oxygen sine-wave perturbation component to the mean FIO2; and (2) QS/QT can be measured from the resultant oxygen perturbation sine-wave amplitudes in the expired gas and in arterial and mixed-venous blood and is independent of the mean blood oxygen partial pressure and oxyhemoglobin saturation values. These calculations can be updated at the sine-wave forcing period, typically 2-4 min.

Air Pressure↗

Vitrectomy with silicone oil or long-acting gas in eyes with severe proliferative vitreoretinopathy: results of additional and long-term follow-up. Silicone Study report 11.

BACKGROUND: The Silicone Study evaluated the outcomes of vitreoretinal surgery for retinal detachment with proliferative vitreoretinopathy (PVR). OBJECTIVE: To evaluate short-term (up to 36 months) outcomes in eyes randomized to silicone oil or perfluoropropane gas and long-term (up to 72 months) outcomes in eyes with attached maculas at 36 months. DESIGN: Prospective, randomized, multicentered surgical trial. SETTING: Community- and university-based vitreoretinal practices. PATIENTS: Two-hundred sixty-five eyes with PVR randomized to perfluoropropane gas and silicone oil with follow-up through 3 years (cohort 1) and 249 eyes with attached maculas at 36 months (121 eyes randomized to long-acting gas [either sulfur hexafluoride or perfluoropropane] and 128 eyes randomized to silicone oil) with follow-up up to 6 years (cohort 2). Both cohorts consisted of eyes that had and had not undergone vitrectomy for PVR (groups 1 and 2, respectively) before randomization. Of the 265 eyes in cohort 1, 24-month follow-up data were available for 218 eyes (82%) and 36-month follow-up data were available for 196 eyes (74%). Of 208 eyes in cohort 2, 48-month follow-up data were available for 146 eyes (70%), 60-month follow-up data for 119 eyes (57%), and 72-month follow-up data for 73 eyes (35%). INTERVENTIONS: Vitrectomy surgery for PVR with a long-acting gas or silicone oil as the intraocular tamponade. MAIN OUTCOME MEASURES: Changes in visual acuity, recurrent retinal detachment, and incidence of complications. RESULTS: In group 1 of cohort 1, compared with oil-treated eyes, gas-treated eyes had a higher rate of complete retinal reattachment from 18 to 36 months (P < .05). No other differences were found. In group 2 of cohort 1, no notable differences were found between treatment arms. In cohort 2, during 6 years of follow-up, attachment of the macula was maintained for all eyes. No notable differences in the rates of complete retinal attachment, visual acuity of 5/200 or better, or glaucoma were found between treatment groups. In contrast, gas-treated eyes had more hypotony (P < .001). Silicone oil-treated eyes that underwent subsequent surgery were more likely to have the oil retained (P = .02). Compared with oil-retained eyes, oil-removed eyes had higher rates of complete posterior attachment (P = .01) and of a visual acuity of 5/200 or better (P < .001) and less keratopathy (P < .05). Compared with oil-removed eyes, gas-treated eyes had a worse visual acuity outcome (P < .05) and more hypotony (P < .01). CONCLUSION: The Silicone Study showed that silicone oil and perfluoropropane gas were equal in most respects for the management of retinal detachments with PVR. Success in the first surgery for PVR is paramount for obtaining better visual results. Overall, surgery for PVR had a high likelihood of retinal reattachment, and if anatomically and visually successful at 3 years, there is an excellent chance that the results will be maintained over the long-term.

Adult↗

Importance of gas-phase proton affinities in determining the electrospray ionization response for analytes and solvents.

The effect of gas-phase proton transfer reactions on the mass spectral response of solvents and analytes with known gas-phase proton affinities was evaluated. Methanol, ethanol, propanol and water mixtures were employed to probe the effect of gas-phase proton transfer reactions on the abundance of protonated solvent ions. Ion-molecule reactions were carried out either in an atmospheric pressure electrospray ionization source or in the central quadrupole of a triple-quadrupole mass spectrometer. The introduction of solvent vapor with higher gas-phase proton affinity than the solvent being electrosprayed caused protons to transfer to the gas-phase solvent molecules. In mixed solvents, protonated solvent clusters of the solvent with higher gas-phase proton affinity dominated the resulting mass spectra. The effect of solvent gas-phase proton affinity on analyte response was also investigated, and the analyte response was suppressed or eliminated in solvents with gas-phase proton affinities higher than that of the analyte.

Atmospheric Pressure↗

Growth of Rhodospirillum rubrum on synthesis gas: conversion of CO to H2 and poly-beta-hydroxyalkanoate.

To examine the potential use of synthesis gas as a carbon and energy source in fermentation processes, Rhodospirillum rubrum was cultured on synthesis gas generated from discarded seed corn. The growth rates, growth and poly-beta-hydroxyalkanoates (PHA) yields, and CO oxidation/H(2) evolution rates were evaluated in comparison to the rates observed with an artificial synthesis gas mixture. Depending on the gas conditioning system used, synthesis gas either stimulated or inhibited CO-oxidation rates compared to the observations with the artificial synthesis gas mixture. Inhibitory and stimulatory compounds in synthesis gas could be removed by the addition of activated charcoal, char-tar, or char-ash filters (char, tar, and ash are gasification residues). In batch fermentations, approximately 1.4 mol CO was oxidized per day per g cell protein with the production of 0.75 mol H(2) and 340 mg PHA per day per g cell protein. The PHA produced from R. rubrum grown on synthesis gas was composed of 86% beta-hydroxybutyrate and 14% beta-hydroxyvalerate. Mass transfer of CO into the liquid phase was determined as the rate-limiting step in the fermentation.

Aldehyde Oxidoreductases↗

Diffusion NMR methods applied to xenon gas for materials study.

We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack.

Diffusion↗