Failure of molecular dynamics to provide appropriate structures for quantum mechanical description of the aqueous chloride ion charge-transfer-to-solvent ultraviolet spectrum.

The lowest band in the charge-transfer-to-solvent ultraviolet absorption spectrum of aqueous chloride ion is studied by experiment and computation. Interestingly, the experiments indicate that at concentrations up to at least 0.25 M, where calculations indicate ion pairing to be significant, there is no notable effect of ionic strength on the spectrum. The experimental spectra are fitted to aid comparison with computations. Classical molecular dynamic simulations are carried out on dilute aqueous Cl-, Na+, and NaCl, producing radial distribution functions in reasonable agreement with experiment and, for NaCl, clear evidence of ion pairing. Clusters are extracted from the simulations for quantum mechanical excited state calculations. Accurate ab initio coupled-cluster benchmark calculations on a small number of representative clusters are carried out and used to identify and validate an efficient protocol based on time-dependent density functional theory. The latter is used to carry out quantum mechanical calculations on thousands of clusters. The resulting computed spectrum is in excellent agreement with experiment for the peak position, with little influence from ion pairing, but is in qualitative disagreement on the width, being only about half as wide. It is concluded that simulation by classical molecular dynamics fails to provide an adequate variety of structures to explain the experimental CTTS spectrum of aqueous Cl-.

Recruitment Maneuvers and Positive End-Expiratory Pressure Titration in Morbidly Obese ICU Patients.

OBJECTIVE: The approach to applying positive end-expiratory pressure in morbidly obese patients is not well defined. These patients frequently require prolonged mechanical ventilation, increasing the risk for failed liberation from ventilatory support. We hypothesized that lung recruitment maneuvers and titration of positive end-expiratory pressure were both necessary to improve lung volumes and the elastic properties of the lungs, leading to improved gas exchange. DESIGN: Prospective, crossover, nonrandomized interventional study. SETTING: Medical and surgical ICUs at Massachusetts General Hospital. PATIENTS: Critically ill, mechanically ventilated morbidly obese (body mass index > 35 kg/m(2)) patients (n = 14). INTERVENTIONS: This study evaluated two methods of titrating positive end-expiratory pressure; both trials were done utilizing positive end-expiratory pressure titration and recruitment maneuvers while measuring hemodynamics and respiratory mechanics. Measurements were obtained at the baseline positive end-expiratory pressure set by the clinicians, at zero positive end-expiratory pressure, at best positive end-expiratory pressure identified through esophageal pressure measurement before and after a recruitment maneuver, and at best positive end-expiratory pressure identified through a best decremental positive end-expiratory pressure trial. MEASUREMENTS AND MAIN RESULTS: The average body mass index was 50.7 ± 16.0 kg/m(2). The two methods of evaluating positive end-expiratory pressure identified similar optimal positive end-expiratory pressure levels (20.7 ± 4.0 vs 21.3 ± 3.8 cm H2O; p = 0.40). End-expiratory pressure titration increased end-expiratory lung volumes (Δ11 ± 7 mL/kg; p < 0.01) and oxygenation (Δ86 ± 50 torr; p < 0.01) and decreased lung elastance (Δ5 ± 5 cm H2O/L; p < 0.01). Recruitment maneuvers followed by titrated positive end-expiratory pressure were effective at increasing end-expiratory lung volumes while decreasing end-inspiratory transpulmonary pressure, suggesting an improved distribution of lung aeration and reduction of overdistension. The positive end-expiratory pressure levels set by the clinicians (11.6 ± 2.9 cm H2O) were associated with lower lung volumes, worse elastic properties of the lung, and lower oxygenation. CONCLUSIONS: Commonly used positive end-expiratory pressure by clinicians is inadequate for optimal mechanical ventilation of morbidly obese patients. A recruitment maneuver followed by end-expiratory pressure titration was found to significantly improve lung volumes, respiratory system elastance, and oxygenation.

Hemibonding between Water Cation and Water.

The hemibonding interaction in the water dimer cation is studied using coupled cluster electronic structure methods. The hemibonded dimer cation geometry is a local minimum structure characterized by the two participating monomers having both a very short separation and a near parallel relative orientation. It is shown that the vertically ionized dimer at its optimum neutral geometry can convert to the hemibonded dimer cation structure with essentially no energetic hindrance. Direct conversion to the hemibonded structure is therefore an energetically facile alternative to the minimum energy path that connects the vertically ionized neutral water dimer to the global minimum proton-transferred structure. A substantial barrier must be surmounted to convert the hemibonded dimer cation to the proton-transferred structure. The optical absorption spectrum of the hemibonded dimer cation is characterized by three excited near-UV states, two of which have very large oscillator strengths. Relative resonance Raman intensities are estimated for the hemibonded dimer cation vibrational modes, finding the intermolecular stretching mode to be the most strongly enhanced when in near resonance with each of the near-UV excited states, and the anharmonicity and overtones of this mode are estimated. These results provide guidance for the possible observation of hemibonded cations in irradiated liquid water.

Composite method for implicit representation of solvent in dimethyl sulfoxide and acetonitrile.

A composite method for implicit representation of solvent previously developed to compute aqueous free energies of solvation is extended to accommodate the polar aprotic solvents dimethyl sulfoxide and acetonitrile. The method combines quantum mechanical calculation of the solute electronic structure with a modern dielectric continuum model for long-range electrostatic interactions with solvent and individual models for short-range interactions arising from dispersion, exchange, and hydrogen bonding. The few parameters involved are optimized to fit a standard data set of experimental solvation energies for neutrals and ions. Results are better than other models in the literature, with average errors for ions comparable to or smaller than the estimated experimental errors. Some circumstantial evidence is also obtained to support one of the competing extrathermodynamic arguments recently used to determine the solvation energies of the proton, which are needed to separate measurements of paired cation plus anion solvation energies into absolute single ion solvation energies in these solvents.

Autologous transfusion of stored red blood cells increases pulmonary artery pressure.

RATIONALE: Transfusion of erythrocytes stored for prolonged periods is associated with increased mortality. Erythrocytes undergo hemolysis during storage and after transfusion. Plasma hemoglobin scavenges endogenous nitric oxide leading to systemic and pulmonary vasoconstriction. OBJECTIVES: We hypothesized that transfusion of autologous blood stored for 40 days would increase the pulmonary artery pressure in volunteers with endothelial dysfunction (impaired endothelial production of nitric oxide). We also tested whether breathing nitric oxide before and during transfusion could prevent the increase of pulmonary artery pressure. METHODS: Fourteen obese adults with endothelial dysfunction were enrolled in a randomized crossover study of transfusing autologous, leukoreduced blood stored for either 3 or 40 days. Volunteers were transfused with 3-day blood, 40-day blood, and 40-day blood while breathing 80 ppm nitric oxide. MEASUREMENTS AND MAIN RESULTS: The age of volunteers was 41 ± 4 years (mean ± SEM), and their body mass index was 33.4 ± 1.3 kg/m(2). Plasma hemoglobin concentrations increased after transfusion with 40-day and 40-day plus nitric oxide blood but not after transfusing 3-day blood. Mean pulmonary artery pressure, estimated by transthoracic echocardiography, increased after transfusing 40-day blood (18 ± 2 to 23 ± 2 mm Hg; P < 0.05) but did not change after transfusing 3-day blood (17 ± 2 to 18 ± 2 mm Hg; P = 0.5). Breathing nitric oxide decreased pulmonary artery pressure in volunteers transfused with 40-day blood (17 ± 2 to 12 ± 1 mm Hg; P < 0.05). CONCLUSIONS: Transfusion of autologous leukoreduced blood stored for 40 days was associated with increased plasma hemoglobin levels and increased pulmonary artery pressure. Breathing nitric oxide prevents the increase of pulmonary artery pressure produced by transfusing stored blood. Clinical trial registered with www.clinicaltrials.gov (NCT 01529502).

Monocarbon cationic cluster yields from N2/CH4 mixtures embedded in He nanodroplets and their calculated binding energies.

The formation of monocarbon cluster ions has been investigated by electron ionization mass spectrometry of cold helium nanodroplets doped with nitrogen/methane mixtures. Ion yields for two groups of clusters, CHmN2(+) or CHmN4(+), were determined for mixtures with different molecular ratios of CH4. The possible geometrical structures of these clusters were analyzed using electronic structure computations. Little correlation between the ion yields and the associated binding energies has been observed indicating that in most cases kinetic control is more important than thermodynamic control for forming the clusters.

Feasibility of Delivering a 5-Day Normobaric Hypoxia Breathing in Healthy Volunteers in a Hospital Setting.

BACKGROUND: Beneficial effects of breathing at FIO2 < 0.21 on disease outcomes have been reported in previous preclinical and clinical studies. However, the safety and intra-hospital feasibility of breathing hypoxic gas for 5 d have not been established. In this study, we examined the physiologic effects of breathing a gas mixture with FIO2 as low as 0.11 in 5 healthy volunteers. METHODS: All 5 subjects completed the study, spending 5 consecutive days in a hypoxic tent, where the ambient oxygen level was lowered in a stepwise manner over 5 d, from FIO2 of 0.16 on the first day to FIO2 of 0.11 on the fifth day of the study. All the subjects returned to an environment at room air on the sixth day. The subjects' SpO2 , heart rate, and breathing frequency were continuously recorded, along with daily blood sampling, neurologic evaluations, transthoracic echocardiography, and mental status assessments. RESULTS: Breathing hypoxia concentration dependently caused profound physiologic changes, including decreased SpO2 and increased heart rate. At FIO2 of 0.14, the mean SpO2 was 92%; at FIO2 of 0.13, the mean SpO2 was 93%; at FIO2 of 0.12, the mean SpO2 was 88%; at FIO2 of 0.11, the mean SpO2 was 85%; and, finally, at an FIO2 of 0.21, the mean SpO2 was 98%. These changes were accompanied by increased erythropoietin levels and reticulocyte counts in blood. All 5 subjects concluded the study with no adverse events. No subjects exhibited signs of mental status changes or pulmonary hypertension. CONCLUSIONS: Results of the current physiologic study suggests that, within a hospital setting, delivering FIO2 as low as 0.11 is feasible and safe in healthy subjects, and provides the foundation for future studies in which therapeutic effects of hypoxia breathing are tested.

New implicit solvation models for dispersion and exchange energies.

Implicit solvation models provide a very efficient means to estimate solvation energies. For example, dielectric continuum models are commonly used to obtain the long-range electrostatic interactions. These may be parametrized to also include in some average manner short-range interactions such as dispersion and exchange, but it is preferable to instead develop additional implicit models specifically designed for the short-range interactions. This work proposes new models for dispersion and exchange interactions between solute and solvent by adapting approaches previously developed for treatment of gas-phase intermolecular forces. The new models are formulated in terms of the charge densities of the solutes and use only three adjustable parameters. To illustrate the performance of the models, electronic structure calculations are reported for a large number of solutes in two nonpolar solvents where short-range interactions dominate and different balances pertain between attractive dispersion and repulsive exchange contributions. After empirical optimization of the requisite parameters, it is found that the errors compared to experimental solvation free energies are only about 0.4 kcal/mol on average, which is better than previous approaches in the literature that invoke many more parameters.

Delivering Low Tidal Volume With Anesthesia and ICU Ventilators in a Neonatal Lung Model.

BACKGROUND: Mechanical ventilation of the neonate requires ventilators than can deliver precise and accurate tidal volume (VT) and PEEP to avoid lung injury. Due to small neonatal VT and the disproportionate effect of endotracheal tube leak in these patients, accomplishing precise and accurate VT delivery is difficult. Whereas neonatal ICU ventilators are validated in this population, thorough studies testing the performance of anesthesia ventilators in delivering small VT in neonates are lacking. METHODS: Three anesthesia ventilators, Dräger Apollo, GE Avance, and Getinge Flow-i; and 2 ICU ventilators, Medtronic PB980 and Nihon Kohden NKV-550, were tested under volume control mode at VT of 5, 20, 40, and 60 mL. Three combinations of lung compliance and airway resistance were tested using a Servo ASL 5000 lung simulator. RESULTS: In a scenario without leak, the measured VT was greater than the set VT by > 10% in the Apollo (21.0% [18.8-26.0]); measured VT was less than the set VT by > 10% in the Flow-i (-19% [-20.8 to -18.7]). The Avance, PB980, and NKV-550 presented a volume error < 10% (-9.50% [-10.8 to -4.4], -5.8% [-11.8 to -3.5], and 5.4% [-4.5 to 18.9], respectively). Considering all combinations of set VT, leaks, and respiratory mechanics, none of the anesthesia ventilators were able to deliver a median measured VT within a 10% error. The bias between measured VT and set VT varied widely among ventilators (from 4.27 mL to -10.59 mL). Additionally, in the Apollo ventilator, PEEP was underdelivered with the largest leak value. CONCLUSIONS: Our results suggest that in comparison with the 2 neonatal ICU ventilators tested, the anesthesia ventilators did not greatly differ in terms of VT delivery in the presence of a gas leak.

Insights into the ultraviolet spectrum of liquid water from model calculations: the different roles of donor and acceptor hydrogen bonds in water pentamers.

With a view toward a better understanding of changes in the peak position and shape of the first absorption band of water with condensation or temperature, results from electronic structure calculations using high level wavefunction based and time-dependent density functional methods are reported for water pentamers. Excitation energies, oscillator strengths, and redistributions of electron density are determined for the quasitetrahedral water pentamer in its C(2v) equilibrium geometry and for many pentamer configurations sampled from molecular simulation of liquid water. Excitations associated with surface molecules are removed in order to focus on those states associated with the central molecule, which are the most representative of the liquid environment. The effect of hydrogen bonding on the lowest excited state associated with the central molecule is studied by adding acceptor or donor hydrogen bonds to tetramer and trimer substructures of the C(2v) pentamer, and by sampling liquid-like configurations having increasing number of acceptor or donor hydrogen bonds of the central molecule. Our results provide clear evidence that the blueshift of excitation energies upon condensation is essentially determined by acceptor hydrogen bonds, and the magnitudes of these shifts are determined by the number of such, whereas donor hydrogen bonds do not induce significant shifts in excitation energies. This qualitatively different role of donor and acceptor hydrogen bonds is understood in terms of the different roles of the 1b(1) monomer molecular orbitals, which establishes an intimate connection between the valence hole and excitation energy shifts. Since the valence hole of the lowest excitation associated with the central molecule is found to be well localized in all liquid-like hydrogen bonding environments, with an average radius of gyration of ~1.6 Å that is much lower than the nearest neighbor O-O distance, a clear and unambiguous connection between hydrogen bonding environments and excitation energy shifts can be established. Based on these results, it is concluded that peak position of the first absorption band is mainly determined by the relative distribution of single and double acceptor hydrogen bonding environments, whereas the shape of the first absorption band is mainly determined by the relative distribution of acceptor and broken acceptor hydrogen bonding environments. The temperature dependence of the peak position and shape of the first absorption band can be readily understood in terms of changes to these relative populations.

Hemibonding between hydroxyl radical and water.

The ultraviolet absorption peak commonly used to identify OH radical in liquid water is mainly due to a charge-transfer-from-solvent transition that is prominent when OH is hemibonded, rather than more stable hydrogen bonded, to H(2)O. This work computationally characterizes the hemibonding interaction and the extent of the geometrical region over which it is significant. Hemibonding is found to be associated with an enlarged energy separation between the two lowest-lying electronic states, which are otherwise always quite close to one another. The lower state, wherein the hemibonding occurs, retains an attractive interaction energy between OH and H(2)O that can be as much as one-half as strong as the optimum hydrogen-bonding interaction, while the enlarged separation between the states is mainly due to the upper state becoming repulsive over most of the hemibonding region. Hemibonding also leads to a considerable drop in the energy and a considerable increase in the oscillator strength of the characteristic charge-transfer transition. The region of significant hemibonding is found to lie within a moderate range of O-O azimuthal angles and over quite wide ranges of O-O separation distances and hydroxyl OH tilt angles. In particular, significant hemibonding interactions can extend down to surprisingly short O-O distances, where the oscillator strength for the charge-transfer-from-solvent transition becomes very large.

Performance of current intensive care unit ventilators during pressure and volume ventilation.

BACKGROUND: Intensive-care mechanical ventilators regularly enter the market, but the gas-delivery capabilities of many have never been assessed. METHODS: We evaluated 6 intensive-care ventilators in the pressure support (PS), pressure assist/control (PA/C), and volume assist/control (VA/C) modes, with lung-model mechanics combinations of compliance and resistance of 60 mL/cm H(2)O and 10 cm H(2)O/L/s, 60 mL/cm H(2)O and 5 cm H(2)O/L/s, and 30 mL/cm H(2)O and 10 cm H(2)O/L/s, and inspiratory muscle effort of 5 and 10 cm H(2)O. PS and PA/C were set to 15 cm H(2)O, and PEEP to 5 and 15 cm H(2)O in all modes. During VA/C, tidal volume was set at 500 mL and inspiratory time was set at 0.8 second. Rise time and termination criteria were set at the manufacturers' defaults, and to an optimal level during PS and PA/C. RESULTS: There were marked differences in ventilator performance in all 3 modes. VA/C had the greatest difficulty meeting lung model demand and the greatest variability across all tested scenarios and ventilators. From high to low inspiratory muscle effort, pressure-to-trigger, time for pressure to return to baseline, and triggering pressure-time product decreased in all modes. With increasing resistance and decreasing compliance, tidal volume, pressure-to-trigger, time-to-trigger, time for pressure to return to baseline, time to 90% of peak pressure, and pressure-time product decreased. There were large differences between the default and optimal settings for all the variables in PS and PA/C. Performance was not affected by PEEP. CONCLUSIONS: Most of the tested ventilators performed at an acceptable level during the majority of evaluations, but some ventilators performed inadequately during specific settings. Bedside clinical evaluation is needed.

How does dielectric solvation affect the size of an ion?

The effect of solvation by a continuum dielectric on the size of an ion is examined using electronic structure calculations. Various measures correlated with size are considered, including the root-mean-square radius of the electronic charge density, the amount of solute charge penetrating outside the cavity, the electronic radial distribution function, the nucleus-electron potential energy, and the electron-electron potential energy. Calculations are made on several representative ionic solutes, and it is found that every measure indicates that the application of a dielectric makes the cations larger and the anions smaller. These counterintuitive trends are examined, and a plausible explanation is offered for the observed behavior.

Insights into the ultraviolet spectrum of liquid water from model calculations.

With a view toward a better molecular level understanding of the effects of hydrogen bonding on the ultraviolet absorption spectrum of liquid water, benchmark electronic structure calculations using high level wave function based methods and systematically enlarged basis sets are reported for excitation energies and oscillator strengths of valence excited states in the equilibrium water monomer and dimer and in a selection of liquid-like dimer structures. Analysis of the electron density redistribution associated with the two lowest valence excitations of the water dimer shows that these are usually localized on one or the other monomer, although valence hole delocalization can occur for certain relative orientations of the water molecules. The lowest excited state is mostly associated with the hydrogen bond donor and the significantly higher energy second excited state mostly with the acceptor. The magnitude of the lowest excitation energies is strongly dependent on where the valence hole is created, and only to a lesser degree on the perturbation of the excited electron density distribution by the neighboring water molecule. These results suggest that the lowest excitation energies in clusters and liquid water can be associated with broken acceptor hydrogen bonds, which provide energetically favorable locations for the formation of a valence hole. Higher valence excited states of the dimer typically involve delocalization of the valence hole and/or delocalization of the excited electron and/or charge transfer. Two of the higher valence excited states that involve delocalized valence holes always have particularly large oscillator strengths. Due to the pervasive delocalization and charge transfer, it is suggested that most condensed phase water valence excitations intimately involve more than one water molecule and, as a consequence, will not be adequately described by models based on perturbation of free water monomer states. The benchmark calculations are further used to evaluate a series of representative semilocal, global hybrid, and range separated hybrid functionals used in efficient time-dependent density functional methods. It is shown that such an evaluation is only meaningful when comparison is made at or near the complete basis set limit of the wave function based reference method. A functional is found that quantitatively describes the two lowest excitations of water dimer and also provides a semiquantitative description of the higher energy valence excited states. This functional is recommended for use in further studies on the absorption spectrum of large water clusters and of condensed phase water.

Vertical electronic excitation with a dielectric continuum model of solvation including volume polarization. I. Theory.

A dielectric continuum model of solvation is developed for use in conjunction with electronic structure calculation on vertical electronic excitation of a solute. Particular attention is paid to volume polarization arising from quantum mechanical penetration of solute charge density outside the cavity that nominally encloses it, which affects both the fast and slow components of the dielectric response. An approximation that closely simulates volume polarization while being easier to implement in practice is also described. These approaches are compared to other related formulations found in the literature.

Vertical electronic excitation with a dielectric continuum model of solvation including volume polarization. II. Implementation and applications.

A practical implementation is described for calculation of solute vertical electronic excitation with a new dielectric continuum model of solvation. Particular attention is given to the specific aspects associated with quantum mechanical treatment of the solute, which leads to volume polarization effects arising from penetration of the solute charge density outside the cavity nominally enclosing it. Some representative computations are presented using this method and several other related methods from the literature for the lowest vertical transitions of an acetone and a water molecule in dielectric continuum models of aqueous solution. These illustrate the two possible extreme behaviors wherein the acetone transition is found to be little affected by volume polarization, while the water transition is found to be quite sensitive to volume polarization, the latter so much so that approximate treatments of volume polarization are inadequate.

Probing silver nanoparticles during catalytic H2 evolution.

Employing silver nanoparticles from a recently developed synthesis [Evanoff, D. D.; Chumanov, G. J. Phys. Chem. B 2004, 108, 13948] and a well-studied probe molecule, p-aminothiophenol, we follow changes at the surface of the particles during the conditioning and eventually the catalytic production of hydrogen from water using strongly reducing radicals. Injection of electrons into the particles causes pronounced variations in the intensity of the surface enhanced Raman scattering (SERS) spectrum of the probe molecule. These spectral changes are caused by changes in the Fermi-level energy that are in turn caused by changes in the silver ion concentrations or in the pH, or by changes in electron density in the particle. This correlation highlights the effect of the chemical potential on the SERS enhancement at the end of the particles synthesis. The intensity of the SERS spectra increases in the presence of the silver ions when excitation at 514 nm is utilized. When the Ag(+) ions in the colloidal suspension are completely reduced by the radicals and the particles operate in the catalytic mode, the SERS spectrum is too weak to record, but it can reversibly be recovered upon the addition of Ag(+). The effect of pH on the SERS intensity is similar in nature to that of the silver ions but is complicated by the pKa of the aminothiol and the point of zero charge (pzc) of the particles. It is hypothesized that as the particles cross the pzc (around neutral pH) the electrostatic interaction between the protonated amine headgroup of the probe and the positively charged surface increases the density of probe molecules in the perpendicular orientation at the expense of a competing species. This conversion results in enhanced SERS signals and is observable during the preconditioning stage of the particles. Indeed, adsorption isotherms of the probe indicate the presence of two species. In analogous previous observations these two species have been attributed to perpendicular and flat adsorption orientations of the deprotonated probe molecule relative to the particle surface. However, preliminary density functional calculations on relevant prototypes raise the possibility that the two species may be the probe molecule and a cationic form produced by charge transfer in the ground state from the chemisorbed probe to the metal. These two forms of the probe have differing electronic structures and vibrational frequencies, with perhaps differing orientations relative to the surface. Whichever is the correct interpretation, a neutral molecule in a flat orientation or a radical cation, this species is easier to replace than the other in competitive adsorption by ethanethiol.

Trigger performance of mid-level ICU mechanical ventilators during assisted ventilation: a bench study.

OBJECTIVE: To compare the triggering performance of mid-level ICU mechanical ventilators with a standard ICU mechanical ventilator. DESIGN: Experimental bench study. SETTING: The respiratory care laboratory of a university-affiliated teaching hospital. SUBJECT: A computerized mechanical lung model, the IngMar ASL5000. INTERVENTIONS: Ten mid-level ICU ventilators were compared to an ICU ventilator at two levels of lung model effort, three combinations of respiratory mechanics (normal, COPD and ARDS) and two modes of ventilation, volume and pressure assist/control. A total of 12 conditions were compared. MEASUREMENTS AND MAIN RESULTS: Performance varied widely among ventilators. Mean inspiratory trigger time was <100 ms for only half of the tested ventilators. The mean inspiratory delay time (time from initiation of the breath to return of airway pressure to baseline) was longer than that for the ICU ventilator for all tested ventilators except one. The pressure drop during triggering (Ptrig) was comparable with that of the ICU ventilator for only two ventilators. Expiratory Settling Time (time for pressure to return to baseline) had the greatest variability among ventilators. CONCLUSIONS: Triggering differences among these mid-level ICU ventilators and with the ICU ventilator were identified. Some of these ventilators had a much poorer triggering response with high inspiratory effort than the ICU ventilator. These ventilators do not perform as well as ICU ventilators in patients with high ventilatory demand.

Absorption spectrum of OH radical in water.

The influence of water on the ultraviolet absorption spectrum of OH radical is investigated with electronic structure calculations. One purpose of the work is to benchmark computational methods for their ability to treat this problem. That is done by applying a number of methods to characterization of the excited states of a variety of arrangements having OH interacting with one H(2)O molecule. In high-level coupled-cluster approaches, it is found that triple excitations are of considerable importance. Two promising methods based on highly efficient time-dependent density functional theory are identified that may provide qualitatively useful results, but no method is found that is both efficient and capable of providing quantitative accuracy. Another purpose of the work is to suggest a plausible interpretation of the experimental absorption spectrum of aqueous OH radical. For this purpose an accurate coupled cluster approach is applied to the various OH x H(2)O structures considered, along with a dielectric continuum representation of the further effects of additional bulk water. The valence transition localized on OH that is found at approximately 300 nm in gas is found to be considerably broadened by hydrogen bonding interactions with water. These transitions are assigned to the very broad shoulder on the experimental aqueous spectrum that extends from approximately 300 to 400 nm. The main experimental aqueous absorption band peaking at approximately 230 nm is found to arise instead mainly from rare hemibonded structures, which contribute out of proportion to their relative populations by virtue of having large oscillator strengths. The region near the experimental peak and on its blue side is primarily due to charge transfer transitions that move an electron to OH from hemibonded water, while the region on the near red side of the peak is primarily due to valence transitions localized on OH that is interacting with hemibonded water.

Performance comparison of 15 transport ventilators.

BACKGROUND: Numerous mechanical ventilators are designed and marketed for use in patient transport. The complexity of these ventilators differs considerably, but very few data exist to compare their operational capabilities. METHODS: Using bench and animal models, we studied 15 currently available transport ventilators with regard to their physical characteristics, gas consumption (duration of an E-size oxygen cylinder), battery life, ease of use, need for compressed gas, ability to deliver set ventilation parameters to a test lung under 3 test conditions, and ability to maintain ventilation and oxygenation in normal and lung-injured sheep. RESULTS: Most of the ventilators tested were relatively simple to operate and had clearly marked controls. Oxygen cylinder duration ranged from 30 min to 77 min. Battery life ranged from 70 min to 8 hours. All except 3 of the ventilators were capable of providing various F(IO2) values. Ten of the ventilators had high-pressure and patient-disconnect alarms. Only 6 of the ventilators were able to deliver all settings as specifically set on the ventilator during the bench evaluation. Only 4 of the ventilators were capable of maintaining ventilation, oxygenation, and hemodynamics in both the normal and the lung-injured sheep. CONCLUSIONS: Only 2 of the ventilators met all the trial targets in all the bench and animal tests. With many of the ventilators, certain of the set ventilation parameters were inaccurate (differed by > 10% from the values from a cardiopulmonary monitor). The physical characteristics and high gas consumption of some of these ventilators may render them less desirable for patient transport.