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Atmospheric pressure photoionization: an ionization method for liquid chromatography-mass spectrometry

Atmospheric pressure photoionization (APPI) has been successfully demonstrated to provide high sensitivity to LC-MS analysis. A vacuum-ultraviolet lamp designed for photoionization detection in gas chromatography is used as a source of 10-eV photons. The mixture of samples and solvent eluting from an HPLC is fully evaporated prior to introduction into the photoionization region. In the new method, large quantities of an ionizable dopant are added to the vapor generated from the LC eluant, allowing for a great abundance of dopant photoions to be produced. Because the ion source is at atmospheric pressure, and the collision rate is high, the dopant photoions react to completion with solvent and analyte molecules present in the ion source. Using APPI, at an LC flow rate of 200 microL/min, it is possible to obtain analyte signal intensities 8 times as high as those obtainable with a commercially available corona discharge-atmospheric pressure chemical ionization source.

Journal Article↗

Survival of deep-sea shrimp (Alvinocaris sp.) during decompression and larval hatching at atmospheric pressure.

We report successful larval hatching of deep-sea shrimp after decompression to atmospheric pressure. Three specimens of deep-sea shrimp were collected from an ocean depth of 1157 m at cold-seep sites off Hatsushima Island in Sagami Bay, Japan, using a pressure-stat aquarium system. Phylogenetic analysis of Alvinocaris sp. based on cytochrome c oxidase subunit gene sequences confirmed that these species were a member of the genus Alvinocaris. All 3 specimens survived to reach atmospheric pressure conditions after stepwise 63-day decompression. Two of the specimens contained eggs, which hatched after 10 and 16 days, respectively, of full decompression. Although no molting of the shrimp larvae was observed during 74 days of rearing under atmospheric pressure, the larvae developed conventional dark-adapted eyes after 15 days.

Animals↗

Low atmospheric pressure is associated with rupture of abdominal aortic aneurysms.

INTRODUCTION: the rate of rupture of abdominal aortic aneurysms (AAAs) has been shown to have a seasonal variation with more ruptures occurring during the winter months. One of the main meterological changes between the seasons is a change in atmospheric pressure. The aim of this study was to investigate whether there was any relationship between atmospheric pressure and the incidence of AAA rupture. METHODS: all cases of ruptured AAA admitted to a single hospital over a ten year period were identified from hospital records. Daily atmospheric pressure readings from the nearest weather recording station to the hospital were obtained for the same period. Cases were only included if rupture could be confirmed by reviewing the patients case-notes. RESULTS: admission rates for ruptured AAA showed a monthly variation with the highest rate in December and the lowest in August. There was a statistically significant correlation between the number of cases admitted in any particular month and the mean atmospheric pressure for the previous month. Neither daily minimum, maximum or mean pressure, weekly mean pressure or daily pressure variability were significantly different between those days when a ruptured AAA was admitted and those when no ruptured AAA was admitted. CONCLUSIONS: low atmospheric pressure is associated with increased rate of AAA rupture. The method by which this change in pressure precipitates rupture cannot be determined from this study.

Aortic Aneurysm, Abdominal↗

The importance of both charge exchange and proton transfer in the analysis of polycyclic aromatic compounds using atmospheric pressure chemical ionization mass spectrometry.

The response of atmospheric pressure chemical ionization (APCI) mass spectrometry to selected polycyclic aromatic compounds (PACs) was examined in a Micromass Quattro atmospheric pressure ion source as a function of both solvents and source gases. Typical PACs found in petroleum samples were represented by mixtures of naphthalene, fluorene, phenanthrene, pyrene, fluoranthene, chrysene, triphenylene, perylene, carbazole, dibenzothiophene, and 9-phenanthrol. A large range of different gases in the APCI source was studied, with emphasis on nitrogen, air, and carbon dioxide. Solvents used included water-acetonitrile, acetonitrile, dichloromethane, and hexanes. The signal responses were dependent on both the gases and solvents used, as was the ionization mechanism, as indicated by the degree of protonation with respect to the level of charge exchange. The combination of carbon dioxide in the nebulizer gas stream with nitrogen in the other streams gave a three- to fourfold better sensitivity than using nitrogen alone for both test mixtures and for complex samples.

Journal Article↗

Do temperature and atmospheric pressure affect the incidence of serious odontogenic infection?

OBJECTIVE: The purpose of this study was to investigate the popular belief that the incidence of odontogenic cellulitis is weather-related. Two meteorologic parameters were examined: temperature and atmospheric pressure. STUDY DESIGN: To test the hypothesis being studied, a retrospective cohort study design was used. Medical reports of all patients with serious odontogenic cellulitis who were treated at the Salpêtrière University Hospital between January 1, 1995, and December 31, 1995, (a total of 301 cases) were evaluated in relation to the weather. Hypothesizing that the incidence of odontogenic cellulitis was constant over a period of 1 year, the authors calculated the probability of observed incidence for each month over a 12-month period. The mean number of cases of odontogenic cellulitis (+/- standard error of the mean) for days on which (1) the temperature was within the same 2 degrees -C (3.6 degrees -F) interval and (2) the atmospheric pressure was within the same 3-hPa (2.25-mmHg) interval was also calculated. RESULTS: When the monthly incidence of odontogenic cellulitis and either the average temperature or the average atmospheric pressure for each month were examined together, fluctuation in the former seemed to be independent of the latter. Similarly, when we calculated the mean number of cases of odontogenic cellulitis for several intervals of temperature and atmospheric pressure without taking the calendar into account, no direct relationship could be observed. CONCLUSION: The results of the study suggest that the occurrence of odontogenic cellulitis is not influenced by the weather, at least insofar as weather is measured by temperature and atmospheric pressure.

Adolescent↗

Functionalized nanoparticles for liquid atmospheric pressure matrix-assisted laser desorption/ionization peptide analysis.

Nanoparticles for the extraction of peptides and subsequent analysis using atmospheric pressure matrix-assisted laser desorption/ionization (APMALDI) have been evaluated. The atmospheric pressure source allows for particles to be directly introduced in the liquid matrix, minimizing sample loss and analysis time. Described in this work are two sample preparation procedures for liquid APMALDI analysis: a C18 functionalized silica nanoparticle for hydrophobic extractions, and an aptamer functionalized magnetite core nanoparticle for rapid, affinity extractions. The C18 particles provide a non-selective support for rapid profiling applications, while the aptamer particles are directed towards reducing the complexity in biological samples. The aptamer functionalized particles provide a more selective analyte-nanoparticle interaction whereby the tertiary structure of the analyte becomes more critical to the extraction. In both cases, the liquid APMALDI matrix provides a support for ionization, and acts as the releasing agent for the analyte-particle interaction. Additionally, analyte enrichment was possible due to the large surface-to-volume ratio of the particles. The experiments conducted with functionalized nanoparticles, in an atmospheric pressure liquid matrix, present a basis for further methodologies and utilities of silica nanoparticles to be developed.

Adsorption↗

Relating landfill gas emissions to atmospheric pressure using numerical modelling and state-space analysis.

Landfill gas (CO2 and CH4) concentrations and fluxes in soil adjacent to an old, unlined Danish municipal landfill measured over a 48-hour period during the passage of a low-pressure weather system were used to identify processes governing gas fluxes and concentrations. Two different approaches were applied: (I) State-space analysis was used to identify relations between gas flux and short-term (hourly) variations in atmospheric pressure. (II) A numerical gas transport model was fitted to the data and used to quantify short-term impacts of variations in atmospheric pressure, volumetric soil-water content, soil gas permeability, soil gas diffusion coefficients, and biological CH4 degradation rate upon landfill gas concentration and fluxes in the soil. Fluxes and concentrations were found to be most sensitive to variations in volumetric soil water content, atmospheric pressure variations and gas permeability whereas variations in CH4 oxidation rate and molecular coefficients had less influence. Fluxes appeared to be most sensitive to atmospheric pressure at intermediate distances from the landfill edge. Also overall CH4 fluxes out of the soil over longer periods (years) were largest during periods with rapidly decreasing atmospheric pressures resulting in emission of large amounts of CH4 during short periods of time. This effect, however, was less significant for the CO2 fluxes.

Air Movements↗

Ammonia synthesis at atmospheric pressure

Ammonia was synthesized from its elements at atmospheric pressure in a solid state proton (H+)-conducting cell-reactor. Hydrogen was flowing over the anode and was converted into protons that were transported through the solid electrolyte and reached the cathode (palladium) over which nitrogen was passing. At 570 degreesC and atmospheric pressure, greater than 78 percent of the electrochemically supplied hydrogen was converted into ammonia. The thermodynamic requirement for a high-pressure process is eliminated.

Journal Article↗

The effects of acute exercise and increased atmospheric pressure on the hemostatic mechanism and plasma catecholamine levels.

The hemostatic response to acute exercise and increased atmospheric pressure was studied in 20 healthy male subjects (18-35 yr of age) exercised to volitional exhaustion on a cycle ergometer in a hyperbaric chamber at 3 atmospheres absolute (ATA). As a means of comparison, 6 of the 20 subjects were exercised in the same manner at 1 ATA. Similar increases in fibrinolytic activity (FA), Factor VIII activity (VIII:C), von Willebrand factor antigen (vWF:Ag) and plasma catecholamine levels were observed following acute exercise at 1 ATA and at 3 ATA. There were no changes in the levels of plasminogen, antithrombin III, Protein C or Fibrinopeptide A (FPA) with exercise either at 1 ATA or at 3 ATA. In addition, there were no changes in plasma catecholamine levels or any of the hemostatic variables measured when atmospheric pressure was increased from 1 ATA to 3ATA without exercise. These findings demonstrate that increasing atmospheric pressure from 1 ATA to 3 ATA does not alter the exercise-induced changes in hemostasis. Therefore, exercise or physical exertion at 3 ATA for a time period not to exceed 30 min does not perturb the hemostatic mechanism and increase the risk of bleeding or thrombosis.

Adolescent↗

Liquid supports for ultraviolet atmospheric pressure matrix-assisted laser desorption/ionization.

Atmospheric pressure (AP) liquid matrices for ultraviolet (UV) matrix-assisted laser desorption/ionization (MALDI) are presented. Doping a known organic chromophore, alpha-cyano-4-hydroxycinnamic acid (CHCA), into liquid media yielded a homogenous sample system with simplified sample preparation, increased sample lifetime, and added utility for APMALDI ion sources. Compared with vacuum situations, AP matrices are not as limited by vapor pressure, so liquid matrix formulations can focus on desorption and ionization versus vacuum stability and source contamination. The parameters studied include chromophore concentration, liquid support variations, and quantitation capability. Chromophore concentration adjustments provided insight into the necessary absorbance for UV-APMALDI and demonstrated the importance of laser penetration depth. Liquid support variations allowed adjustments of sample lifetime and analyte solvents. Extended sample lifetime is beneficial for instrument tuning and source optimization; however, increased liquid viscosity lowers signal intensity. The shot-to-shot reproducibility, as examined with individual ion packets, suggests that the liquid matrix can alleviate some inconsistencies seen with solid MALDI, suggesting a possibility for better quantitation. The measurements for laser penetration depth, solution viscosity, and solvent additives could add to the information on MALDI mechanisms. The liquid matrix offers advantages that complement current MALDI methods.

Atmospheric Pressure↗

Study of polybrominated diphenyl ethers using both positive and negative atmospheric pressure photoionization and tandem mass spectrometry.

Atmospheric pressure photoionization (APPI) was assessed for the mass spectrometric analysis of polybromodiphenyl ethers (PBDEs) on the basis of a set of 17 standard compounds. Positive and negative ionization modes were both investigated. M(+.) ions were formed under positive ion conditions whereas the negative ion mode yielded [M-Br+O](-) ions. The behavior of these APPI-produced ions towards collisional activation was studied using an ion trap mass spectrometer. In positive ion mode, the loss of Br(2) was one of the major fragmentation pathways, and was favored for ortho-substituted PBDEs. Conversely, the loss of COBr(.) occurred only for non-ortho-substituted congeners. The collisional excitation of [M-Br+O](-) ions in the ion trap also led to the loss of Br(2), to the elimination of HBr, and to the formation of product ions by cleavage of the ether bond. The formation of para-quinone radical anions was observed for PBDEs ranging from penta- to hepta-congeners, whereas brominated aromatic carbanions were formed preferentially for the most brominated PBDEs studied in this work (hepta- or deca-BDEs). M(+.) ions did not undergo this fragmentation process.

Atmospheric Pressure↗

[The development of a gas chromatograph used in gas analysis below atmospheric pressure].

During the process of setting up a carbon monoxide infrared laser generator, it's necessary to analyze the gaseous components produced in laser cavity under reduced pressure for understanding its charging regularity. In this paper a self-made gas chromatograph for analysis of some special gas mixtures is described. This instrument can analyze O2, N2, CO (with normal contents) and trace CO2 simultaneously below atmospheric pressure. The gas sample below atmospheric pressure was taken into a small piston cylinder and then compressed by pushing the piston for injection. The injected sample was carried by He into two parallel chromatographic columns and detected separately. The gases with normal contents were detected by a thermalconductivity detector (TCD) and the trace CO2 was detected by a He ionization detector (HeID). The detection sensitivity of CO2 is in the order of magnitude of 10(-6) V/V. The experimental results show that this instrument with advantages of simple design, easy operation and good stability is suitable for on-line analysis of gas samples below atmospheric pressure. We have successfully analyzed on-line the gaseous components produced in the laser cavity by using this equipment. The technique described here can be used for complete analysis of gas samples below atmospheric pressure in many other fields.

English Abstract↗

Analysis of solids, liquids, and biological tissues using solids probe introduction at atmospheric pressure on commercial LC/MS instruments.

Direct analysis of samples using atmospheric pressure ionization (API) provides a more rapid method for analysis of volatile and semivolatile compounds than vacuum solids probe methods and can be accomplished on commercial API mass spectrometers. With only a simple modification to either an electrospray (ESI) or atmospheric pressure chemical ionization (APCI) source, solid as well as liquid samples can be analyzed in seconds. The method acts as a fast solids/liquid probe introduction as well as an alternative to the new direct analysis in real time (DART) and desorption electrospray ionization (DESI) methods for many compound types. Vaporization of materials occurs in the hot nitrogen gas stream flowing from an ESI or APCI probe. Ionization of the thermally induced vapors occurs by corona discharge under standard APCI conditions. Accurate mass and mass-selected fragmentation are demonstrated as is the ability to obtain ions from biological tissue, currency, and other objects placed in the path of the hot nitrogen stream.

Atmospheric Pressure↗

The effect of changes in atmospheric pressure on the occurrence of the spontaneous onset of labor in term pregnancies.

OBJECTIVE: Our purpose was to determine whether there is a relationship between changes in atmospheric pressure and spontaneous onset of labor in term pregnancy. STUDY DESIGN: All women admitted to Medical Center of Central Massachusetts-Memorial Hospital with spontaneous onset of labor at term and who were delivered on the service during a 12-month period represent the cohort for this study. Each maternal chart was abstracted to ensure that each member of the cohort met the inclusion criteria. Hourly recordings of atmospheric pressure made at the Worcester Station of the National Weather Service, Department of Commerce, were used as the meteorologic data points of interest. Least-squares regression was used to determine an equation that expresses the probability of the onset of labor in this cohort as a function of gestational age, which was used to calculate expected numbers for the statistical analyses. Two relationships were studied: (1) the ratio of the observed to the expected number of onsets of labor and (2) the initiation of labor and atmospheric pressure changes in the preceding 3 hours. RESULTS: Three-hour periods of falling atmospheric pressure were less often followed by initiation of labor than were the periods with other types of pressure sequences. No association was observed between the onset of labor and days of low mean pressure. CONCLUSION: Although there was an observed statistically significant association between falling barometric pressure and onset of labor, the magnitude of the difference is not of clinical significance.

Atmospheric Pressure↗

Passive landfill gas emission - Influence of atmospheric pressure and implications for the operation of methane-oxidising biofilters.

A passively vented landfill site in Northern Germany was monitored for gas emission dynamics through high resolution measurements of landfill gas pressure, flow rate and composition as well as atmospheric pressure and temperature. Landfill gas emission could be directly related to atmospheric pressure changes on all scales as induced by the autooscillation of air, diurnal variations and the passage of pressure highs and lows. Gas flux reversed every 20 h on average, with 50% of emission phases lasting only 10h or less. During gas emission phases, methane loads fed to a connected methane oxidising biofiltration unit varied between near zero and 247 g CH4 h(-1)m(-3) filter material. Emission dynamics not only influenced the amount of methane fed to the biofilter but also the establishment of gas composition profiles within the biofilter, thus being of high relevance for biofilter operation. The duration of the gas emission phase emerged as most significant variable for the distribution of landfill gas components within the biofilter.

Air Movements↗

Atmospheric pressure MALDI-fourier transform mass spectrometry.

The coupling of atmospheric pressure matrix-assisted laser desorption/ionization (AP MALDI) with Fourier transform mass spectrometry (FTMS) is described, and its significance for the high-resolution analysis of complex peptide mixtures is demonstrated. High kinetic energy and extensive metastable decay characteristic of ions generated by vacuum MALDI have been known to constitute a possible obstacle to high-resolution analysis by FTMS. Since the initial coupling of laser desorption techniques with FTMS was realized two decades ago, several different solutions have been proposed to control the energy of the ions and fulfill the promise of high sensitivity and high resolution offered by this analytical method. Initial results obtained on quadrupole time-of-flight and ion trap analyzers have shown that ions generated by MALDI at atmospheric pressure are intrinsically less energetic than those provided by vacuum MALDI. Our report indicates that this characteristic is particularly beneficial for FTMS applications in which a sharp reduction of metastable decay can make larger ion currents available for detection and possible tandem experiments. In our hands, AP MALDI-FTMS has enabled the analysis of complex peptide mixtures with resolution and accuracy comparable to those obtained by analogous electrospray ionization-FTMS experiments, with no evidence of either metastable decomposition or significant formation of matrix adducts. Analysis of a trypsin digest of bovine serum albumin provided signal-to-noise ratios and limits of detection similar to those obtained by ion trap analyzers, but with unmatched resolution and accuracy. AP MALDI has been shown to provide stable precursor ions in amounts that allowed for informative tandem experiments. Finally, the potential of AP MALDI-FTMS for the high-resolution screening of complex mixtures was demonstrated by the analysis of isobaric peptides differing in mass by less than 0.04 Da.

Animals↗

Plant adaptation to low atmospheric pressures: potential molecular responses.

There is an increasing realization that it may be impossible to attain Earth normal atmospheric pressures in orbital, lunar, or Martian greenhouses, simply because the construction materials do not exist to meet the extraordinary constraints imposed by balancing high engineering requirements against high lift costs. This equation essentially dictates that NASA have in place the capability to grow plants at reduced atmospheric pressure. Yet current understanding of plant growth at low pressures is limited to just a few experiments and relatively rudimentary assessments of plant vigor and growth. The tools now exist, however, to make rapid progress toward understanding the fundamental nature of plant responses and adaptations to low pressures, and to develop strategies for mitigating detrimental effects by engineering the growth conditions or by engineering the plants themselves. The genomes of rice and the model plant Arabidopsis thaliana have recently been sequenced in their entirety, and public sector and commercial DNA chips are becoming available such that thousands of genes can be assayed at once. A fundamental understanding of plant responses and adaptation to low pressures can now be approached and translated into procedures and engineering considerations to enhance plant growth at low atmospheric pressures. In anticipation of such studies, we present here the background arguments supporting these contentions, as well as informed speculation about the kinds of molecular physiological responses that might be expected of plants in low-pressure environments.

Acclimatization↗

Direct antagonism of ethanol's effects on GABA(A) receptors by increased atmospheric pressure.

Previous studies have shown that exposure to 12 times normal atmospheric pressure of helium-oxygen gas (heliox) directly antagonizes a range of ethanol's acute and chronic behavioral effects. The present study extends the investigation to the biochemical level by investigating the effects of pressure on ethanol-induced potentiation of GABA(A) receptor function in mouse membrane vesicles (microsacs). Exposure to 12 atmospheric pressure heliox significantly antagonized ethanol (25 to 100 mM) potentiation of GABA-activated 36Cl- uptake, but did not significantly alter baseline GABA(A) receptor function measured by the response of the system to GABA (10 to 100 microM), bicuculline (3 and 100 microM), or picrotoxin (100 microM). These findings add essential support for the hypothesis that hyperbaric exposure is a direct ethanol antagonist that can be used as a tool to help identify ethanol's initial cellular and molecular sites of action that cause its behavioral effects. Taken in context with previous behavioral studies, the present results also provide important new evidence for a cause-effect relationship between ethanol potentiation of GABA(A) receptor function and ethanol's anesthetic and behavioral effects.

Alcoholic Intoxication↗