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Atmospheric pressure laser desorption/ionization on porous silicon.

A recently developed commercial atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) source (MassTech, Inc.) was modified to adopt commercially available DIOS plates (Mass Consortium Corp.) for the studies of laser desorption from the surface of porous silicon under atmospheric pressure conditions. The feasibility of atmospheric pressure laser desorption/ionization from the surface of porous silicon (AP-DIOS) was demonstrated. The advantages of this new AP-DIOS technique include reasonably good sensitivity (subpicomole range for standard peptide mixtures), simplicity of sample preparation, uniformity of target spots and the absence of matrix peaks in the spectra. The AP-DIOS source was interfaced with a commercial ion trap (LCQ Classic, Thermo Finnigan) which additionally provides a unique MS(n) capability. The AP-DIOS spectrum of 250 fmol of unseparated tryptic digest of bovine serum albumin (BSA) was compared with that of AP-MALDI for the same compound. AP-DIOS offers significantly better coverage for the digest components in the mass range 200-1000 Da. The combined data of both techniques enabled us to nearly double the number of matched peaks in BSA digest analysis compared with AP-DIOS or AP-MALDI analysis separately.

Angiotensins↗

On the mechanism of ion formation from the aqueous solutions irradiated with 3 microm IR laser pulses under atmospheric pressure.

The mechanism of atmospheric pressure (AP) laser ionization of water and water/glycerol liquid samples at a 3-microm wavelength is studied experimentally. For the ion desorption, an in-house built Yb : YAG-pumped optical parametric oscillator (OPO) infrared (IR) laser has been coupled with AP MALDI ion source interfaced to an ion trap mass spectrometer (MS). It has been shown that water is primarily responsible for ion generation in water/glycerol samples, while glycerol increases the solution viscosity and decreases the water evaporation rate and sample losses. In contrast to AP UV-MALDI, the electric field in the case of AP IR-MALDI does not assist in ion production. It was found that the absence of the electrical field provides the optimum ionization condition both for water and water/glycerol liquid samples at the 3-microm laser irradiation. A two-stage ion formation mechanism, which includes the initial emission of microdroplets and release of molecular ions at the second stage, can explain the experimentally observed ion signal dependencies upon the voltage applied between MS inlet and the MALDI sample plate. Postionization using additional corona discharge APCI increases the observed signal by approximately 50%, which indicates that some portion of the analyte is desorbed in the form of neutral molecules.

Air Pressure↗

Multi-atmospheric pressure ionisation interface for liquid chromatography-mass spectrometry.

We describe the structure of a multi-atmospheric pressure ionisation (multi-API) interface for liquid chromatography-mass spectrometry (LC-MS). This interface includes five modes of atmospheric pressure spray with electron impact ionisation (APEI), atmospheric pressure chemical ionisation (APCI), atmospheric pressure spray ionisation (APSI), electrospray ionisation (ESI) and sonic spray ionisation (SSI). This LC-MS system was realised by developing an APEI interface which resembles other API interfaces and a highly sensitive API interface using advanced collision induced dissociation in a differential pumping region and an electrostatic ion guide. This system can deal with a wide variety of organic compounds from hydrocarbons with low polarity to proteins with high polarity by using the five modes.

Atmospheric Pressure↗

Study of a bisquaternary ammonium salt by atmospheric pressure photoionization mass spectrometry.

A comprehensive atmospheric pressure photoionization (APPI) mass spectrometry investigation of hexamethonium bromide is reported. This bisquaternary ammonium salt is a model system for the investigation of multiply charged species and elucidation of ion formation processes. It has been used to elucidate the physicochemical phenomenon occurring when photoionization is carried out at atmospheric pressure. First, the in-source fragmentations were studied for aqueous solutions of the salt with the photoionization lamp switched off, i.e. under thermospray conditions. It is shown that, in this mode of operation, fragmentations are minor and may be classified into two classes, namely dequaternization and charge separation, arising from the two precursors, M2+ and [M+Br]+. Second, the fragmentation patterns have been monitored in dopant- assisted APPI for different dopants (toluene, toluene-d8, anisole and hexafluorobenzene) at various amounts. At low dopant flow rates, the [M+Br]+ and M2+ ions are still observed. As the flow rate is increased, these precursor ions lose intensity and are finally suppressed for all three dopants. Comparison of toluene and toluene-d8 reveals that H atoms may be transferred from the dopant to the molecular ions, very likely mediated by the solvent. The role of the solvent (water) was also investigated by using heavy water. Apart from the thermospray fragmentations, which are also observed in APPI, several fragmentation pathways appear to be specific to the photoionization process. Photoionization efficiencies are measured by determination of the relative photoionization cross sections with respect to toluene. It is found that, when the ionization efficiencies are taken into account, the depletion of the precursors as a function of the dopant flow rates is the same for all three dopant molecules. This result shows that the precursor ions are depleted by reactions with the photoelectrons released from the dopant. Three additional mechanisms are proposed to account for this effect: electron transfer or H atom transfer from negatively charged water nanodroplets and H atom transfer from the dopant.

Journal Article↗

The effects of extra-low-frequency atmospheric pressure oscillations on human mental activity.

Slight atmospheric pressure oscillations (APO) in the extra-low-frequency range below 0.1 Hz, which frequently occur naturally, can influence human mental activity. This phenomenon has been observed in experiments with a group of 12 healthy volunteers exposed to experimentally created APO with amplitudes 30-50 Pa in the frequency band 0.011-0.17 Hz. Exposure of the subjects to APO for 15-30 min caused significant changes in attention and short-term memory functions, performance rate, and mental processing flexibility. The character of the response depended on the APO frequency and coherence. Periodic APO promoted purposeful mental activity, accompanied by an increase in breath-holding duration and a slower heart rate. On the other hand, quasi-chaotic APO, similar to the natural perturbations of atmospheric pressure, disrupted mental activity. These observations suggest that APO could be partly responsible for meteorosensitivity in humans.

Adult↗

Periods of low atmospheric pressure are associated with high abdominal aortic aneurysm rupture rates in Northern Ireland.

Seasonal and circadian variation in the incidence of ruptured abdominal aortic aneurysm (RAAA) has been reported. We explored the role of atmospheric pressure changes on rupture incidence and its relationship to cardiovascular risk factors. During a three year-period, 1st April 1998 and 31st March 2001, data was prospectively acquired on 144 Ruptured Abdominal Aortic Aneurysm (RAAA) presenting to the Regional Vascular Surgery Unit at the Royal Victoria Hospital, Belfast, Northern Ireland. For each patient the chronology of acute onset of symptoms and presentation to the regional vascular unit was recorded, along with details of standard cardiovascular risk factors. During the same period meteorological data including atmospheric pressure and air temperature were recorded daily at the regional meteorological research unit, Armagh. We then analyzed the monthly mean values for daily rupture incidence in relation to the monthly values for atmospheric pressure, pressure change and temperature. Furthermore atmospheric pressure on the day of rupture, and day preceding rupture, were also analyzed in relation to days without rupture presentation and between individual ruptures for various cardiovascular risk factors. Data demonstrated a significant monthly variation in aneurysm rupture frequency, (p<0.03, ANOVA). There was also a significant monthly variation in mean barometric atmospheric pressure, (p<0.0001, ANOVA), months with high rupture frequency also exhibiting low average pressures in the months of April (0.24 +/- 0.04 ruptures per day and 1007.78 +/- 1.23 mB) and September (0.16 +/- 0.04 ruptures per day and 1007.12 +/- 1.14 mB), respectively. The average barometric pressures were found to be significantly lower on those days when ruptures occurred (n=1127) compared to days when ruptures did not occur (n=969 days), (1009.98 +/- 1.11 versus 1012.09 +/- 0.41, p<0.05). Full data on risk factors was available on 103 of the 144 rupture patients and was further analyzed. Interestingly, RAAA with a known history of hypertension, (n=43), presented on days with significantly lower atmospheric pressure than those without, (n=60), (1008.61 +/- 2.16 versus 1012.14 +/- 1.70, p<0.05). Further analysis of ruptures grouped into those occurring on days above or below mean annual atmospheric pressure 1013.25 (approximately 1 atmosphere), by Chi-square test, revealed three cardiovascular risk factors significantly associated with low-pressure rupture, (p<0.05). Data represents mean +/- SEM, statistical comparisons with Student t-test and ANOVA. These data demonstrate a significant association between periods of low barometric pressure and high incidence of ruptured aneurysm, especially in those patients with known hypertension. The association between rupture incidence and barometric pressure warrants further study as it may influence the timing of elective AAA repair.

Adult↗

Atmospheric pressure ionization in a miniature mass spectrometer.

A miniature cylindrical ion trap mass spectrometer featuring an atmospheric pressure interface allowing atmospheric pressure chemical ionization and electrospray ionization is described together with its analytical performance characteristics. The vacuum system, ion optics, mass analyzer, control electronics system, and detection system have all been designed and built in-house. The design is based upon a three-stage, differentially pumped vacuum system with the instrument capable of being interfaced to many types of atmospheric pressure ionization sources. Ions are transferred through home-built ion optics, and instrument control is achieved through custom-designed electronics and LabView control software. Corona discharge ionization and electrospray ionization sources are implemented and used to allow the analysis of both gaseous- and solution-phase samples during the characterization of the instrument. An upper mass/charge limit of approximately 450 Th with unit resolution was achieved using a 2.5-mm-internal radius cylindrical ion trap as the mass analyzer. The specificity of the instrument can be increased by employing the MS/MS capabilities of the ion trap and has been demonstrated for nitrobenzene. Limits of detection for the trace analysis in air of the chemical warfare agent simulant methyl salicylate (1.24 ppb) and for nitrobenzene (629 pptr) are achieved. The dynamic range of the instrument is currently limited to approximately 2 orders of magnitude by saturation of the detection electronics. Isolation and collision-induced dissociation efficiencies in MS/MS experiments both greater than 50% are reported. Electrospray/nanospray data are presented on solutions including 100 microM (D,L)-arginine, 10 microM (-)-ephedrine, and 10 microM lomefloxacin.

Journal Article↗

Intracapsular and atmospheric pressure in the dynamics and stability of the hip. A biomechanical study.

A cadaver study was undertaken to evaluate (a) the relations between the rotation around the axis of the neck of the femur, intracapsular effusion, and intracapsular pressure; and (b) the importance of the atmospheric pressure in stabilizing the hip joint. The following conclusions were reached: (1) There is no increase in intracapsular pressure within the normal range of rotation ("flexion") around the axis of the neck of the femur. (2) Intracapsular fluid (e.g., blood, pus, synovial edema and/or free synovial fluid) decreases this pressureless range of rotation, a likely cause of pain and subsequently flexion contractures. (3) Joint stability is primarily maintained by the atmospheric pressure within the normal range of rotation. The joint capsule is tightened only in extreme extension or flexion and contributes to stability only in these positions. (4) The traction force needed to overcome the stabilizing effect of the atmospheric pressure and thus subluxate the adult joint is approximately 200 N, in a child less, proportional to the square of the diameter of the femoral head. We also propose that intracapsular fluid makes the joint potentially unstable, a prerequisite for unfavorable mechanical cartilage load. These findings have clinical implications in synovitis, septic and juvenile arthritis, congenital dislocation of the hip, arthroplasty, and trauma.

Adult↗

Analysis of triglycerides using atmospheric pressure chemical ionization mass spectrometry.

Atmospheric pressure chemical ionization (APCI) mass spectrometry was investigated as a new method for analysis of a mixture of triglycerides separated by reverse-phase high-performance liquid chromatography. A mixture of homogeneous (monoacid) triglyceride standards containing fatty acids with zero to three double bonds was analyzed to demonstrate the quality of mass spectra obtained by using the APCI interface. The mass spectra showed that minimal fragmentation occurs, resulting primarily in diglyceride [M-RCOO]+ ions and [M + 1]+ protonated molecular ions. The degree of unsaturation within the acyl chains had a marked effect on the proportion of diglyceride ions vs. the [M + 1]+ ions formed in the APCI source. The mass spectra of triglycerides containing fatty acids with two or three double bonds showed predominantly protonated triglyceride ions, with diglyceride peaks representing 13 to 25% of the base peak. The triglycerides containing singly unsaturated fatty acids gave diglyceride ions as the base peak, and [M + 1]+ ions with an intensity 20 to 28% that of the base peak. Only diglyceride ions were observable in the spectra of triglycerides containing saturated fatty acids.

Atmospheric Pressure↗

Liquid sample injection using an atmospheric pressure direct current glow discharge ionization source.

An atmospheric pressure DC glow discharge in helium has been used as an ionization source for organic samples introduced by liquid injection into atmospheric pressure ionization mass spectrometry (API/MS). The glow source operates typically in the range up to 1 mA of current at less than 1 kV, although the source can be operated up to a discharge current of 10 mA. Even at the high current used in this work, the protonated molecule, MH+, is observed with little or no fragmentation for many of the samples studied. The detection limits achieved for API glow discharge detection are typically in the low femtomole region for small organic molecules including small biological neurotransmitters, drugs, pesticides, phenylthiohydantoin-substituted amino acids, and explosives. A detection limit of approximately 2 pg has been achieved for tyramine with linear quantitation over at least 3 orders of magnitude. The sensitivity in these experiments has been further improved by optimization of the skimmer-interface system and the liquid injection/nebulization design.

Amino Acid Sequence↗

Determination of chloramphenicol residues in fish meats by liquid chromatography-atmospheric pressure photoionization mass spectrometry.

A liquid chromatography-atmospheric pressure photoionization (APPI) mass spectrometry method was developed for the determination of chloramphenicol (CAP) in fish meats (young yellowtail and flatfish). For the optimization of APPI, several APPI ion source parameters and mobile phases were investigated. CAP with APPI using the optimized parameters gave simple mass spectra and a strong signal corresponding to [M-H]- was observed. Further, APPI was compared with atmospheric pressure chemical ionization (APCI) and APPI gave similar results in terms of structural information and a better signal-to-noise ratio. The samples were extracted with acetonitrile and evaporated to dryness followed by a clean-up step using the liquid-liquid distribution between acetonitrile and n-hexane. The mean recoveries of chloramphenicol from a young yellowtail meat and a flatfish meat spiked at 0.1-2 ng/g were 89.3-102.5 and 87.4-94.8%, respectively. The limit of detection (signal-to-noise ratio = 3) of the young yellowtail meat and the flatfish meat were 0.1 and 0.27 ng/g.

Anti-Bacterial Agents↗

Effect of atmospheric pressure on maize root growth and ethylene production.

Maize (Zea mays) seedlings were exposed to elevated atmospheric pressures while growing in moist sand in open plastic envelopes to evaluate the effects of directly applied atmospheric pressure on ethylene production and root growth. Effects were evaluated after 24 h. The threshold pressures necessary to promote ethylene production and decrease root elongation were about 600 and 400 kPa, respectively. Direct atmospheric pressure, at levels up to 300 kPa, mimicked the control decrease in root diameter and increased diameter only slightly at 500 to 1200 kPa. In contrast, in previous work it was shown that physical impedance resulting from compression of the growth medium by external application of 100 kPa increased the ethylene production rate 4-fold and the root diameter 7-fold while reducing elongation 75% in 10 h. The relative insensitivity of roots to direct atmospheric pressure suggests that they perceive physical impedance, achieved experimentally by compressing the growth medium, via a surface mechanism rather than via a pressure-sensing mechanism.

Journal Article↗

Mass spectrometry of N-linked oligosaccharides using atmospheric pressure infrared laser ionization from solution.

An atmospheric pressure (AP) infrared (IR) laser ionization technique, implemented on a quadrupole ion trap mass spectrometer, was used to analyze underivatized, N-linked oligosaccharides in solution. Experiments were conducted on an atmospheric pressure infrared ionization from solution (AP-IRIS) ion source which differed from previous AP IR matrix-assisted laser desorption/ionization (MALDI) interfaces in that the ion source operated in the absence of an extraction electric field with a higher power 2.94 microm IR laser. The general term 'IRIS' is used as the mechanism of ionization differs from that of MALDI, and is yet to be fully elucidated. The AP-IRIS ion source demonstrated femtomole-level sensitivity for branched oligosaccharides. AP-IRIS showed approximately 16 times improved sensitivity for oligomannose-6 and the core-fucosylated glycan M3N2F over optimal results obtainable on a AP UV-MALDI with a 2,4,6-trihydroxyacetophenone matrix. Comparison between IR and UV cases also showed less fragmentation in the IR spectrum for a glycan with a conserved trimannosyl core, core-substituted with fucose. A mixture of complex, high-mannose and sialylated glycans resulted in positive ion mass spectra with molecular ion peaks for each sugar. Tandem mass spectrometry of the sodiated molecular ions in a mixture of glycans revealed primarily glycosidic (B, Y) cleavages. The reported results show the practical utility of AP-IRIS while the ionization mechanism is still under investigation.

Air Pressure↗

Liquid chromatography/mass spectrometric determination of patulin in apple juice using atmospheric pressure photoionization.

This paper describes a comparison between atmospheric pressure chemical ionization (APCI) and the recently introduced atmospheric pressure photoionization (APPI) technique for the liquid chromatography/mass spectrometric (LC/MS) determination of patulin in clear apple juice. A column switching technique for on-line extraction of clear apple juice was developed. The parameters investigated for the optimization of APPI were the ion source parameters fragmentor voltage, capillary voltage, and vaporizer temperature, and also mobile phase composition and flow rate. Furthermore, chemical noise and signal suppression of analyte signals due to sample matrix interference were investigated for both APCI and APPI. The results indicated that APPI provides lower chemical noise and signal suppression in comparison with APCI. The linear range for patulin in apple juice (correlation coefficient >0.999) was 0.2-100 ng mL(-1). Mean recoveries of patulin in three apple juices ranged from 94.5 to 103.2%, and the limit of detection (S/N = 3), repeatability and reproducibility were 1.03-1.50 ng mL(-1), 3.9-5.1% and 7.3-8.2%, respectively. The total analysis time was 10.0 min.

Beverages↗

A stress protein is induced in the deep-sea barophilic hyperthermophile Thermococcus barophilus when grown under atmospheric pressure.

The whole-cell protein inventory of the deep-sea barophilic hyperthermophile Thermococcus barophilus was examined by one-dimensional SDS gradient gel electrophoresis when grown under different pressure conditions at 85 degrees C (Topt). One protein (P60) with a molecular mass of approximately 60 kDa was prominent at low pressures (0.3 MPa hydrostatic pressure and 0.1 MPa atmospheric pressure) but not at deep-sea pressures (10, 30, and 40 MPa). About 17 amino acids were sequenced from the N-terminal end of the protein. Sequence homology analysis in the GenBank database showed that P60 most closely resembled heat-shock proteins in some sulfur-metabolizing Archaea. A high degree of amino acid identity (81%-93%) to thermosome subunits in Thermococcales strains was found. Another protein (P35) with molecular mass of approximately 35.5 kDa was induced at 40 MPa hydrostatic pressure but not under low-pressure conditions. No amino acid sequence homology was found for this protein when the 40 amino acids from the N-terminal end were compared with homologous regions of proteins from databases. A PTk diagram was generated for T. barophilus. The results suggest that Phabitat is about 35 MPa, which corresponds to the in situ pressure where the strain was obtained.

Amino Acid Sequence↗

Relation of atmospheric pressure changes and the occurrences of acute myocardial infarction and stroke.

Previous studies have demonstrated variation in vascular events with respect to season and time of day. Changes in barometric pressure display daily and seasonal variations and could modulate the occurrence of vascular events. The objective of this study was to determine whether a relation exists between changes in barometric pressure and occurrence of stroke or acute myocardial infarction (AMI). A retrospective analysis of hospital admissions for AMI and stroke from 1993 to 1996 in central Texas was related to changes in atmospheric pressure that were obtained from the National Climatic Data Center. Patients who had AMI (n = 1,327) or stroke (n = 839) were identified from a computerized hospital database. Mean atmospheric pressure, greatest change in pressure, and rate of change in pressure per 24-hour period were computed. One-, 2-, and 3-day and seasonal groupings of cardiovascular events were related to corresponding changes in barometric pressure. The fall and winter seasons had the highest variability in atmospheric pressure readings. There was a significant correlation (p = 0.0083) between a decrease in atmospheric pressure and the occurrence of AMI the day after a pressure decrease, especially during the fall and winter seasons. No relation between stroke and atmospheric pressure was demonstrated. In conclusion, we conclude that rapid decreases in barometric pressure are associated with the occurrence of AMI but not of stroke.

Atmospheric Pressure↗