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At least 145 records · Page 8Linked to original sources
PubMed2000

Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry.

A novel ionization source for biological mass spectrometry is described that combines atmospheric pressure (AP) ionization and matrix-assisted laser desorption/ionization (MALDI). The transfer of the ions from the atmospheric pressure ionization region to the high vacuum is pneumatically assisted (PA) by a stream of nitrogen, hence the acronym PA-AP MALDI. PA-AP MALDI is readily interchangeable with electrospray ionization on an orthogonal acceleration time-of-flight (oaTOF) mass spectrometer. Sample preparation is identical to that for conventional vacuum MALDI and uses the same matrix compounds, such as alpha-cyano-4-hydroxycinnamic acid. The performance of this ion source on the oaTOF mass spectrometer is compared with that of conventional vacuum MALDI-TOF for the analysis of peptides. PA-AP MALDI can detect low femtomole amounts of peptides in mixtures with good signal-to-noise ratio and with less discrimination for the detection of individual peptides in a protein digest. Peptide ions produced by this method generally exhibit no metastable fragmentation, whereas an oligosaccharide ionized by PA-AP MALDI shows several structurally diagnostic fragment ions. Total sample consumption is higher for PA-AP MALDI than for vacuum MALDI, as the transfer of ions into the vacuum system is relatively inefficient. This ionization method is able to produce protonated molecular ions for small proteins such as insulin, but these tend to form clusters with the matrix material. Limitations of the oaTOF mass spectrometer for singly charged high-mass ions make it difficult to evaluate the ionization of larger proteins.

Animals↗
PubMed1993

Effects of atmospheric pressure variation on spontaneous, transiently evoked, and distortion product otoacoustic emissions in normal human ears.

The effects of atmospheric pressure changes on the frequency and amplitude of spontaneous (SOAEs), transiently evoked (TEOAEs) and distortion product (DPOAEs) otoacoustic emissions in normally hearing humans were compared. The purpose was to determine if the transmission of each form of OAE was influenced differently by the middle ear. Sixty-one subjects were tested in a pressure chamber. Twenty-seven SOAEs with a frequency range between 535 to 4729 Hz from 21 subjects were examined. Transiently evoked OAEs were studied in 20 subjects using clicks and tone-bursts at 0.5, 1, 2, 3, and 4 kHz. Distortion-product OAEs were generated at seven geometric mean frequencies between 1 and 8 kHz in another 20 subjects. Spontaneous OAEs were examined by applying atmospheric pressure up to 9 kPa and down to -2.5 kPa, for the measurement of TEOAEs and DPOAEs the pressure was varied from 0 kPa up to 8 kPa. In spite of large interindividual differences, results suggest that the influence of pressure on the three OAEs is frequency specific. The frequency and amplitude change of SOAEs, the modification of the amplitude and spectra of TEOAEs, and the amplitude change of DPOAEs are more influenced by changes in middle ear pressure below 4 kHz than are OAEs in the range at 4 kHz and above.

Acoustic Stimulation↗
PubMed2002

Laser desorption-atmospheric pressure chemical ionization: a novel ion source for the direct coupling of polyacrylamide gel electrophoresis to mass spectrometry.

Laser desorption-atmospheric pressure chemical ionization-mass spectrometry (LD-APCI-MS) is presented for the atmospheric pressure (AP) sampling of tryptic peptides directly from a polyacrylamide gel. In contrast to other gel sampling mass spectrometric approaches, this technique does not require the addition of any exogenous matrices to the gel to assist with ionization. In this arrangement, a CO(2) laser at 10.6 micro m is used to desorb intact neutral peptide molecules from the gel, followed by ionization in the gas-phase with APCI. The ions are then sampled via a heated capillary inlet and transferred to a quadrupole ion trap mass spectrometer for mass analysis. Preliminary results suggest the polyacrylamide gel electrophoresis-LD-APCI-MS technique provides several advantages that could translate into a more convenient, robust methodology for the rapid identification and characterization of proteins. Finally, strategies regarding the further development of the method are presented.

Amino Acid Sequence↗
PubMed2004

Atmospheric pressure matrix-assisted laser desorption/ionization with analysis by ion mobility time-of-flight mass spectrometry.

The use of an atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) source was employed with an atmospheric pressure ion mobility spectrometer (APIMS) and an orthogonal acceleration reflector time-of-flight mass spectrometer (TOFMS) to analyze dipeptide and biogenic amine mixtures from a liquid glycerol 2,5-dihydroxybenzoic acid (DHB) matrix. Improved sensitivities were obtained by the addition of a localized electrical (corona) discharge in conjunction with the AP-MALDI source. Enhanced sample ionization efficiency created by this combination provided an overall elevation in signal intensity of approximately 1.3 orders in magnitude. Combinations of three dipeptides (Gly-Lys, Ala-Lys, and Val-Lys) and nine biogenic amines (dopamine, serotonin, B-phenylethylamine, tyramine, octopamine, histamine, tryptamine, spermidine, and spermine) were resolved in less than 18 ms. In many cases, reduced mobility constants (K(o)) were determined for these analytes for the first time. Ion mobility drift times, flight times, arbitrary signal intensities, and collision-induced dissociation (CID) fragmentation product signatures are reported for each of the samples.

Atmospheric Pressure↗
PubMedDate not supplied

Direct atmospheric pressure coupling of polyacrylamide gel electrophoresis to mass spectrometry for rapid protein sequence analysis.

Using laser desorption-atmospheric pressure chemical ionization we describe a novel approach for coupling mass spectrometry to polyacrylamide gel electrophoresis. In contrast to other approaches, the method allows for the direct sampling of a polyacrylamide gel-embedded protein without the addition of any exogenous matrixes and is performed at atmospheric pressure. After electrophoresis and enzymatic digestion, the gel is analyzed at AP by photons that desorb neutral peptide molecules, followed by corona discharge ionization in the gas-phase, and subsequent mass analysis. Our experimental results demonstrate the method to (1) rapidly identify electrophoresed proteins via "peptide fingerprinting" using protein databases, (2) detect single-amino acid polymorphisms, and (3) has potential for sub-picomole sensitivity while still maintaining in situ gel desorption-ionization at ambient conditions.

Atmospheric Pressure↗
PubMed2004

Atmospheric pressure MALDI with pulsed dynamic focusing for high-efficiency transmission of ions into a mass spectrometer.

The atmospheric pressure (AP) matrix-assisted laser desorption/ionization (MALDI) technique described to date has proven to be a convenient and rapid method for soft ionization of biomolecules. However, this technique, like other AP ionization methods, has so far suffered from a low efficiency in transmitting ions from atmospheric pressure into the vacuum of the mass spectrometer (MS). In this work, a novel technique we termed pulsed dynamic focusing, or PDF, which improves the ion transmission efficiency and sensitivity of AP-MALDI by over an order of magnitude, is described. Pulsed dynamic focusing operates on the basis of pulsing a high-voltage extraction field to zero, when ions are just outside of the MS entrance, to allow the intake gas flow of the MS to effectively entrain the ions into the MS. Results from application of the PDF technique to an AP-MALDI ion trap MS demonstrated that in comparison to static AP-MALDI operation (1). up to 2.1 times more ions from a given laser shot could be transferred into the MS, (2). applying higher voltages in combination with the switching scheme yielded up to 1.6-times-higher ion intensities, and (3). a 3-times-larger laser spot area could be utilized. The combination of these factors produced an enhancement in throughput and sensitivity, as measured by the ions detected per unit time, of over 12 times for a digest sample of bovine serum albumin. In addition, the PDF technique proved to make AP-MALDI less sensitive to laser positioning, creating a more robust ion source in comparison to static AP-MALDI.

Atmospheric Pressure↗
PubMed2000

Development of multi-ESI-sprayer, multi-atmospheric-pressure-inlet mass spectrometry and its application to accurate mass measurement using time-of-flight mass spectrometry.

The atmospheric pressure sampling nozzle (orifice, heated capillary, or inlet) of a high mass accuracy time-of-flight mass spectrometer (TOF-MS) was modified by replacing its single nozzle with multiple atmospheric pressure nozzles. This allowed multiple streams of liquids to be introduced into the MS in parallel (an electrosprayer for each nozzle), with minimum analyte interactions between the streams. The chemical contents of all liquid streams were analyzed concurrently using a single mass spectrometer. To obtain a higher mass accuracy by providing internal reference on each scan (acquisition) and to evaluate the suitability of TOF-MS for molecular-formula confirmation, a dual-ESI-sprayer, dual-nozzle version of this design was used. The accurate masses of tens of organic compounds in the mass range of 200-3000 Da were measured, and the results were compared with those obtained using dual-sprayer, single-nozzle TOF-MS. A significant improvement in mass accuracy was observed when the former technique was used. Comparison between the mass accuracy using dual-ESI-sprayer, dual-nozzle TOF-MS and that obtained using a double-focusing mass spectrometer operating under chemical ionization (CI) and fast atom bombardment (FAB) shows the suitability of the technique for elemental-composition confirmation. Approximately 85% of samples analyzed had mass errors of less than 5 ppm, and the other 15% had mass errors less than 8 ppm. Using a high-performance liquid chromatography (HPLC) as a device for introduction of one liquid stream (sample) and a syringe pump as a device for introduction of the second liquid stream (reference standard), the accurate mass of a tryptic digest of cytochrome c was measured. The range of mass errors was from -6.1 ppm to +3.6 ppm, a significant improvement over our previously reported mass accuracy for this digest using single-nozzle TOF-MS. The interactions between analytes in the liquid streams also were investigated using a variety of sample-introduction and nozzle-design combinations, including single-ESI-sprayer, single-nozzle; dual-ESI-sprayer, single-nozzle; dual-ESI-sprayer, Y-shaped inlet; and dual-ESI-sprayer, dual-inlet. The results demonstrated that the dual-ESI-sprayer, dual-inlet design provides reference peaks on every acquisition with minimum analyte-reference interaction and, therefore, higher consistent mass accuracy.

Atmospheric Pressure↗
PubMed1995

Application of a new atmospheric pressure ionization source for double focusing sector instruments.

In three application examples we demonstrate how the capabilities of a modern atmospheric pressure ionization (API) source, as a universal LC-MS coupling tool, are supplemented by the high mass resolution available on double focusing sector instruments. The examples include charge state determination in complex electrospray ionization-collisional induced dissociation (ESI-CID) spectra of multiply charged ions, mixture analysis of multicomponent samples without prior chromatographic separation, and very sensitive and highly specific detection of pesticides using atmospheric pressure chemical ionization (APCI).

Amino Acid Sequence↗
PubMed2004

Modeling of microwave-sustained plasmas at atmospheric pressure with application to discharge contraction.

The modeling of microwave-sustained discharges at atmospheric pressure is much less advanced than at reduced pressure (<10 Torr) because of the greater complexity of the mechanisms involved. In particular, discharge contraction, a characteristic feature of high-pressure discharges, is not well understood. To describe adequately this phenomenon, one needs to consider that the charged-particle balance in atmospheric-pressure discharges relies on the kinetics of molecular ions, including their dissociation through electron impact. Nonuniform gas heating plays a key role in the radial distribution of the density of molecular ions. The onset of contraction is shown to depend only on radially nonuniform gas heating. The radial nonuniformity of the electric field intensity also plays an important role allowing one, for instance, to explain the lower degree of contraction observed in microwave discharges compared to dc discharges. We present a numerical fluid-plasma model that aims to bring into relief the main features of discharge contraction in rare gases. It calls for surface-wave discharges because of their wide range of operating conditions, enabling a closer check between theory and experiment.

Journal Article↗
PubMed2003

Fourier transform ion cyclotron resonance mass spectrometry using atmospheric pressure photoionization for high-resolution analyses of corticosteroids.

Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) was coupled with atmospheric pressure photoionization (APPI) for the first time and used for the analysis of several corticosteroids.1 The analytes showed excellent response using APPI when compared with both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). APPI has the advantage of requiring less heat for desolvation, resulting in less thermal degradation of the analytes and higher signal-to-noise than APCI. In terms of ultimate sensitivity, APPI is more efficient than either ESI or APCI for the analysis of corticosteroids. With some compounds, the high-resolution capability of FTICRMS was necessary to obtain an accurate mass due to contributions of the M(+.) (13)C isotope in the [M+H](+) ion peak.

Adrenal Cortex Hormones↗
PubMed1988

Periodontal wound healing responses to varying oxygen concentrations and atmospheric pressures.

Oxygen effects on healing gingival wedge excisions were tested using Sprague-Dawley rats. 40 operated controls were maintained at normal pressure in room air. 3 experimental groups of 40 rats each were exposed for 90 min daily to one of the following: (1) 20.8% oxygen at 2.4 atmospheres pressure, (2) 100% oxygen at 1 atmosphere, or (3) 100% oxygen at 2.4 atmospheres. 5 animals in each group were sacrificed at the following times: 30, 54, 78 h and weeks 1, 2, 3, 6 and 12. Histometric analysis was performed using light microscopy. The connective tissue healing above a reference notch on the maxillary first molar mesial root was assessed. The controls failed to show healing comparable to experimental animals until the end of 2 weeks. Enhanced connective tissue healing above the notch was most significant (p less than or equal to 0.05) in the 2.4 atmospheres pressure groups at 3 and 6 weeks when compared to controls. However, by 12 weeks, no significant differences could be detected. New cementum formation was rare and occasional root resorption was observed. Early connective tissue adaptation does not imply eventual attachment as epithelial downgrowth progressively displaced the connective tissue adjacent to the root in both experimental and control groups of this study.

Animals↗
PubMed1980

An atmospheric pressure ionography system suitable for mammography.

Ionography is a possible replacement for silver halide based imaging systems in diagnostic radiology. This type of imaging depends upon the ionisation produced in a gas by incident x-radiation. The ions formed are collected on a plastic foil and the image is made visible by a suitable development process. The physical design properties which can affect sensitivity and image quality of an ionography system are outlined in this paper. Based upon the requirements of adequate sensitivity and resolution an atmospheric pressure ionography system is described which has been designed primarily for use in mammography. Freon 13B1 gas was chosen as the x-ray absorbing medium because it contains a relatively high atomic number atom (bromine, Z = 35) and also has a high density. It is a relatively cheap gas, has a high breakdown potential and has satisfactory resolving capability, particularly when employed at atmospheric pressure with low energy x-ray beams. The performance of the system is discussed in terms of sensitivity and resolution. Problems associated with an atmospheric pressure system are outlined and possible solutions described. Preliminary clinical results obtained with the system are also presented.

Atmospheric Pressure↗
PubMed1992

Thymine photoproduct formation and inactivation of intact spores of Bacillus subtilis irradiated with short wavelength UV (200-300nm) at atmospheric pressure and in vacuo.

Vacuum exposure renders the survival of spores of Bacillus subtilis approximately five times more sensitive to ultraviolet light irradiation than exposure under atmospheric conditions. The photoproduct formation in spores irradiated under ultrahigh vacuum (UHV) conditions is compared to the photoproduct formation in spores irradiated at atmospheric pressure. Compared to irradiation at atmospheric pressure, where only the "spore photoproduct" 5-thyminyl-5,6-dihydrothymine (TDHT) can be detected, two additional photoproducts, known as the c,s and t,s isomers of thymine dimer (T<>T) are produced in vacuo. The spectral efficiencies for photoproduct formation in spores under atmospheric and vacuum conditions are compared. Since there is no increased formation of TDHT after irradiation in vacuum, TDHT cannot be made responsible for the observed vacuum effect. "Vacuum specific" photoproducts may cause a synergistic response of spores to the simultaneous action of ultraviolet light (UV) and UHV. Three different mechanisms are discussed for the enhanced sensitivity of B. subtilis spores to UV radiation in vacuum. The experiments described contribute valuable research information on the chance for survival of microorganisms in outer space.

Bacillus subtilis↗