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Katrin Fuhrer

Publications and source records attributed to Katrin Fuhrer.

6 recordsLinked to original sources

Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer.

The development of a new high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is reported. The high-resolution capabilities of this instrument allow the direct separation of most ions from inorganic and organic species at the same nominal m/z, the quantification of several types of organic fragments (CxHy, CxHyOz, CxHyNp, CxHyOzNp), and the direct identification of organic nitrogen and organosulfur content. This real-time instrument is field-deployable, and its high time resolution (0.5 Hz has been demonstrated) makes it well-suited for studies in which time resolution is critical, such as aircraft studies. The instrument has two ion optical modes: a single-reflection configuration offers higher sensitivity and lower resolving power (up to approximately 2100 at m/z 200), and a two-reflectron configuration yields higher resolving power (up to approximately 4300 at m/z 200) with lower sensitivity. The instrument also allows the determination of the size distributions of all ions. One-minute detection limits for submicrometer aerosol are <0.04 microg m(-3) for all species in the high-sensitivity mode and <0.4 microg m(-3) in the high-resolution mode. Examples of ambient aerosol data are presented from the SOAR-1 study in Riverside, CA, in which the spectra of ambient organic species are dominated by CxHy and CxHyOz fragments, and different organic and inorganic fragments at the same nominal m/z show different size distributions. Data are also presented from the MIRAGE C-130 aircraft study near Mexico City, showing high correlation with independent measurements of surrogate aerosol mass concentration.

Journal Article↗

Evaluation of a pulsed glow discharge time-of-flight mass spectrometer as a detector for gas chromatography and the influence of the glow discharge source parameters on the information volume in chemical speciation analysis.

The figures of merit of a pulsed glow discharge time-of-flight mass spectrometer (GD-TOFMS) as a detector for gas chromatography (GC) analysis were evaluated. The mass resolution for the GD-TOFMS was determined on FWHM in the high mass range (208Pb+) as high as 5,500. Precision of 400 subsequent analyses was calculated on 63Cu+ to be better than 1% RSD with no significant drift over the time of the analysis. Isotope precision based on the 63Cu+/65Cu+ ratio over 400 analyses was 1.5% RSD. The limits of detection for gaseous analytes (toluene in methanol as solvent) were determined to be as low as several hundred ppb or several hundred pg absolute without using any pre-concentration technique. Furthermore, the different GD source parameters like capillary distance, cathode-anode spacing, and GD source pressure with regards to the accessible elemental, structural, and molecular information were evaluated. It was demonstrated that each of these parameters has severe influence on the ratio of elemental, structural, and parent molecular information in chemical speciation analysis.

Journal Article↗

Lipid/peptide/nucleotide separation with MALDI-ion mobility-TOF MS.

Matrix-assisted laser desorption/ionization when combined with ion mobility-orthogonal time-of-flight mass spectrometry is a viable technique for fast separation and analysis of biomolecules in complex mixtures. Isobaric lipid, peptide, and oligonucleotide ions are preseparated before mass analysis by differences of up to 30% in mobility drift time. Ions of similar chemical type fall along well-defined "trend lines" (with deviations of approximately 3%) when plotted in two-dimensional representations of ion mobility as a function of m/z. Discussion of fundamental and technical limitations of the technique point to its potential for being most useful when applied to systems such as bodily fluids and intact tissue, where an alternative chemical or chromatographic preseparation step prior to mass analysis is either impractical or undesirable.

Analgesics, Opioid↗

Angiotensin II-acetylcholine noncovalent complexes analyzed with MALDI-ion mobility-TOF MS.

Matrix-assisted laser desorption ionization-ion mobility-orthogonal time-of-flight mass spectrometry (MALDI-IM oTOF MS) is a new technique that allows laser desorbed ion to be preseparated on the basis of their shape prior to mas analysis. Using this instrument, we tested the postulate that addition of a quaternary ammonium compound such as acetylcholine to the model phosphorylated peptide angio tensin II would enhance its detection by MALDI in two ways. First of all, the acetylcholine-peptide complex could ionize more efficiently than the bare phosphopeptide. Furthermore the ion mobility could separate the complex ion on the basis of its charge/volume from isobaric interferences, which would otherwise limit detection sensitivity.

Acetylcholine↗

Oligonucleotide analysis with MALDI-ion-mobility-TOFMS.

Matrix-assisted laser-desorption ionization followed by ion-mobility separation and time-of-flight mass analysis (MALDI-IM-TOFMS) has been used to characterize native and chemically modified DNA oligonucleotides up to eight bases in length. Mobility resolution between 20 and 30 can be used to separate oligonucleotides of different length, but not to differentiate between isomers or even different compositions of the same length. MALDI-IM-TOFMS does, however, have additional utility in the analysis of mixtures of DNA oligonucleotides and peptides, because these classes of molecules can be distinguished on the basis of differences in their mobility. Oligonucleotide sequencing is also possible by MALDI-IM-TOFMS. Ion signals corresponding to nucleobase losses, w-type, and y-type fragments were identified by use of differences in ion mobility. MALDI-IM-TOFMS was also used to resolve DNA-platinum adducts from the corresponding unmodified oligonucleotides.

Ions↗

A study of peptide-peptide interactions using MALDI ion mobility o-TOF and ESI mass spectrometry.

Matrix-assisted laser desorption ionization ion mobility coupled to orthogonal time-of-flight mass spectrometry (MALDI-IM-oTOF MS) is evaluated as a tool for studying non-covalent complex (NCX) formation between peptides. The NCX formed between dynorphin 1-7 and Mini Gastrin I is used as a model system for comparison to previous MALDI experiments (Woods, A. S.; Huestis, M. A. J. Am. Soc. Mass Spectrom. 2001, 12, 88-96). The dynorphin 1-7/Mini Gastrin I complex is stable after more than a ms drift time through the He filled mobility cell. Furthermore, the effects of solution pH on NCX ion signal intensity is measured both by MALDI-IM-MS analysis and by nanoelectrospray mass spectrometry. When compared to the previous MALDI study this work shows that all three techniques give similar results. In addition, fragmentation can be observed from of the non-covalent complex parent ion that occurs prior to TOF mass analysis but after mobility separation, thus providing NCX composition information.

Cyclic GMP-Dependent Protein Kinases↗