Sensitivity and Fragmentation Calibration of the ROSINA Reflectron-type Time-Of-Flight Mass Spectrometer

The goal of this work was to increase the performance and to calibrate one of the ROSINA sensors, the Reflectron-type Time-Of-Flight mass spectrometer, currently flying aboard the ESA Rosetta spacecraft. Different optimization techniques were applied to both the lab and space models, and a static calibration was performed using different gas species expected to be detected in the vicinity of comet 67P/Churyumov-Gerasimenko. The database thus created was successfully applied to space data, giving consistent results with the other ROSINA sensors.

Timing performances of a data acquisition system for time of flight PET

We are investigating the performances of a data acquisition system for Time of Flight PET, based on LYSO crystal slabs and 64 channels Silicon Photomultipliers matrices (1.2 cm2 of active area each). Measurements have been performed to test the timing capability of the detection system (SiPM matices coupled to a LYSO slab and the read-out electronics) with both test signal and radioactive source.

Probing the oligomeric structure of an enzyme by electrospray ionization time-of-flight mass spectrometry.

Electrospray ionization time-of-flight (ESI-TOF) mass spectrometry was used to study the quaternary structure of 4-oxalocrotonate tautomerase (EC 5.3.2; 4OT), and four analogues prepared by total chemical synthesis. Wild-type 4OT is a hexamer of 62 amino acid subunits and contains no cysteine residues. The analogues were: (desPro1)4OT, a truncated construct in which Pro1 was deleted; (Cpc1)4OT in which Pro1 was replaced with cyclopentane carboxylate; a derivative [Met(O)45]4OT in which Met45 was oxidized to the sulfoxide; and an analogue (Nle45)4OT in which Met45 was replaced with norleucine. ESI of (Nle45)4OT, (Cpc1)4OT, and 4OT from solution conditions under which the native enzyme was fully active (5 mM ammonium bicarbonate buffer, pH 7.5) gave the intact hexamer as the major species detected by TOF mass spectrometry. In contrast, analysis of [Met(O)45]4OT and (desPro1)4OT under similar conditions yielded predominantly monomer ions. The ESI-TOF measurements were consistent with structural data obtained from circular dichroism spectroscopy. In the context of kinetic data collected for 4OT and these analogues, ESI-TOF mass spectrometry also provided important evidence for the structural and mechanistic significance of the catalytically important Pro1 residue in 4OT.

DNA sequencing by delayed extraction-matrix-assisted laser desorption/ionization time of flight mass spectrometry.

Matrix-assisted laser desorption/ionization (MALDI) time of flight mass spectrometry was used to detect and order DNA fragments generated by Sanger dideoxy cycle sequencing. This was accomplished by improving the sensitivity and resolution of the MALDI method using a delayed ion extraction technique (DE-MALDI). The cycle sequencing chemistry was optimized to produce as much as 100 fmol of each specific dideoxy terminated fragment, generated from extension of a 13-base primer annealed on 40- and 50-base templates. Analysis of the resultant sequencing mixture by DE-MALDI identified the appropriate termination products. The technique provides a new non-gel-based method to sequence DNA which may ultimately have considerable speed advantages over traditional methodologies.

Untersuchung des Einflusses der point spread function (PSF)- und time-of-flight (TOF)-Bilddatenrekonstruktion auf die F18-FDG-PET/CT-basierte Zielvolumendefinition kolorektaler Lebermetastasen

Universität Magdeburg, Dissertation, 2016

Peptide quantification by matrix-assisted laser desorption ionisation time-of-flight mass spectrometry: Investigations of the cyclotide kalata B1 in biological fluids

A rapid method has been developed for the quantification of the prototypic cyclotide kalata B I in water and plasma utilizing matrix-assisted laser desorption ionisation time-of-flight (MALDI-TOF) mass spectrometry. The unusual structure of the cyclotides means that they do not ionise as readily as linear peptides and as a result of their low ionisation efficiency, traditional LC/MS analyses were not able to reach the levels of detection required for the quantification of cyclotides in plasma for pharmacokinetic studies. MALDI-TOF-MS analysis showed linearity (R-2 > 0.99) in the concentration range 0.05-10 mu g/mL with a limit of detection of 0.05 mu g/mL (9 fmol) in plasma. This paper highlights the applicability of MALDI-TOF mass spectrometry for the rapid and sensitive quantification of peptides in biological samples without the need for extensive extraction procedures. (c) 2005 Elsevier B.V. All rights reserved.

Design and development of a time of flight fast scattering spectrometer : a quantitative surface analysis technique and a new approach towards the experimental investigation of the surface particle interactions

A new surface analysis technique has been developed which has a number of benefits compared to conventional Low Energy Ion Scattering Spectrometry (LEISS). A major potential advantage arising from the absence of charge exchange complications is the possibility of quantification. The instrumentation that has been developed also offers the possibility of unique studies concerning the interaction between low energy ions and atoms and solid surfaces. From these studies it may also be possible, in principle, to generate sensitivity factors to quantify LEISS data. The instrumentation, which is referred to as a Time-of-Flight Fast Atom Scattering Spectrometer has been developed to investigate these conjecture in practice. The development, involved a number of modifications to an existing instrument, and allowed samples to be bombarded with a monoenergetic pulsed beam of either atoms or ions, and provided the capability to analyse the spectra of scattered atoms and ions separately. Further to this a system was designed and constructed to allow incident, exit and azimuthal angles of the particle beam to be varied independently. The key development was that of a pulsed, and mass filtered atom source; which was developed by a cyclic process of design, modelling and experimentation. Although it was possible to demonstrate the unique capabilities of the instrument, problems relating to surface contamination prevented the measurement of the neutralisation probabilities. However, these problems appear to be technical rather than scientific in nature, and could be readily resolved given the appropriate resources. Experimental spectra obtained from a number of samples demonstrate some fundamental differences between the scattered ion and neutral spectra. For practical non-ordered surfaces the ToF spectra are more complex than their LEISS counterparts. This is particularly true for helium scattering where it appears, in the absence of detailed computer simulation, that quantitative analysis is limited to ordered surfaces. Despite this limitation the ToFFASS instrument opens the way for quantitative analysis of the 'true' surface region to a wider range of surface materials.

Characterisation of atmospheric single particles in industrial and regional background environments using aerosol time of flight mass spectrometry

The composition of atmospheric particles is an important factor in determining their impact on climate and health. In this study, an aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the chemical composition of ambient single particles at two contrasting locations – an industrial site in Dunkirk, France and a regional background site in Corsica. The ATOFMS data were combined with meteorological information and other particle measurements to determine the various sources of the particles observed at the sites. The particle classes detected in Dunkirk included carbonaceous species from fossil fuel combustion and biomass burning, metal-containing types from local industries and seasalt. Highest particle number concentrations and mass concentrations of PM2.5, black carbon, organics, nitrate, ammonium and several metallic species (Fe, Mn, Pb, Zn) were found during periods heavily influenced by local industry. Particles from a ferromanganese alloy manufacturing facility were identified by comparing ambient ATOFMS data with single particle mass spectra from industrial chimney filters and ores. Particles from a steelworks were identified based on comparison of the ambient data with previous studies. Based on these comparisons, the steelworks was identified as the dominant emitter of Fe-rich particles, while the ferromanganese alloy facility emitted Mn-rich particles. In Corsica, regional transport of carbonaceous particles from biomass burning and fossil fuel combustion was identified as the major source of particles in the Mediterranean background aerosol. Throughout the campaign the site was influenced by air masses altering the composition of particles detected. During North Atlantic air masses the site was heavily influenced by fresh sea salt. Regional stagnation was the most common type of air mass regime throughout the campaign and resulted in the accumulation of carbonaceous particles during certain periods. Mass concentrations were estimated for ATOFMS particle classes, and good agreement was found between the major carbonaceous classes and other quantitative measurements. Overall the results of this work serve to highlight the excellent ability of the ATOFMS technique in providing source-specific composition and mixing state information on atmospheric particles at high time resolution.

Automatic Identification of Large Fragments in a Pile of Broken Rock Using a Time-of-Flight Camera

This paper presents a solution to part of the problem of making robotic or semi-robotic digging equipment less dependant on human supervision. A method is described for identifying rocks of a certain size that may affect digging efficiency or require special handling. The process involves three main steps. First, by using range and intensity data from a time-of-flight (TOF) camera, a feature descriptor is used to rank points and separate regions surrounding high scoring points. This allows a wide range of rocks to be recognized because features can represent a whole or just part of a rock. Second, these points are filtered to extract only points thought to belong to the large object. Finally, a check is carried out to verify that the resultant point cloud actually represents a rock. Results are presented from field testing on piles of fragmented rock. Note to Practitioners—This paper presents an algorithm to identify large boulders in a pile of broken rock as a step towards an autonomous mining dig planner. In mining, piles of broken rock can contain large fragments that may need to be specially handled. To assess rock piles for excavation, we make use of a TOF camera that does not rely on external lighting to generate a point cloud of the rock pile. We then segment large boulders from its surface by using a novel feature descriptor and distinguish between real and false boulder candidates. Preliminary field experiments show promising results with the algorithm performing nearly as well as human test subjects.

Comprehensive metabolite profiling of Plantaginis Semen using ultra high performance liquid chromatography with electrospray ionization quadrupole time-of-flight tandem mass spectrometry coupled with elevated energy technique

Plantaginis Semen is commonly used in traditional medicine to treat edema, hypertension, and diabetes. The commercially available Plantaginis Semen in China mainly comes from three species. To clarify the chemical composition and distinct different species of Plantaginis Semen, we established a metabolite profiling method based on ultra high performance liquid chromatography with electrospray ionization quadrupole time-of-flight tandem mass spectrometry coupled with elevated energy technique. A total of 108 compounds, including phenylethanoid glycosides, flavonoids, guanidine derivatives, terpenoids, organic acids, and fatty acids, were identified from Plantago asiatica L., P. depressa Willd., and P. major L. Results showed significant differences in chemical components among the three species, particularly flavonoids. This study is the first to provide a comprehensive chemical profile of Plantaginis Semen, which could be involved into the quality control, medication guide, and developing new drug of Plantago seeds.