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Ion processes in gases for the trace analysis of volatile compounds in air
Spesyvyi, Anatolii ; Španěl, Patrik (advisor) ; Matejčík, Štefan (referee) ; Tichý, Milan (referee)
This thesis describes development of the new selected ion flow-drift tube mass spectrometry technique, SIFDT-MS, for online quantification of volatile organic compounds, VOCs, based on gas phase ion-molecule reactions. SIFDT-MS represents a new generation of the successfully used selected ion flow tube, SIFT- MS, analytical method. The essential extension of SIFDT-MS is the uniform electric field E applied across the flow tube reactor, thus converting it to the flow-drift tube where the ion processes can be governed by strength of field E. Newly introduces Hadamard modulation of the gate lens before the flow-drift tube enables direct ion residence, and correspondently ion-molecule reaction, time measurement that is necessary for the precise concentration calculations under variable conditions. The detailed experimental study of these processes results was carried out to form a basis of the analytical method. In order to overcome a well-known issue of SIFT-MS, when mass spectral peaks of isobaric ions overlap, the pseudoinverse matrix multiplication for isobaric mixtures was demonstrated. Finally two data mining approaches were successfully tested on the data of the fragmentation signals of seven monoterpene isomers obtained in SIFT-MS.
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Laboratory studies of ion-molecule reactions with molecular and atomic hydrogen at temperatures relevant to astrochemistry
Mulin, Dmytro ; Glosík, Juraj (advisor) ; Kotrík, Tomáš (referee) ; Španěl, Patrik (referee)
The results of the laboratory study of reaction rate coefficients of several ion- molecule reactions with atomic and molecular hydrogen and molecular deuterium at low temperatures are presented in the thesis. The reaction rate coefficients of the N+ and H+ reaction with H2 were measured with respect to the nuclear spin configuration and rotational excitation of H2. The reactions of anions were a subject of the isotope exchange and isotope effect study. The measurements of the rate coefficients of H2O and D2O formation in the reaction of O- with H2 and D2, isotope exchange reactions OH- + D2 and OD- + H2, and associative detachment and charge transfer channels of D- + H interaction were performed. Experiments were carried out using an AB-22PT instrument with an ion trap. It has producing, guiding, trapping, and detecting systems for ions and a separate source of atomic H. The cooling system allowed to measure the temperature dependencies of the reaction rate coefficients at temperatures relevant to astrochemistry (10 K - 300 K)
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Identification and quantification of biomarkers of gastrointestinal diseases using mass spectrometry
Pospíšilová, Veronika ; Španěl, Patrik (advisor) ; Jelínek, Ivan (referee)
6 Abstract This thesis focuses on the identification and quantification of volatile metabolites in the exhaled breath that might be used as possible biomarkers of Gastroesophageal Reflux Disease. Animal tissue samples were exposed to conditions simulating the gastric environment to identify specific volatile compounds that would be chosen for real-time quantification in exhaled breath of GERD patients and healthy controls using selected ion flow tube mass spectrometry. Solid phase microextraction, was used in combination with gas chromatography mass spectrometry, for qualitative analyses of the headspace of these samples. Only acetic acid was significantly elevated and so it has been elected for the quantitative analysis in the breath of the patients. The median concentration of acetic acid measured by SIFT-MS in the exhaled breath of twenty-two GERD patients was found to be higher (85 ppbv) in comparison to the control group (31 ppbv). The results show that breath acetic acid could be valuable marker for GERD diagnosis and monitoring.
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Selected ion flow tube mass spectrometry, SIFT-MS
Sovová, Kristýna ; Španěl, Patrik (advisor) ; Glosík, Juraj (referee) ; Matejčík, Štefan (referee)
This thesis describes research that has been carried out during the years 2009-2013 as a part of my PhD project related to the method of selected ion flow tube mass spectrometry (SIFT-MS) and its application in interdisciplinary areas of research. SIFT-MS is a method that allows accurate quantification of trace gases and vapours presented in humid air with the focus on human breath; without any sample preparation and in real time. The thesis is divided into several parts. The first part reviews the history of mass spectrometry as a background for the quantitative analytical methods as PTR-MS and SIFT-MS. The second part discusses the detailed history of development of SIFT-MS, starting from principles of selected ion flow tube (SIFT) technique that has been used for study of ion-molecule reactions in the gas phase and forms the basis of SIFT-MS. The next part discusses volatile organic compounds of different biological origin: bacterial, plant and human breath metabolites that can be analyzed in real time using SIFT-MS. The main part "Results and Discussion" is divided into several subsections that serve as commentaries to the enclosed research papers published in peer reviewed journals. The first is a detailed step by step overview of the kinetics of ion molecule reactions which is the basis of...
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Study of state selected interactions of ions with molecular hydrogen at temperatures relevant to astrochemistry
Zymak, Illia ; Glosík, Juraj (advisor) ; Bánó, Gregor (referee) ; Španěl, Patrik (referee)
In this work are presented results of the experimental study of state selected reactions of H+ and N+(3PJa) ions with molecular hydrogen H2(J = 0, 1) at temperatures in the range 10 - 100 K using 22-pole rf ion trap apparatus. These reactions are important for the formation of interstellar trihydrogen cations and ammonia. To determine the temperature of ions, calibration measurements of the Doppler broadening of spectral lines using N2+ + Ar Ar+ + N2 laser induced reaction and rate of the ternary association He+ + 2He He2+ + He were performed. Both ternary and radiative channels of the H+ + H2(J) association reaction were observed at hydrogen number densities in the range 1012 - 1014 cm-3 and 1011 - 1012 cm-3 respectively. Obtained temperature dependences at 11 - 33 K demonstrate substantial role of the H2 rotational energy, results cannot be explained with the existed theories of the stabilization of collisional complexes. Measurements of the rate coefficient of N+(3PJa) + H2(J) reaction at different ortho fractions of H2 show dependence on internal energy of both reactants. State specific rate coefficients of the reaction of nitrogen and hydrogen ions were derived. The adiabatic model and collisional relaxations of N+(3PJa) fine structure levels were considered. Powered by TCPDF (www.tcpdf.org)
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Creation and characterization of cold molecules and molecular radicals in supersonic plasmatic nozzle
Mašát, Milan ; Votava, Ondřej (advisor) ; Glosík, Juraj (referee) ; Španěl, Patrik (referee) ; Kania, Patrik (referee)
Title: Creation and characterization of cold molecules and molecular radicals in supersonic plasmatic nozzle Author: Milan Mašát Department: J. Heyrovsky Institute of Physical Chemistry of the ASCR, v. v. i. (32-UFCHAV) Supervisor: Mgr. Ondřej Votava, Ph. D., J. Heyrovsky Institute of Physical Chemistry of the ASCR, v. v. i. (32-UFCHAV) Abstract: The aim of this work is the development and characterization of experimental apparatus designed for study of expansion-cooled stable and unstable molecule species in near infrared region, as well as associated methodology. This device consists of discharge source of cold molecular radicals and a system for their spectroscopic analysis. The source and the spectroscopic part changes and upgrades are described in detail. Characterization of radical source and its methodology was done on the OH radical model. Changes in radical properties under different experimental conditions, such as stagnation pressure, used voltage and different geometries of both the nozzle and electrodes are measured. Methodology of spectroscopic analysis was carried out on methane molecule in unassigned part of spectra, so called icosad region. Keywords: supersonic expansion, molecular radical source, high resolution spectroscopy
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Teoretické studium difúze iontů dúležitých pro analýzu dechu metodou SIFT-MS
Dryahina, K. ; Španěl, Patrik
Accuracy of quantitative Selected Ion Flow Tube Mass Spectrometry SIFT-MS is ultimately determined by the proper accounting in the data analysis for the effect of differential diffusion. Diffusion loss of the product ions can be typically lower by a factor of up to 3 in comparison with the precursor ions. Hard sphere model of diffusion of polyatomic ions in helium has been used to calculate diffusion coefficients of the precursor and product ions involved in SIFT-MS quantification of common breath metabolites ammonia, acetone, isoprene, acetaldehyde and ethanol. Calculation involves semiempirical PM3 method for determination of the geometries of the ions, numerical averaging of the geometrical cross section for collisions with helium atoms and construction of a model interaction (12, 4) model potential followed by the analytical calculation of ionic mobility using momentum-transfer collision integral. Finally the values of diffusion enhancement factors have been calculated.
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