Kinetic data is presented for a variety of ion-neutral reactions which are relevant to the atmosphere of Titan and to the chemistry occurring in interstellar clouds. The data were recorded with a Selected Ion Flow Tube (SIFT) operating at room temperature (294 ± 4 K) and at a pressure of 0.46 Torr. Results of the recent Cassini-Huygens mission to Saturn and Titan have identified several species in the atmosphere of Titan not predicted by pre-Cassini models of the atmosphere. In order to determine the fate of three of these species (methylenimine, propionitrile and cyanodiacetylene) in Titan's ionosphere, their reactivity with the principal ions in Titan's upper ionosphere has been examined. As expected, collision rate proton transfer reactions dominate the chemistry with association channels also observed with many of the hydrocarbon ions. The results of the Cassini mission also identified several individual reactions as being of potential importance to models of Titan's atmosphere and this chemistry has also been examined. The above studies are also relevant to the interstellar medium where each of the neutral reactants have also been detected. The results of some proton transfer equilibrium studies are also presented. The gas phase basicities of propyne and acetylene have been determined to be 681 kJ mol⁻¹ and 617.4 kJ mol⁻¹ respectively. Their relative proton affinities can be estimated from these values. A combined experimental/theoretical study of the proton affinity of cyanodiacetylene (HC₅N) has enabled this value to be estimated at 770 ± 20 kJ mol⁻¹. Details of an attempt to complete the first laboratory measurement of the crucial reaction between H₃⁺ and atomic carbon are presented. The generation of atomic carbon in sufficient quantities for reaction in the SIFT was not possible with the microwave discharge source used. Other generation methods have also been explored with the laser photolysis of carbon suboxide expected to provide a possible solution to the problems encountered. The results of an investigation into the applicability of lithium ions (Li⁺) to SIFT-MS are presented. The lithium ions associated with each of the twenty-one neutral analytes examined to form pseudo-molecular ions. The association reactions were rapid (k ~ 10⁻⁹ cm³ s⁻¹) for large hydrocarbons but were much slower for smaller analytes (k < 10⁻¹¹ cm³ s⁻¹). In order to clarify some unusual experimental observations, the effect of water molecules on the observed chemistry has been examined in detail. The measured chemistry has important consequences for the applicability of Li⁺ to SIFT-MS where the presence and detection of an identifiable ion of the analyte is essential. Details of new SIFT operating software which can be run on a modern computer are given. Mass spectra and kinetic data recorded with the new software are also presented.

Kinetic data is presented for a variety of ion-neutral reactions which are relevant to the atmosphere of Titan and to the chemistry occurring in interstellar clouds. The data were recorded with a Selected Ion Flow Tube (SIFT) operating at room temperature (294 ± 4 K) and at a pressure of 0.46 Torr. Results of the recent Cassini-Huygens mission to Saturn and Titan have identified several species in the atmosphere of Titan not predicted by pre-Cassini models of the atmosphere. In order to determine the fate of three of these species (methylenimine, propionitrile and cyanodiacetylene) in Titan's ionosphere, their reactivity with the principal ions in Titan's upper ionosphere has been examined. As expected, collision rate proton transfer reactions dominate the chemistry with association channels also observed with many of the hydrocarbon ions. The results of the Cassini mission also identified several individual reactions as being of potential importance to models of Titan's atmosphere and this chemistry has also been examined. The above studies are also relevant to the interstellar medium where each of the neutral reactants have also been detected. The results of some proton transfer equilibrium studies are also presented. The gas phase basicities of propyne and acetylene have been determined to be 681 kJ mol⁻¹ and 617.4 kJ mol⁻¹ respectively. Their relative proton affinities can be estimated from these values. A combined experimental/theoretical study of the proton affinity of cyanodiacetylene (HC₅N) has enabled this value to be estimated at 770 ± 20 kJ mol⁻¹. Details of an attempt to complete the first laboratory measurement of the crucial reaction between H₃⁺ and atomic carbon are presented. The generation of atomic carbon in sufficient quantities for reaction in the SIFT was not possible with the microwave discharge source used. Other generation methods have also been explored with the laser photolysis of carbon suboxide expected to provide a possible solution to the problems encountered. The results of an investigation into the applicability of lithium ions (Li⁺) to SIFT-MS are presented. The lithium ions associated with each of the twenty-one neutral analytes examined to form pseudo-molecular ions. The association reactions were rapid (k ~ 10⁻⁹ cm³ s⁻¹) for large hydrocarbons but were much slower for smaller analytes (k < 10⁻¹¹ cm³ s⁻¹). In order to clarify some unusual experimental observations, the effect of water molecules on the observed chemistry has been examined in detail. The measured chemistry has important consequences for the applicability of Li⁺ to SIFT-MS where the presence and detection of an identifiable ion of the analyte is essential. Details of new SIFT operating software which can be run on a modern computer are given. Mass spectra and kinetic data recorded with the new software are also presented.

The application of Selected Ion Flow Tube Mass Spectrometry (SIFT MS) to the analysis of olive oil shows several distinct advantages over more conventional analysis techniques. The two areas described in this thesis examining olive oil quality are the analysis of Volatile Organic Compounds (VOCs) and the assessment of antioxidant activity. VOCs are responsible for the aroma and much of the taste of olive oil, while antioxidants afford some protection from harmful reactions involving radical species inside the body by scavenging radicals when olive oil is ingested. The VOCs of olive oil are used by sensory panel judges to classify oils by their degree of suitability for human consumption. The major parameters used for this evaluation are the strengths of any defects and the degree of fruitiness. A defect is an indication of an undesired process which has occurred in the oil, while fruitiness is a fragile attribute which denotes a good quality oil and is easily masked by defects. SIFT MS was used to measure the strengths of the olive oil defects rancid, winey, musty, fusty and muddy. Great potential was demonstrated for all defects except musty and the concentrations of VOCs in olive oil head space were correlated with the peroxide value, a measure of the degree of oil oxidation. A study aimed at correlating the strength of the fruitiness attribute as determined by a sensory panel with the concentrations of VOCs in olive oil head space was unsuccessful. The SIFT MS Total Oxyradical Scavenging Capacity (TOSC) assay was used to measure olive oil antioxidants. This assay measures all antioxidants in oil, not only those removed by extraction with a solvent, as it is conducted in an emulsion. SIFT MS TOSC assay results were found to correlate well with those of the widely used Folin Ciocalteu assay and the total concentration of phenolic compounds present in olive oil. Discrepancies between the two assays were most likely due to hydrophobic antioxidants which are measured by the SIFT MS TOSC assay but not the other tests.

Data is presented for a range of experiments that have been performed using a selected ion flow tube (SIFT) instrument operated at room temperature (~ 298K) with carrier gas pressures typically in the range of 0.3 – 0.6 Torr. The majority of the experiments discussed are performed on a Voice100 instrument that has not been described in detail previously. The Voice100 is a novel instrument that has been designed particularly for quantitative trace gas analysis using the SIFT-MS technique. A mixture of helium and argon carrier gases are employed in the Voice100 flow tube. By mixing carrier gases, the flow dynamics and diffusion characteristics of a flow tube are altered when compared to classic single carrier gas models. Therefore firstly, optimal flow conditions for the operation of a Voice100 are characterised. The diffusion of an ion in a mixture of carrier gases is then characterised using theoretical models and experimental techniques. This research requires that a new parameter Mp be defined regarding the mass discrimination of an ion in the non-field-free region near the downstream ion sampling orifice. Furthermore, a new method is described for the simultaneous measurement of rate coefficients for the reactions of H₃O⁺.(H₂O)n (n = 1, 2, 3) ions with analytes. Rate coefficients and branching ratios for the reactions of SIFT-MS precursor ions with specific analytes related to four individual applications are presented. For each application, the kinetic parameters are determined so as to facilitate the quantitative detection of the analytes relevant to that application. The GeoVOC application involves the measurement of hydrocarbon concentrations in the headspace of soil and water across a range of humidities. Alkyl esters are investigated to allow for the quantitative detection of each compound in fruits and vegetables. Chemical warfare agents, their surrogates and precursor compounds are studied which allows for the quantitative or semi-quantitative detection of a range of highly toxic compounds. Finally, 17 compounds classified by the US-EPA as hazardous air pollutants are studied that enables SIFT-MS instruments to replicate sections of the TO-14A and TO-15 methods.

The application of Selected Ion Flow Tube Mass Spectrometry (SIFT MS) to the analysis of olive oil shows several distinct advantages over more conventional analysis techniques. The two areas described in this thesis examining olive oil quality are the analysis of Volatile Organic Compounds (VOCs) and the assessment of antioxidant activity. VOCs are responsible for the aroma and much of the taste of olive oil, while antioxidants afford some protection from harmful reactions involving radical species inside the body by scavenging radicals when olive oil is ingested. The VOCs of olive oil are used by sensory panel judges to classify oils by their degree of suitability for human consumption. The major parameters used for this evaluation are the strengths of any defects and the degree of fruitiness. A defect is an indication of an undesired process which has occurred in the oil, while fruitiness is a fragile attribute which denotes a good quality oil and is easily masked by defects. SIFT MS was used to measure the strengths of the olive oil defects rancid, winey, musty, fusty and muddy. Great potential was demonstrated for all defects except musty and the concentrations of VOCs in olive oil head space were correlated with the peroxide value, a measure of the degree of oil oxidation. A study aimed at correlating the strength of the fruitiness attribute as determined by a sensory panel with the concentrations of VOCs in olive oil head space was unsuccessful. The SIFT MS Total Oxyradical Scavenging Capacity (TOSC) assay was used to measure olive oil antioxidants. This assay measures all antioxidants in oil, not only those removed by extraction with a solvent, as it is conducted in an emulsion. SIFT MS TOSC assay results were found to correlate well with those of the widely used Folin Ciocalteu assay and the total concentration of phenolic compounds present in olive oil. Discrepancies between the two assays were most likely due to hydrophobic antioxidants which are measured by the SIFT MS TOSC assay but not the other tests.

Data is presented for a range of experiments that have been performed using a selected ion flow tube (SIFT) instrument operated at room temperature (~ 298K) with carrier gas pressures typically in the range of 0.3 – 0.6 Torr. The majority of the experiments discussed are performed on a Voice100 instrument that has not been described in detail previously. The Voice100 is a novel instrument that has been designed particularly for quantitative trace gas analysis using the SIFT-MS technique. A mixture of helium and argon carrier gases are employed in the Voice100 flow tube. By mixing carrier gases, the flow dynamics and diffusion characteristics of a flow tube are altered when compared to classic single carrier gas models. Therefore firstly, optimal flow conditions for the operation of a Voice100 are characterised. The diffusion of an ion in a mixture of carrier gases is then characterised using theoretical models and experimental techniques. This research requires that a new parameter Mp be defined regarding the mass discrimination of an ion in the non-field-free region near the downstream ion sampling orifice. Furthermore, a new method is described for the simultaneous measurement of rate coefficients for the reactions of H₃O⁺.(H₂O)n (n = 1, 2, 3) ions with analytes. Rate coefficients and branching ratios for the reactions of SIFT-MS precursor ions with specific analytes related to four individual applications are presented. For each application, the kinetic parameters are determined so as to facilitate the quantitative detection of the analytes relevant to that application. The GeoVOC application involves the measurement of hydrocarbon concentrations in the headspace of soil and water across a range of humidities. Alkyl esters are investigated to allow for the quantitative detection of each compound in fruits and vegetables. Chemical warfare agents, their surrogates and precursor compounds are studied which allows for the quantitative or semi-quantitative detection of a range of highly toxic compounds. Finally, 17 compounds classified by the US-EPA as hazardous air pollutants are studied that enables SIFT-MS instruments to replicate sections of the TO-14A and TO-15 methods.

This dissertation thesis summarizes results of experiments that have been carried out during my PhD studies related to the new mass spectrometric methods for trace gas analysis of human breath. The thesis is divided into the theoretical and experimental part. The chapter at the beginning of this dissertation summarizes the current research in the area of breath analysis. It is describing the common breath metabolites, benefits and challenges of the method for therapeutic monitoring and clinical diagnosis and current applications. The next chapter of the theoretical introduction describes the techniques suitable for this area of research, with a special emphasis on mass-spectrometric techniques (in particular the selected ion flow tube mass spectrometry, SIFT-MS, method that allows accurate quantification of trace gases and vapours in humid air/human breath). All these parts are elaborated via the scientific literature review. The following chapters are then directly related to my own research and describes the conducted experiment, including the results obtained. This experimental part "Results and Discussion" is divided to the individual subsections, which are conceived as the commentaries to the enclosed research papers published in peer reviewed journals. The first is the detailed step by step...

京都大学 / 新制・論文博士 / 博士(医学) / 乙第13579号 / 論医博第2301号 / 新制||医||1069(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 古川 壽亮, 教授 大鶴 繁, 教授 平井 豊博 / 学位規則第4条第2項該当 / Doctor of Medical Science / Kyoto University / DFAM

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