Indiana University-Purdue University Indianapolis (IUPUI) / Ion Mobility Spectrometry (IMS) is an analytical technique for separation of charged particles in the gas phase. The history of IMS is not very old, and in this century, the IMS technique has grown rapidly in the advent of modern instruments. Among currently available ion mobility spectrometers, the DTIMS, FAIMS, TWIMS, DMA are notable. Though all the IMS systems have some uniqueness in case of particle separation and detection, however, all instruments have common shortcomings. They lack in resolution, which is independent of mobility of different charged particles and they are not able to separate bigger particles (20 120 nm) with good accuracy. The work presented here demonstrates a new concept of IMS technique at atmospheric pressure which has a resolution much higher than that of the currently available DTIMS (Drift Tube Ion Mobility Spectrometry) instruments. The unique feature of this instrument is the diffusion auto-correction. Being tunable, It can separate the wide range of particles of different diameters. The working principle of this new IMS technique is different from the typical DTIMS and to simply put, it can be considered as an inversion of commonly used technique, so termed as Inverted Drift Tube (IDT).The whole work performed here can be divided into three major phases. In the first phase, the analytical solution was derived for two new separation techniques: IPF (Intermittent push flow) and NSP (Nearly stopping potential) separations. In the next phase, simulations were done to show the accuracy of the analytical solution. An ion optics simulator software called SIMION 8.1 was used for conducting the simulation works. These simulations adopted the statistical diffusion (SDS) collision algorithm to emulate the real scenario in gas phase more precisely. In the last phase, a prototype of experimental setup was built. The experimental results were then validated by simulated results.

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第21004号 / 医博第4350号 / 新制||医||1028(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 戸口田 淳也, 教授 妻木 範行, 教授 開 祐司 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

Measurements of the target thickness dependence of the target x-ray production yield for incident fast heavy ions are reported for thin solid Cu targets as a function of both incident projectile atomic number and energy. The incident ions were F, Al, Si, S, and CI. The charge state of the incident ions was varied in each case to study the target x-ray production for projectiles which had an initial charge state, q, of q = Z₁, q = Z₁ - 1, and q < Z₁ - 1 for F, Al, Si, and S ions and q = Z₁ - 1 and q < Z₁ - 1 for C1 ions. The target thicknesses ranged from 2 to 183 ug/cm². In each case the Cu K x-ray yield exhibits a complex exponential dependence on target thickness. A two-component model which includes contributions to the target x-ray production due to ions with 0 and 1 K vacancies and a three-component model which includes contributions due to ions with 0, 1, and 2 K vacancies are developed to describe the observed target K x-ray yields. The two-component model for the C1 data and the three-component model for the F, Al, Si, S, and C1 data are fit to the individual data for each projectile, and the cross sections for both the target and projectile are determined. The fits to the target x-ray data give a systematic representation of the processes involved in x-ray production for fast heavy ions incident on thin solid targets.

Mass spectrometry has frequently been employed in the analysis of biologically relevant molecules; however, mass spectrometry alone may not always be sufficient for the differentiation and characterization of isomeric and isobaric ions. In this work, infrared multiple photon dissociation (IRMPD) spectroscopy and ion mobility spectrometry (IMS) were evaluated as complementary techniques for the characterization and separation of isomeric and isobaric ions of biological relevance. In the first project, analysis of experimental IRMPD spectroscopy data shows that this technique is useful in the differentiation of hydroxyproline isomers. Absorption bands allow for the differentiation of three isomeric species: 1640 cm-1 (trans-4-hydroxyproline), 1718 cm-1 (cis-4-hydroxyproline), and 1734 cm-1 (cis-3-hydroxyproline). In the second project, theoretical CCS and IR spectroscopy predictions of isobaric modified amino acids and isomeric drugs have been carried out as predictions of IMS and IRMPD spectroscopy suitability. Preliminary IMS measurements suggest that the CCS predictions are at least qualitatively useful.

This study investigated the regulation of Na⁺ Ca²⁺ Cl⁻ during development in embryonic rainbow trout (Oncorhynchus mykiss). Because there is a close relationship between pH regulation and ion uptake mechanisms in adult teleosts, pH, pCO₂, and NH₄⁺ levels in unstirred layers (USLs) adjacent to whole eggs and dechorionated embryos were determined using double-barrel ion-selective microelectrodes (ISMEs). Whole eggs accumulated Na⁺, Ca²⁺ and Cl⁻ during the last 20 days of embryonic development, suggesting an ionoregulatory ability prior to hatching. Na⁺ uptake by whole eggs was linearly related to external [Na⁺], suggesting that Na⁺ crosses the chorion by diffusion. The uptake by dechorionated embryos was saturable, indicating the presence of active transport or facilitated diffusion mechanisms on the surface of embryos prior to hatching. Ca²⁺ uptake by whole eggs and dechorionated embryos was saturable, suggesting that specific pathways or binding sites are present in the chorion, and that active transport or facilitated diffusion mechanisms are present at the surface of embryos. The much higher Jₘₐₓ for whole eggs than dechorionated embryos suggests a role of the perivitelline fluid (pvf) or chorion in ion uptake. Jₘₐₓ was lower in dechorionated embryos than in hatchlings suggesting that Ca²⁺ uptake mechanisms may not be fully developed in dechorionated embryos. Low pH and high [NH₄⁺] were measured in the USLs adjacent to whole eggs and dechorionated embryos, relative to the bulk water. A high Pcₒ₂ measured adjacent to the gills suggests that CO₂ excretion was the primary source of USL acidification. pH was lower in the USL adjacent to the gills and trunk than in the USL adjacent to the yolk sac. [NH₄⁺] was highest adjacent to the gills and trunk than adjacent to the yolk sac. There was no change in the extent of USL acidification or in [NH₄⁺] over the last half of embryonic development. After hatching, however, there was a significant increase in [NH₄⁺] adjacent to the gills, which was not accompanied by a change in USL pH. It is possible that a change in permeability of the transporting surfaces (i.e. gills, trunk, yolk sac) occurs after hatching. / Thesis / Master of Science (MS)

Metallic bilayer samples of Mo(400 Å)/ Al(substrate) were characterized using Rutherford Backscattering Spectroscopy after first being irradiated with Xe ion beam having an energy of 1.8 MeV. The computer code RUMP was then used to simulate the RBS spectra. The interdiffusion at the interface was considered in terms of thermal spike induced atomic migration. It was found that the coupling of the chemical effect with spike is significant with regard to mixing of the bilayer samples. Furthermore, in addition to the initial contamination of carbon atoms on the surface and at the interface, more carbon atoms were found to be picked up by the surface, this carbon w.as from the vacuum pumps and tended to migrate into the surface once irradiation dose exceeded 11 x 10¹⁵cm². A semi-empirical model was developed for ion beam mixing taking into account collisional mixing and thermal spike effects, as well as the thermal spike shape. The collisional mixing part was accounted for by the Kinchin-Pease model, or, alternatively dynamic Monte Carlo simulation. For the thermal spike, the ion beam mixing parameter Dt/Φ was derived to be proportional to ( - F_D /ΔH_coh)^2+μ, where F_D is the damage energy deposited per unit path length, ΔH_coh is the cohesive energy of the target materials, and µ is a constant dependent on the spike shape and point defect density in the spike regions. The thermal spike introduces a nonlinear effect in the mixing process, distinguishing itself from the linear effect of ballistic mixing. The shape of the thermal spike that best fit the experimental results depends on the magnitude of the cascade density. For relatively high density collisional cascades, where thermal spikes start to be important, it was found that a spherical spike model was more consistent with experimental measurements at low temperatures. However, for extremely high density collisional cascade regions, a cylindrical shaped spike gave better results. The atomic migration energy in the spike regions is scaled by a factor of one out of 8.6 of cohesive energy. The migration mechanism was recognized to be interstitial-dominated one. / M.S.

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