Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Two-dimensional atom localization and Raman cooling of tripod-type atoms

Both atom localization and Raman cooling, considered in the thesis, reflect recent progress in the area of all-optical methods. We focus on twodimensional (2D) case, using a four-level tripod-type atomic scheme for atom localization within the optical half-wavelength as well as for efficient subrecoil Raman cooling. In the first part, we discuss the principles of 1D atom localization, accompanying by an example of the measurement of a spontaneously-emitted photon. Modifying this example, one archives sub-wavelength localization of a three-level -type atom, measuring the population in its upper state. We go further and obtain 2D sub-wavelength localization for a four-level tripod-type atom. The upper-state population is classified according to the spatial distribution, which in turn forms such structures as spikes, craters and waves. The second part of the thesis is devoted to Raman cooling. The cooling process is controlled by a sequence of velocity-selective transfers from one to another ground state. So far, 1D deep subrecoil cooling has been carried out with the sequence of square or Blackman pulses, applied to -type atoms. In turn, we discuss the transfer of atoms by stimulated Raman adiabatic passage (STIRAP), which provides robustness against the pulse duration if the cooling time is not in any critical role. A tripod-type atomic scheme is used for the purpose of 2D Raman cooling, allowing one to increase the efficiency and simplify the realization of the cooling.

Laser cladding with scanning optics

Scanning optics create different types of phenomena and limitation to cladding process compared to cladding with static optics. This work concentrates on identifying and explaining the special features of laser cladding with scanning optics. Scanner optics changes cladding process energy input mechanics. Laser energy is introduced into the process through a relatively small laser spot which moves rapidly back and forth, distributing the energy to a relatively large area. The moving laser spot was noticed to cause dynamic movement in the melt pool. Due to different energy input mechanism scanner optic can make cladding process unstable if parameter selection is not done carefully. Especially laser beam intensity and scanning frequency have significant role in the process stability. The laser beam scanning frequency determines how long the laser beam affects with specific place local specific energy input. It was determined that if the scanning frequency in too low, under 40 Hz, scanned beam can start to vaporize material. The intensity in turn determines on how large package this energy is brought and if the intensity of the laser beam was too high, over 191 kW/cm2, laser beam started to vaporize material. If there was vapor formation noticed in the melt pool, the process starts to resample more laser alloying due to deep penetration of laser beam in to the substrate. Scanner optics enables more flexibility to the process than static optics. The numerical adjustment of scanning amplitude enables clad bead width adjustment. In turn scanner power modulation (where laser power is adjusted according to where the scanner is pointing) enables modification of clad bead cross-section geometry when laser power can be adjusted locally and thus affect how much laser beam melts material in each sector. Power modulation is also an important factor in terms of process stability. When a linear scanner is used, oscillating the scanning mirror causes a dwell time in scanning amplitude border area, where the scanning mirror changes the direction of movement. This can cause excessive energy input to this area which in turn can cause vaporization and process instability. This process instability can be avoided by decreasing energy in this region by power modulation. Powder feeding parameters have a significant role in terms of process stability. It was determined that with certain powder feeding parameter combinations powder cloud behavior became unstable, due to the vaporizing powder material in powder cloud. Mainly this was noticed, when either or both the scanning frequency or powder feeding gas flow was low or steep powder feeding angle was used. When powder material vaporization occurred, it created vapor flow, which prevented powder material to reach the melt pool and thus dilution increased. Also powder material vaporization was noticed to produce emission of light at wavelength range of visible light. This emission intensity was noticed to be correlated with the amount of vaporization in the powder cloud.

Mechanical design and optics simulation of the illuminated Volvo Iron mark

Utilization of light and illumination systems in automotive industry for different purposes has been increased significantly in recent years. Volvo as one of the leading companies in manufacturing of luxury cars has found the great capacity in this area. The performance of such an illumination systems is one of the challenges that engineers in this industry are facing with. In this study an effort has been made to design a system to make the iron mark of Volvo being illuminated and the system is being evaluated by optics simulation in software using Ray optics method. At the end, results are assessed and some optimizations are carried out. Different kind of light guides, front side of the iron mark and some possible arrangement for LED also evaluated and different materials tested. The best combination from uniformity, color and amount of luminance aspect selected as a possible solution for this special project which can be used as a base for further studies in Volvo.