This thesis covers the synthesis and the characterization of sodium lanthanide oxide phosphates, rare earth added strontium pyrophosphates and the Rietveld structural analysis of rare earth orthoborates. Solid state and microwave-assisted synthesis method was employed for the synthesis of desired materials. The formation of the produced phases was confirmed by X-ray Diffraction (XRD), Infrared FT-IR, Raman, Scanning Electron Microscopy (SEM) methods. By using Rietveld Refinement method, structural analysis of rare earth orthoborates were done and three dimensional crystal structures were found. In the first part of the thesis, some new sodium lanthanide oxide phosphates were synthesized by solid state reaction method from Ln2O3 (where Ln= La, Nd, Sm, Gd, Dy, Ho, Er, Yb), Na2CO3, NH4H2PO4 at 1100 oC. Na2LaOPO4, Na2NdOPO4, and Na2SmOPO4 produced with the space group is Pmm2. With the help of the same procedure new orthorhombic Na2DyOPO4, Na2HoOPO4, Na2ErOPO4, and Na2YbOPO4 were synthesized for the first time in the literature at 1100 oC with the same space group Pmm2. v In the second part of the thesis, Sr2P2O7 - ZrP2O7 solid solution was obtained by the solid state reaction and they were characterized for the first time in literature and subjected to thermoluminescence measurements showing Sr2P2O7 has glow curve around 100 oC. Then CuO and some rare earth oxides (Y2O3, La2O3, CeO2, Pr6O11, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3) 0.5-15% (by weight) were added to pure Sr2P2O7. After structural determinations by XRD, thermoluminescence studies showed two glow peaks of Pr, Ho, and Nd along with Cu-added samples, one of them is always at around 90 oC and the other TLthermoluminescence- peak around 180, 275, and 285 oC, respectively. This study showed that rare earth added Sr2P2O7 materials can be promising material for dosimetric applications. In the third part of this work, time saving microwave-assisted synthesis method was applied to produce pure LnBO3 (Ln=La, Nd, Dy, Ho) by using urea and sucrose as a microwave active organic additive. For LaBO3 and NdBO3, space group found as Pnma and for DyBO3 and HoBO3 powders crystallized in hexagonal unit cell with P-6c2 space group. All microwave-assisted products have particle sizes lower than 1 micrometer. In the final part of this study, pure LnBO3 (Ln=Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu) powder samples were produced by using solid state reactions of Ln2O3 and H3BO3 (ratio=1:2) heated at 900 oC for 10 hours and 1000 oC for 5 hours. The crystallographic studies conducted with rietveld structural refinement and unit cell parameters, background functions, profile parameters, zero shift, atomic positions, and unisotropic thermal parameters were refined. LaBO3 and NdBO3 were solved based on Pnma orthorhombic structure while the crystal structure of YBO3, DyBO3 and HoBO3 were monoclinic C2/c. SmBO3 showed triclinic P-1 structure.

Abstract Aqueous solution containing tin chloride as precusor was traditionally added with NH3(aq) to promote hydrolysis and hence condensation. This results in a particulate sol which possesses little viscosity and the aggregation of precusor particles makes the subsequcently spin-coated thin film very rough in the surface and poorly-adhered with the substrate. One objective of this work is to improve the film quality by refluxing the sol to reduce precursor aggregation, enhance hydrolysis and promote HCl(g) evaporation. Experimtntal results show that, after refluxing the sol with DI-water or methanol as solvent, one obtains better films when basic sol (NH3(aq) added) and SnCl2 precursor is used instead of acidic sol (HCl(aq)added) and SnCl4 precursor. Moreover, to further reduce the effect of Cl¡Ð ion in aggregation and increase viscosity, ethylene glycol was used as solvent and two-stage heating-stirring of the sol in 80 oC and 130 oC ~150 oC was carried out to promote generation of H2O(g) and HCl(g). The evaporation of H2O(g) and HCl(g) enhances the polymerization of precursor and increase the viscosity of the sol. The aggregation caused by Cl¡Ð ions is thus reduced due to the steric effect present in the polymerical sol. XRD, SEM, FT-IR , TGA and DSC were used to examine the evolution from sol to films. FT-IR results show that absorbtion peaks of the xerogel appear at 636 cm-1(O-Sn-O) and 500 cm-1 (Sn-O). XRD results of the calcined (4 hr) powders show that rutile (SnO2) crystallization starts at 200 oC for that derived from the SnCl2-containing sol while powder derived from the SnCl4-containing sol starts crystallization at 250 oC. However, grain growth is faster in powder derived from SnCl4-containing sol as their XRD peaks become sharper than that corresponding to SnCl2 precursor as calcination temperature is raised. Based on the examination of the evolution process, it is concluded that SnCl2 polymerizes in ethylene glycol as a one dimensional chain while SnCl4 forming a 3-D network after polymerizing in ethylene glycol.

Zugl.: Aachen, Techn. Hochsch., Diss., 2009

Zugl.: Bielefeld, Univ., Diss., 2008

No description available.

Control de calidad sensorial de bebidas alcohólicas utilizando rápidos sensores químicosEn la presente tesis Doctoral, han sido aplicados dos sensores artificiales para el análisis debebidas alcohólicas: la nariz electrónica basada en la espectrometría de masas (MS) y la lenguaelectrónica basada en la espectroscopía infrarroja con transformada de Fourier (FTIR). Elpropósito fue desarrollar nuevas estrategias para analizar la autenticidad de estos productos,desde un punto de vista sensorial, por medio de técnicas las espectrales antes mencionadas.Adicionalmente, ha sido utilizado un espectrofotómetro UV-visible como ojo electrónico. Eltrabajo presentado pretende ser un avance significativo hacia el desarrollo de un catadorelectrónico mediante la fusión de los tres sensores químicos: nariz electrónica, lenguaelectrónica y ojo electrónico.Sensory quality control of alcoholic beverages using fast chemical sensorsIn the present Doctoral Thesis, two chemical artificial sensors are applied to the analysis ofalcoholic beverages: the Mass Spectrometry (MS)-based electronic-noses and Fouriertransform infrared (FTIR)-based electronic-tongue. The aim was developing new strategies totest the authenticity of these products, from a sensory point of view, by means of the spectraltechniques above mentioned. Additionally, has been used an UV-visible spectrophotometer aselectronic eye. The work presented wants to be a significant advance towards the developmentof an electronic taster through the fusion of three chemical sensors: electronic nose, electronictongue and electronic eye.

High blood glucose levels induce metabolic disorders that initiate a sequence of events including renal, arterial, cardiac and retinal disorders. Diabetes mellitus increases oxidative stress in tissues of animals including humans. The resulting oxidative stress might play role in the development of diabetic complications. In the present study, 36 male Wistar rats (250-300g) were divided into 5 groups as Control (n=6), Diabetic (n=7), Diabetic + Vit C (n=7), Diabetic + &amp / #945 / -Lipoic acid (n=6) and Diabetic + Combination of Vit C and &amp / #945 / -Lipoic acid (n=10). From the livers of all groups cytoplasmic and microsomal membrane fractions were prepared from liver and antioxidant enzymes namely, superoxide dismutase, glutathione peroxidase, catalase and glutathione S-transferase activities were measured. Microsomal lipid peroxidation, total lipid, total protein, reduced glutathione levels of each group was determined and compared. Microsomal fractions were also analyzed by FT-IR spectroscopy. The total protein levels of diabetic rats were found to be decreased significantly (p&lt / 0.05) compared to controls and the &amp / #945 / -lipoic acid and vitamin C supplemented groups tend to compensate the decreased levels of total proteins. Decreased catalase activity in diabetic group compared to control was restored by &amp / #945 / -lipoic acid, vitamin C treatment and/or combination of both. Increased glutathione peroxidase activity was decreased to control levels by the treatement of both &amp / #945 / -lipoic acid and vitamin C. Superoxide dismutase activities of diabetic rats were increased (p&lt / 0.05) compared to control group. Whereas glutathione S-transferase activities though showed some fluctuations, the results were not statistically significant. Total glutathione levels decreased in all groups significantly (p&lt / 0.0.5) compared to control group but any of the agent failed to compensate the reduced levels of glutathione. As an index of lipid peroxidation, TBA-reactivity (MDA) levels increased significantly in all diabetic groups and only combination group&rsquo / s TBARS levels decreased significantly compared to diabetic group. FT-IR study of rat liver microsomal membranes was carried out in order to understand the effects of diabetes on membrane order, dynamics and lipid peroxidation status. For this purpose CH2 symmetric wavenumber, CH2 antisymmetric bandwidth, =CH olefinic band area were compared. In temperature dependent FT-IR studies microsomal membrane phase behavior, order and dynamics were analyzed. Diabetic samples showed apparent decrease in both frequency and bandwidth. =CH olefinic band integrated area was increased for diabetic samples compared to controls. Alpha-lipoic acid and vitamin C supplemented groups showed similar effects. They tend to restore decreased levels of band frequency and bandwidth. Additive effect between &amp / #945 / -lipoic acid and vitamin C was seen in some cases that only the combination group achieved to restore control values while &amp / #945 / -lipoic acid and vitamin C were failed to restore alone. In conclusion, STZ-induced diabetes mainly caused an increase in antioxidant enzyme activities. Also, increase in lipid peroxidation caused a decrease in the fluidity and order of the membrane resulting in more rigid membrane structures. The loss of cooperation between the antioxidant network may play a role in the secondary complications of diabetes.

Previous research has underscored the importance of protein dynamics during light-induced electron transfer; however, specific interactions have not been well characterized. It is of particular importance to understand the role of protein dynamics and cofactor interactions in controlling electron transfer in oxygenic photosynthesis. These factors include hydrogen bonding, ð-stacking and electrostatic interactions. Reaction-induced FT-IR spectroscopy is sensitive to these interactions as well as isotopic incorporation, and is useful to probe protein dynamics associated with light-induced electron transfer in Photosystem I (PSI). Density functional theory (DFT) provides information concerning the vibrational frequencies of molecules as well as the amplitudes of the vibrations and sensitivity to isotope incorporation. Combining these approaches, protein dynamics associated with light-induced electron transfer in PSI were studied. The work presented here describes specific protein cofactor interactions and specific protein relaxation events associated with light-induced electron transfer. The results reported here are consistent with noncovalent protein cofactor interactions that modulate the redox potential of the secondary electron acceptor of PSI. Furthermore, the studies presented here describe novel protein dynamics associated with the oxidation of the terminal electron donor of PSI. These results characterize specific protein dynamics that may be associated with interactions of the soluble electron donors. These studies highlight the importance of protein dynamics in oxygenic photosynthesis.

Vibrational spectroscopy, mainly infrared spectroscopy, has been applied to bacteria, yeast and archaea cells for many years, for example, for the purpose of developing a rapid method of identification. More recently microcolonies have been used for consistency with the preparation and culture protocols of traditional microbiological methods. Heterogeneity of microcolonies has not been well studied. Investigation of heterogeneity may provide detailed biochemical information leading to an understanding of how colonies grow and the link to the growth cycle. Investigation of regions within bacterial colonies using FT-IR microspectroscopy was applied to two prokaryotes, the Gram-negative archaeon Halobacterium salinarium and the Gram-positive bacterium Bacillus stearothermophilus. Two-dimensional maps of the entire colony and point maps, spectra taken from key regions such as the periphery and centre of the colony, were acquired. The approximate size of the colonies ranged from 250-950 μm. The infrared data for the Gram-negative archaeon, H. salinarium supports that for the Gram-positive bacterium, B. stearothermophilus, despite the microorganisms being of different domains and Gram types. It was concluded that the periphery of the microcolony approximately equates to the exponential growth phase (and possibly the lag phase) where the younger cells reside, while the centre approximates to the death and stationary phases. However the spatial resolution proved to be a limiting factor, so Raman microspectroscopy was employed to address this. Raman spectra across the diameter of microcolonies ranging from 100-300 μm of the pigmented bacterial species Halobacterium salinarium revealed variations in the carotenoid bands. It was suggested that these variations correspond to growth rings, which relate to the growth cycle and the consolidation and migration phase of the cells. The carotenoid variation was rather clear mainly due to the enhanced spectral intensity due to resonance with the laser excitation source. Hence, pigmented bacterial colonies are ideal to study by Raman spectroscopy. The results of this particular aspect of the research are to be published in the Journal of Raman Spectroscopy [1]. In addition, a connection between the consolidation and migration phases and the phases of the growth cycle has been postulated as a novel hypothesis to link the periodic dynamics of the colony and the growth mechanisms at the cellular level. The Raman microspectroscopic study was extended to non-pigmented bacterial colonies directly on the growth medium. This was a more difficult endeavour as the spectra taken do not have the resonance enhanced advantage of a pigmented bacterium. In addition the sampling volume can consist of variable amounts of growth medium thus decreasing the signal-to-noise ratio and reducing the accuracy of subsequent spectral calculations. However, this was overcome to a large extent by the use of confocal microscopy. The non-pigmented bacterial colonies investigated were Bacillus stearothermophilus and Bacillus subtilis. Analysis, by band area ratios and by chemometric approaches, of radial line map spectra of both Bacillus species revealed variation of nucleic acid concentration. The higher nucleic acid concentration is likely to be a result of cells in the exponential growth phase as rapid growth of new cells is occurring.

Stuttgart, Univ., Diss., 2008.