The goal of the present study is to explore the functional involvement of the N-terminal region in the biological activity of phospholipase A2 (PLA2) enzyme. Native PLA2 from the venoms of Naja naja atra and Bungarus multicinctus and N-terminally mutated N. naja atra PLA2, i.e. an additional Met before Asn-1(M-PLA2), substitution of Asn-1 with Met-1(PLA2(N1M)) and removal of N-terminal seven residues (PLA2(¡µN7)), were employed in this study. Mutations on the N-terminal region insignificantly perturbed the binding ability of PLA2 for Ca2+ and ANS, but the enzymatic activity of mutants drastically decreased. Moreover, an alteration in the secondary structure was observed as revealed by CD spectra. Compared to other mutants, the fine structure of Ca2+-binding site within PLA2(¡µN7)) changed. Additionally, removal of the N-terminal region caused significant alternation in the structures of active site and substrate-binding site as evidenced by the results of fluorescence measurement, chemical modification and denaturation with detergents. In all N-terminal mutants, substituting Ans-1 with Met-1 affected the NNA-PLA2 structure to a least extent. The membrane-damage activity of PLA2(N1M) and M-PLA2 was 89% and 34% that of NNA-PLA2, respectively. PLA2(¡µN7) did not exhibit the membrane-damage activity. Studies on the biological activities of chemically modified N. naja atra PLA2 reflected a dissociation of the enzymatic activity from membrane-damage activity, and suggested the involvement of Trp-18, Trp-61, Lys-65, Tyr-3 and Tyr-63 in membrane-damage activity. Collectively, our data indicate that the intact N-terminus was crucial for maintaining of the functional conformation of PLA2 in the manifestation of the enzymatic activity and membrane-damage activity, and the enzymatic activity of PLA2 is in aid of but not exclusively essential for the membrane-damage effect.

Twenty-two sediment samples were collected from Kaohsiung Harbour, and it¡¦s neighboring coastal area, Taiwan and analysed for a suite of n-C10-C35 aliphatic hydrocarbons and fifteen polycycilc aromatic hydrocarbons (PAHs). The average total concentration of n-alkanes was 4.327 £gg/g dry wt. (0.461-22.601 £gg/g dry wt.) and PAHs was 0.588 £gg/g dry wt. (0.088-1.75 £gg/g dry wt.). The highest n-alkanes and PAHs concentrations were recorded in samples from D and A stations in Kaohsiung Harbour ; stations D and A are near the outlets of Chyan-Jenn and Jen-Ai rivers, respectively. The sources of n-alkanes are probably contributed form origins of petrogenic, biogenic and higher plants according to the value of CPI (carbon preference index), chromatogram of UCM (unresolved complex materials), and n-C16 ratio etc.; while PAHs were contributed mainly from combustion in coastal areas and petrogenic in harbour areas based on the ratios of total combustion and LMW/HMW ratios. Overall, sediment concentrations of n-alkanes and PAHs in Kaohsiung coastal area were similar to literature in the world. The potential for biological effects due to PAHs is found to be low based as their individual PAHs concentrations are in general lower than effects most existed sediment quality guidelines, except Acenaphthaene, Anthracene, Benzo[a]anthracene, and Fluorene.

An ISM-band frequency synthesizer is introduced in this thesis. The technique allows digital phase/frequency modulation to be achieved in a closed phase locked loop (PLL) without mixers and D/As. According to the simulation results using ADS, quantization noise will be filtered by the PLL bandwidth. But the data rate is also bounded by the PLL bandwidth. Two key components of this closed-loop architecture, Gaussian filter and delta-sigma modulator have been implemented by FPGA together with the Qualcomm Q3236 synthesizer IC.

Photoreflectance (PR) of surface-intrinsic-n+ type GaAs has been measured for various temperatures, then we can get the energy of E0+£G0 transition in various temperatures. The spectra exhibited many Franz-Keldysh oscillations, when probe beam¡¦s energy is larger than energy gap. Electric field (F) and transition energy can be determined from analyzing the Franz-Keldysh oscillation. Further more we can get the surface¡¦s Fermi level from the dependence of surface¡¦s electric field (Fs) on temperature (T).

A library of iridium complexes featuring oxazoline and imidazol-2-ylidene ligands were synthesized by reaction of a library of imidazoles with a second library of oxazoline iodides. These complexes were active catalysts for hydrogenations of aryl substituted monoenes. Tri- and 1,1-disubstituted alkenes were hydrogenated quantitatively with ee??s up to 99% at 1 atm hydrogen pressure. Catalyst, substrate, temperature and pressure effects were studied. The iridium complexes were also used for the kinetic study of hydrogenation of 2,3- diphenylbutadiene. This hydrogenation is a stepwise reaction: one double bond was hydrogenated first, then the second one. Both step hydrogenations were zero order in alkene. The consumption of 2,3-diphenylbutadiene was first order in catalyst, and probably first order in hydrogen pressure too. The enantioselectivity for the first step hydrogenation was low. There were match and mismatch catalyst-substrate relationships for the second step hydrogenation, and the enantioselectivities for this step were catalyst controlled. NMR studies indicated that the initiation of the reaction involved both hydrogen and alkene substrate. A competitive experiment was designed to explore the formation of meso-alkane at first step hydrogenation, and the results indicated that the alkane was formed predominantly via an associative mechanism. Four types of conjugate dienes were synthesized and hydrogenated. Different reactivities and selectivities were obtained for each type of dienes. In the best case, a diene was hydrogenated quantitatively with an excellent ent/meso ratio of 20:1.0 and 99% enantioselectivity. The scope, limitation and potential applications of the reactions were discussed. A selection of the dienes was hydrogenated with the Crabtree??s catalyst, for comparison, and the yields, conversions and diastereoselectivities were inferior to those from iridium-oxazoline-imidazol-2-ylidene catalysts.

This study examines the carcinogenic effect of HZE radiation and protective effects of different types of diets against colon carcinogenesis in a rat model. The effect of HZE radiation on health state and colon cancer development was evaluated. HZE radiation was found to suppress food consumption (P<0.0001) leading to lower body weight gain of irradiated rats when compared to the non-irradiated rats (P<0.05). The animals exposed to HZE radiation were found to start dying and/or getting pathologies 11 weeks earlier and at the end of the study had morbidity/mortality rate 14.2% higher (P=0.0005) than non-irradiated rats. There was no significant effect of HZE radiation on colon cancer incidence. The effects of dietary fibers and oils on health state and colon carcinogenesis were evaluated. Morbidity/mortality was found to be delayed in rats fed with pectinbased diets when compared to cellulose-based diet, regardless of radiation treatment. Similarly, fish oil was found to beneficially affect health of the experimental animals when compared to corn oil. Ten- and twenty-week delayed morbidity/mortality for irradiated and non-irradiated groups, respectively, was observed for rats fed with fish oil-based diets when compared to corn oil-based diets. Fish oil was also found to significantly reduce colon tumor incidence and multiplicity in non-irradiated rats (P<0.05). A similar trend was observed for the irradiated animals. No significant effect of fiber on colon cancer incidence was found. Finally, the effect of diets on general health and colon cancer development was investigated. Rats fed with corn oil/cellulose diet started dying and/or getting a disease earlier than rats fed with other diets, regardless of radiation treatment. The effect of diet on colon cancer development was found to depend on radiation treatment. Thus, in the absence of radiation treatment fish oil/cellulose was found to significantly reduce tumor incidence and multiplicity when compared to corn oil/pectin diet (P<0.05). In the presence of radiation treatment fish oil/pectin was found to lower the values of tumor incidence and tumor multiplicity, though the data obtained were not significant.

To examine how dietary n-3 polyunsaturated fatty acids affect Th2 cell development, female C57BL/6 mice were fed a washout corn oil (CO) diet for 1 wk followed by 2 wk of either the same CO diet or a fish oil (FO) diet. CD4+ T cells were isolated from spleens and cultured under both neutral (anti-CD3 and phorbol myristate acetate (PMA)) and Th2 polarizing conditions (anti-CD3 and PMA, in presence of rIL-4, rIL-2, and anti-IFN-γ) in the presence of homologous mouse serum (HMS) or fetal bovine serum (FBS) for 2 d. Dietary n-3 PUFA significantly enhanced Th2 cell development and suppressed Th1 development under neutral conditions as assessed by intracellular cytokine staining for IL-4 and IFN-γ as the two prototypic Th2 and Th1 cytokines, respectively. However, under Th2 polarizing conditions, while the suppression of Th1 cells was maintained in FO-fed mice, no dietary effect was observed in Th2 cells. Dietary FO increased the Th2/Th1 ratio under both neutral and Th2 polarizing conditions with HMS in the cultures. To examine the effect of dietary n-3 PUFA on Th1 development, DO11.10 Rag2-/- mice expressing transgenic T cell receptor specific for ovalbumin (OVA) peptide were used. CD4+ T cells were isolated from spleens and lymph nodes and stimulated with ovalbumin (OVA) peptide and irradiated BALB/c splenocytes in the presence of rIL-12, anti-IL-4, and rIL-2 in HMS for 2d. Cells were expanded for another 3 d in the presence of rIL-2 and rIL-12. Dietary n-3 PUFA did not affect Th1 differentiation as assessed by the proportion of IFN-γ+, IL-4- T cells in the cultures, but suppressed rIL-2 induced expansion. The suppressed expansion was due to suppressed proliferation (p<0.05). In vivo expansion of antigen-specific T cells was visualized by flow cytometric analysis of CFSE-positive transgenic T cells. Dietary n-3 PUFA did not appear to affect antigen-induced CD4+ T cell cycle progression in vivo. Overall, these results suggest dietary n-3 PUFA have no direct effect on Th2 cell development but do directly suppress Th1 cell development following both mitogenic and antigenic stimulation in vitro.

In this study, the characteristics of low-pressure chemical vapor deposition deposited silicon nitride films on n-GaN substrate were investigated. The physical and chemical properties were measured and surveyed. And an Al/LPCVD-Si3N4/n-GaN MOS structure was used for the electrical characterizations. For the electrical property improvements, we investigated the low-pressure chemical vapor deposition deposited silicon nitride films by (NH4)2Sx treatment. Furthermore, the silicon nitride films were passivated by fluorine ions to improve the electrical characterizations that came from the liquid phase deposited SiO2 stacks. After the (NH4)2Sx treatment and fluorine ions passivation, the dielectric constant of low-pressure chemical vapor deposition deposited silicon nitride films were maintained and the leakage current density were improved. The highest dielectric constant is 12.13, and lowest leakage current density are 1.73¡Ñ10-10 A/cm2 at 1 MV/cm and 3.81¡Ñ10-10 A/cm2 at 1 MV/cm for the LPCVD-Si3N4 film after fluorine passivation and (NH4)2Sx treatment.

Diamond-Like Carbon (DLC) films have been deposited on ITO glass substrate. DLC thin film was electrodeposited at low DC potential using a mixture of acetic acid and DI water. The DLC film deposition parameters include DC potential, deposited temperature, the concentration of electrolyte were used to study the characteristics of DLC film measured by the Ellipsometer, XPS, SEM and Raman spectroscopy in detail. The Raman spectra shows two peaks located near 1358cm-1 and 1580cm-1 assigned as the characteristics peaks of DLC films. That is an evidence for DLC film deposited successfully on ITO glass. Scanning electron microscopy (SEM) can make insight into accurately the surface morphology and uniformity of DLC films so as used to grow the best quality of DLC films. From the variations of the I-t curve and the surface morphology observed by SEM, the properties of DLC film depend on a verity of growth parameters such as applied voltage, the concentration of electrolyte and deposition temperature. The shift of G-peak increase with the applied voltage, and the sp2/sp3 ratio of the content C1s decreases with the applied voltage. Finally, based on the I-t curve and results of SEM, XPS, Raman, and Ellipsometer for n, k coefficients measured, we obtain a deeply understanding for the growth conditions of DLC films and their surface morphology. We achieve the consistent results between various measurements. Finally, the optimizing growth of DLC film is to be studied and discussed in future

Sowohl bei der Forschung der Maillard-Reaktion in Lebensmitteln als auch im menschlichen Körper lag das Hauptaugenmerk bislang auf der Reaktion der Carbonylfunktion mit den Aminofunktionen der Seitenketten wie Lysin oder Arginin, da sie in vielen Lebensmitteln oder physiologischen Proteinen die größte Quelle an Aminofunktionen darstellen. Dagegen wurde eine vergleichbare Reaktion mit dem N-Terminus von Aminosäuren, Peptiden oder Proteinen weniger beachtet, obgleich in lysinarmen oder peptidhaltigen Lebensmitteln die N-terminalen Aminofunktionen dominieren und die Seitenketten körpereigener Proteine räumlich für einen Angriff der Carbonylfunktion unzugänglich sein können. Da in den HA-Nahrungen die allergieauslösenden Proteine hydrolytisch gespalten vorliegen, stehen für eine mögliche Amadori-Produktbildung gegenüber den konventionellen Säuglingsnahrungen quantitativ mehr alpha-Aminogruppen als epsilon-Aminogruppen zur Verfügung. Demzufolge sollte für die Beurteilung von HA-Nahrungen eine Methode entwickelt werden, mit deren Hilfe eine Aussage über die Amadori-Produktbildung auch am N-Terminus getroffen werden kann. Aufbauend auf den Ergebnissen der Furoylmethylderivate-Bestimmung (FMAA-Bestimmung) in peptidhaltigen Lebensmitteln, war es ein weiteres Ziel der vorliegenden Dissertation die entwickelte Methode auch auf ihre Anwendbarkeit auf die Beurteilung des Glykierungsstatus des Hämoglobin in vivo zu testen. Nach der N-terminalen Amadori-Produktbildung im Zuge der frühen Phase der Maillard-Reaktion lag im zweiten Teil der Dissertation das Hauptaugenmerk auf die fortgeschrittene Phase der Maillard-Reaktion am N-Terminus von Peptiden oder Proteinen. Der Schwerpunkt lag dabei auf der Bildung von 2-(1H)-Pyrazinonen im komplexen trockenen Lebensmittel und in vivo.