Tyrosinase is a widespread, highly studied and important enzyme involved in processes ranging from the browning of mushrooms to roles in mammalian cancer. The enzyme suffers from a noticeable lag phase while the enzyme generates all necessary cofactors from available substrates. There have not been significant studies of the effect on lag from moving through a family of substituted substrates. This thesis reports the results of one such study using a family of N-acyltyramines. The selection of N-acyltyramines was ideal because the substrates in this reaction may be related to synthesis of N-acyldopamines, which serve many important physiological functions. It was concluded that the product formed from N-acetyltyramine is 1-acetyl-2,3-dihydro-1H-indole-6,7-dione, a quinone.

No description available.

<p>It is known that there is an intraindividual amplitude variation in motor electroneurography when the same person is examined at different times. This variation affects the evaluation the status of the patient. The aim of this study was to investigate if the intraindividual amplitude variation decreased by photographing the electrode position, that later is used in the follow-up study. Twenty test persons were examined by four laboratory scientists. The nerves that were examined were median, ulnar, peroneal and tibial nerve. At the first examination the laboratory scientists used method guidelines and took photographs of the electrode position. The photographs were then used in the follow-up. The results showed that there was an indication of decreased of the intraindividual amplitude variation when photographic documentation was used instead of method guidelines.</p>

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

RESUME Le travail de thèse porte sur le développement d’électrodes sélectives originales et performantes pour l’analyse de composés d’intérêt pharmaceutique. La partie introductive traite des notions relatives à l’électrochimie mais également de notions sur les molécules médicamenteuses étudiées, en l’occurrence les principes antipaludéens et l’iode. La partie expérimentale se subdivise en deux parties distinctes selon le type d’électrodes sélectives auxquelles font appel les techniques électrochimiques. La première partie concerne l’élaboration, la caractérisation et l’application des électrodes potentiométriques à membrane polymérique incluant une paire d’ions et sélectives à diverses molécules organiques pharmacologiquement actives (antipaludéens). Leur application aussi bien en analyse pharmaceutique qu’en cinétique de dissolution est décrite. La deuxième partie est consacrée à l’élaboration d’un type de senseur ampérométrique original à pâte de carbone à base d’argent micronisé ou colloïdal et à la comparaison de ses performances avec l’électrode d’argent métallique. L’intérêt analytique est mis en évidence par la détermination quantitative des iodures. Les différents aspects susceptibles d’influencer leur comportement, dont la nature des agents précipitants (tétraphénylborate de sodium et le tétrakis (4-chlorophényl) borate de potassium) et de plastifiants ont été investigués. Les bonnes performances des ces électrodes en analyse quantitative ont permis d’explorer les possibilités de leur utilisation à l’étude de la cinétique de dissolution. L’ampérométrie à électrode à pâte de carbone modifiée à base d’argent à l’échelle micronisée (35% m/m) couplée à la chromatographie liquide ionique s’est avérée très sensible vis-à-vis des iodures en particulier et des halogénures en général. Les facteurs susceptibles d’influencer les grandeurs de séparation et la réponse de l’électrode ont été investigués et l’exploitation du signal ampérométrique permet le dosage sélectif et rapide de faibles concentrations en iodures. Les informations fournies par les mesures réalisées en voltampérométrie cyclique à l’aide des mêmes électrodes permettent une bonne compréhension mécanistique quant au mode de détection ampérométrique évitant ainsi toute confusion à ce sujet et permettant l’optimisation du processus de détection. ------------------------------------------------ ABSTRACT This thesis describes the development of original and high performance selective electrodes for the analysis of several pharmaceutical compounds. The introduction describes the pharmaceutical compounds of interest (antimalarial drugs and iodine) and provides an overall understanding of the electrochemical groundwork pertaining to their analysis. The experimental aspect of the thesis is divided into two parts, each according to the type of electrode and electrochemical technique used for the analysis. The first part describes the design, characterization, and application of polymer membrane based ion selective potentiometric electrodes. Selectivity was provided by including ion pairs of several antimalarial drugs into the membrane. The feasibility of use of these electrodes in pharmaceutical analysis as well as in dissolution trials is also described in this part. The second part describes the design of an original silver-modified carbon paste amperometric sensor and compares its performances to those of a plain metallic silver electrode. The electrode has been modified by silver microparticles or by silver nanoparticles. Quantitative iodine determination serves to prove the usefulness of this new sensor in analytical chemistry. Different aspects, such as the nature of the counter ions (sodium tetraphenylborate and potassium tetrakis (4-chlorophenyl) borate) and the plastifying agents that are likely to influence electrode behaviour have been investigated. Since the electrodes have been shown to perform well in quantitative analysis, the possibility of use in dissolution trials was explored. Micronized silver-modified carbon paste electrode (35% Ag m/m) coupled to anionic-exchange liquid chromatography with amperometric detection was shown to be very sensitive with regards to the assay of halogenides in general and iodide in particular. After having investigated the various factors likely to influence chromatographic separation and electrode response, it was shown that the sensor could be used to rapidly and selectively determine low iodide concentrations in complex samples. Cyclic voltammetric analysis provided information concerning the mechanisms allowing amperometric detection, thus allowing an optimisation of the detection procedures.

It is known that there is an intraindividual amplitude variation in motor electroneurography when the same person is examined at different times. This variation affects the evaluation the status of the patient. The aim of this study was to investigate if the intraindividual amplitude variation decreased by photographing the electrode position, that later is used in the follow-up study. Twenty test persons were examined by four laboratory scientists. The nerves that were examined were median, ulnar, peroneal and tibial nerve. At the first examination the laboratory scientists used method guidelines and took photographs of the electrode position. The photographs were then used in the follow-up. The results showed that there was an indication of decreased of the intraindividual amplitude variation when photographic documentation was used instead of method guidelines.

Glucose-6-phosphate (G6P) plays an important role in carbohydrate metabolism of all living organisms. Compared to the conventional analytical methods available for estimation of G6P, the biosensors having relative simplicity, specificity, low-cost and fast response time are a promising alternative. We have reported a G6P biosensor based on screen-printed electrode utilizing Prussian Blue (PB) nanoparticles and enzymes, glucose-6-phosphate dehydrogenase and glutathione reductase. The PB nanoparticles acted as a mediator and thereby enhanced the rate of electron transfer in a bi-enzymatic reaction. The Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy study confirmed the formation of PB, whereas, the atomic forced microscopy revealed that PB nanoparticles were about 25-30 nm in diameter. Various optimization studies, such as pH, enzyme and cofactor loading, etc. were conducted to obtain maximum amperometric responses for G6P measurement. The developed G6P biosensor showed a broad linear response in the range of 0.01-1.25 mM with a detection limit of 2.3 mM and sensitivity of ­63.3 mA/mM at a signal-to-noise ratio of 3 within 15 s at an applied working potential of -100 mV. The proposed G6P biosensor also exhibited good stability, excellent anti-interference ability and worked well for serum samples.

TerraPower LLC is designing a fast breed and burn reactor intended to operate for up to 40 years without refueling, designated as the Travelling Wave Reactor (TWR). Various U-Zr alloy fuel designs have been proposed for the TWR that may require a powder feed for fabrication. A simple and economic option for laboratory scale powder production is the Rotating Electrode Process (REP), which produces microsphere shaped powder by melting the tip of a rotating bar with an electric arc. In order to fully characterize this process for various U-Zr alloys and provide the feed material for testing fabrication techniques, a Rotating Electrode System (RES) was designed and built. The RES is largely based on a combination of two designs; an early REP system developed by Starmet Corporation in the 19xxa and a later design optimized for U-Mo powder production by Idaho National Laboratory (INL). The RES designed for this work was improved based on input from vendors specializing in their respective areas of expertise and is capable of atomizing up to a 1.26 cm diameter metal alloy rod at 40,000 RPM. Every component of the machine can be disassembled and transferred through a 35.56 cm (14 in) diameter air lock of a glovebox so that it can operate in a controlled environment. The RES was tested by atomizing various diameter copper rods to prove system functionality. The tests were carried out in air using an argon cover gas in the powder collection chamber, known as the catch pan to limit oxidation rates of the newly generated microspheres. The powder produced showed strong sphericity ranging from 50 µm to 500 µm in diameter. Problems and areas of concern that were encountered during operation have been addressed so that the RES can be further optimized to better atomize U-Zr alloys once transferred into the glovebox.

No description available.

In order to apply to S-Band (1-4.5 GHz) of wireless communication system, we designed and fabricated a high-insolating RF-MEMS switch by surface micromachining technology in this study. In terms of the micro switch, we performed the structural design, high frequency simulation, components process integration and high-frequency measurement in this study. Especially for making components be high-isolation, low-loss and low-driving voltage, we proposed the following three methods: (i) adjusting the space and width of the transmission lines to improve the RF performance; (ii) applying the stress imbalance, by using dual metal composite top electrode, to form a arched contact electrode and reduce the drive voltage efficiently; (iii) using non-isometric spring structure to stabilize the electrode movement of the components. Besides, we did the optimizing simulation for this study, which were supported by Ansoft-HFSS and ADS, in terms of the micro switch which has different structural design as mentioned above. The size of the optimized RF micro-switch which we developed for this study is only 145 £gm ¡Ñ 205 £gm. Switched from on-state to off-state, the component needs 36.5V drive voltage only. According to the result of the commercial network analyzer in 1-4.5GHz frequency range, the isolation rate of the components reaches -59.721dB while off-state; the insert los reaches -1.625dB while on-state.