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Title: Part I. Carbon and mercury-carbon optically transparent electrodes. Part II. Investigation of redox properties of technetium by cyclic voltammetry and thin layer spectroelectrochemistry

Abstract

A carbon optically transparent electrode (C OTE) has been prepared by vapor-deposithing a thin carbon film (150 to 310 A thick) on glass and quartz. Optical transparency is good throughout the ultraviolet-visible region. Electrochemical and spectroelectrochemical measurements were made with ferricyanide and o-tolidine respectively. The C OTE serves as a good substrate for deposition of a thin mercury film to form a mercury film transparent electrode (Hg-C OTE). The Hg-C OTE exhibits electrochemical properties of conventional mercury film electrodes as evidenced by Pb/sup 2 +/ cyclic voltammograms. The Hg-C OTE exhibits electrochemical properties of conventional mercury film electrodes as evidenced by Pb/sup 2 -/ cyclic VOHammograms. The Hg-C OTE enabled the spectrochemical characterization of cysteine oxidation, which was shown to involve the oxidation of mercury to form mercurous cysteinate. An 8080 based microcomputer has been interfaced with a Harrick oscillating mirror rapid scanning uv-visible spectrophotometer. Two different approaches are compared for controlling the galvanometer. The first utilizes the digital hardware on the Harrick processing module to derive the mirror drive waveform, while the second creates the waveform under direct software control. A potentiostat is also interfaced and the system is demonstrated by the spectroelectrochemical determination of the redox potential ofmore » o-tolidine. Redox potentials are also determined for a series of technetium complexes by the spectropotentiostatic technique. These include hexahalogens, ditertiary arsine, and 1,2-bis(diphenylphosphino) ethane complexes of technetium. Transient hexavalent technetium is produced, detected, and characterized in aqueous alkaline media by pulse radiolysis and very fast scan cyclic voltammetry. The lifetime is of the order of milliseconds. This species is potentially useful in the preparation of technetium radiopharmaceuticals.« less

Authors:
Publication Date:
Research Org.:
Cincinnati Univ., OH (USA)
OSTI Identifier:
5555047
Resource Type:
Thesis/Dissertation
Resource Relation:
Other Information: Thesis (Ph. D.)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; CYSTEINE; ELECTROCHEMISTRY; OXIDATION; ELECTRODES; MATERIALS; PERFORMANCE; TECHNETIUM COMPLEXES; REDOX POTENTIAL; ARSENIC COMPOUNDS; CARBON; GLASS; MERCURY; MICROPROCESSORS; ORGANIC HALOGEN COMPOUNDS; ORGANIC PHOSPHORUS COMPOUNDS; PH VALUE; QUARTZ; RADIOLYSIS; SPECTROPHOTOMETERS; VOLTAMETRY; AMINO ACIDS; CARBOXYLIC ACIDS; CHALCOGENIDES; CHEMICAL RADIATION EFFECTS; CHEMICAL REACTIONS; CHEMISTRY; COMPLEXES; COMPUTERS; DECOMPOSITION; ELECTRONIC CIRCUITS; ELEMENTS; MEASURING INSTRUMENTS; METALS; MICROELECTRONIC CIRCUITS; MINERALS; NONMETALS; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; OXIDE MINERALS; OXIDES; OXYGEN COMPOUNDS; RADIATION CHEMISTRY; RADIATION EFFECTS; SILICON COMPOUNDS; SILICON OXIDES; THIOLS; TRANSITION ELEMENT COMPLEXES; 400400* - Electrochemistry; 400201 - Chemical & Physicochemical Properties; 400702 - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials

Citation Formats

Hurst, R.W. Part I. Carbon and mercury-carbon optically transparent electrodes. Part II. Investigation of redox properties of technetium by cyclic voltammetry and thin layer spectroelectrochemistry. United States: N. p., 1980. Web.
Hurst, R.W. Part I. Carbon and mercury-carbon optically transparent electrodes. Part II. Investigation of redox properties of technetium by cyclic voltammetry and thin layer spectroelectrochemistry. United States.
Hurst, R.W. 1980. "Part I. Carbon and mercury-carbon optically transparent electrodes. Part II. Investigation of redox properties of technetium by cyclic voltammetry and thin layer spectroelectrochemistry". United States. doi:.
@article{osti_5555047,
title = {Part I. Carbon and mercury-carbon optically transparent electrodes. Part II. Investigation of redox properties of technetium by cyclic voltammetry and thin layer spectroelectrochemistry},
author = {Hurst, R.W.},
abstractNote = {A carbon optically transparent electrode (C OTE) has been prepared by vapor-deposithing a thin carbon film (150 to 310 A thick) on glass and quartz. Optical transparency is good throughout the ultraviolet-visible region. Electrochemical and spectroelectrochemical measurements were made with ferricyanide and o-tolidine respectively. The C OTE serves as a good substrate for deposition of a thin mercury film to form a mercury film transparent electrode (Hg-C OTE). The Hg-C OTE exhibits electrochemical properties of conventional mercury film electrodes as evidenced by Pb/sup 2 +/ cyclic voltammograms. The Hg-C OTE exhibits electrochemical properties of conventional mercury film electrodes as evidenced by Pb/sup 2 -/ cyclic VOHammograms. The Hg-C OTE enabled the spectrochemical characterization of cysteine oxidation, which was shown to involve the oxidation of mercury to form mercurous cysteinate. An 8080 based microcomputer has been interfaced with a Harrick oscillating mirror rapid scanning uv-visible spectrophotometer. Two different approaches are compared for controlling the galvanometer. The first utilizes the digital hardware on the Harrick processing module to derive the mirror drive waveform, while the second creates the waveform under direct software control. A potentiostat is also interfaced and the system is demonstrated by the spectroelectrochemical determination of the redox potential of o-tolidine. Redox potentials are also determined for a series of technetium complexes by the spectropotentiostatic technique. These include hexahalogens, ditertiary arsine, and 1,2-bis(diphenylphosphino) ethane complexes of technetium. Transient hexavalent technetium is produced, detected, and characterized in aqueous alkaline media by pulse radiolysis and very fast scan cyclic voltammetry. The lifetime is of the order of milliseconds. This species is potentially useful in the preparation of technetium radiopharmaceuticals.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 1980,
month = 1
}

Thesis/Dissertation:
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  • The work presented herein describes a fundamental investigations of carbon as electrode material by using the pyrolysis of photoresist to create an optically transparent material. The development of these carbon-based optically transparent electrodes (C-OTEs) enables investigations of molecular interactions within the electrical double layer, processes that are central to a wide range of important phenomena, including the impact of changes in the surface charge density on adsorption. The electrochemical importance of carbon cannot be understated, having relevance to separations and detection by providing a wide potential window and low background current in addition to being low cost and light weight.more » The interactions that govern the processes at the carbon electrode surface has been studied extensively. A variety of publications from the laboratories of McCreery and Kinoshita provide in depth summaries about carbon and its many applications in electrochemistry. These studies reveal that defects, impurities, oxidation, and a variety of functional groups create adsorption sites on carbon surfaces with different characteristics. The interest in C-OTEs was sparked by the desire to study and understand the behavior of individual molecules at electrified interfaces. It draws on the earlier development of Electrochemically Modulated Liquid Chromatography (EMLC), which uses carbon as the stationary phase. EMLC takes advantage of changing the applied potential to the carbon electrode to influence the retention behavior of analytes. However, perspectives gained from, for example, chromatographic measurements reflect the integrated response of a large ensemble of potentially diverse interactions between the adsorbates and the carbon electrode. Considering the chemically and physically heterogeneous surface of electrode materials such as glassy carbon, the integrated response provides little insight into the interactions at a single molecule level. To investigate individual processes, they have developed C-OTEs in order to couple electrochemistry with single molecule spectroscopy (SMS). Like EMLC, the novel merger of SMS with electrochemistry is a prime example of how a hybrid method can open new and intriguing avenues that are of both fundamental and technological importance. They show that by taking the benefits of total internal reflection fluorescence microscopy (TIRFM) and incorporating carbon as electrode material observations central to the interactions between single DNA molecules and an electrified carbon surface can be delineated. Using TIRFM while applying a positive potential to the electrode, individual molecules can be observed as they reversibly and irreversibly adsorb to the carbon surface. The positive potential attracts the negatively charged DNA molecules to the electrode surface. Dye labels on the DNA within the evanescent wave are excited and their fluorescence is captured by an intensified charge coupled device (ICCD) camera. Results are therefore presented regarding the interactions of λ-DNA, 48,502 base pairs (48.5 kbp), HPV-16, 7.9 kbp, and 1 kbp fraction of pBR322 DNA. In addition to the influence of molecular size on adsorption, the fabrication, characterization, and more conventional spectroelectrochemical applications of these novel C-OTEs are presented.« less
  • In the foregoing portions of this thesis, the substrate film technique of Daoust has been studied with respect to the pertinent world literature and by means of certain new experimental approaches. A consideration of the literature indicates that many problems are potentially inherent in substrate definition.
  • Transparent conducting electrodes with the combination of high optical transmission and good electrical conductivity are essential for solar energy harvesting and electric lighting devices. Currently, indium tin oxide (ITO) is used because ITO offers relatively high transparency (>80%) to visible light and low sheet resistance (R s = 10 ohms/square (Ω /2)) for electrical conduction. However, ITO is costly due to limited indium reserves, and it is brittle. These disadvantages have motivated the search for other conducting electrodes with similar or better properties. There has been research on a variety of electrode structures involving carbon nanotube networks, graphene films, nanowiremore » and nanopatterned meshes and grids. Due to their novel characteristics in light manipulation and collection, photonic crystal structures show promise for further improvement. Here, we report on a new architecture consisting of nanoscale high aspect ratio metallic photonic structures as transparent electrodes fabricated via a combination of processes. For (Au) and silver (Ag) structures, the visible light transmission can reach as high as 80%, and the sheet resistance of the structure can be as low as 3.2Ω /2. The optical transparency of the high aspect ratio metal structures at visible wavelength range is comparable to that of ITO glass, while their sheet resistance is more than 3 times lower, which indicates a much higher electrical conductivity of the metal structures. Furthermore, the high aspect ratio metal structures have very high infrared (IR) reflection (90%) for the transverse magnetic (TM) mode, which can lead to the development of fabrication of metallic structures as IR filters for heat control applications. Investigations of interdigitated structures based on the high aspect ratio metal electrodes are ongoing to study the feasibility in smart window applications in light transmission modulation.« less
  • The nuclear magnetic resonance frequencies of /sup 201/Hg (l = 3/2) and /sup 199/Hg (l = 1.2) were compared in driven optically-pumped atomic light-absorption oscillators to see if the relative frequencies depend on the orientation of the quantization axis in space. The null result obtained (deltanu < 500 nanoHertz, 95% confidence) reduces the most recent limits on possible vector and quadrupole interactions, which violate spatial isotropy by three orders of magnitude. Using the same apparatus, the author searched for a permanent atomic electric dipole moment by measuring the /sup 199/Hg nuclear magnetic resonance frequency in the presence of a reversiblemore » electric field of 9 kV/cm. The null result obtained (d/sub A/ < 5e cm) reduces previous limits on possible time-reversal violating interactions in atoms by an order of magnitude.« less