The results of studies designed to obtain information about the factors that control the chemical efficiencies/regioselectivities and quantum yields of single electron transfer (SET)-promoted reactions of acceptor-polydonor systems are reported. Photochemical and photophysical investigations were carried out with bis-donor tethered phthalimides and naphthalimides of general structure N-phthalimido- and N-naphthalimido-CH2CH2-D-CH2CH2-NMsCH2-E (E = SiMe3 or CO2NBu4 and D = NMs, O, S, and NMe). These substrates contain common terminal donor groups (NMsCH2SiMe3 or NMsCH2CO2NBu4) that have known oxidation potentials and cation radical fragmentation rates. Oxidation potentials and fragmentation rates at the other donor site in each of these substrates are varied by incorporating different heteroatoms and/or substituents. Photoproduct distribution, reaction quantum yield, and fluorescence quantum yield measurements were made. The results show that photocyclization reactions of alpha-trimethylsilylmethansulfonamide (E = SiMe3)- and alpha-carboxymethansulfonamide (E = CO2NBu4)-terminated phthalimides and naphthalimides that contain internal sulfonamide, ether, and thioether donor sites (D = NMs, O, or S) are chemically efficient (80-100%) and that they take place exclusively by a pathway involving sequential photoinduced SET (zwitterionic biradical desilylation or decarboxylation) biradical cyclization. In contrast, photoreactions of alpha-trimethylsilylmethansulfonamide- and alpha-carboxymethansulfonamide-terminated phthalimides and naphthalimides that that contain an internal tertiary amine donor site (D = NMe) are chemically inefficient and follow a pathway involving alpha-deprotonation at the tertiary amine radical cation center in intermediate, iminium radical-containing, zwitterionic biradicals. In addition, the quantum efficiencies for photoreactions of alpha-trimethylsilylmethansulfonamide- and alpha-carboxymethansulfonamide-terminated phthalimides are dependent on the nature of the internal donor (eg., phi = 0.12 for D = NMs, E = SiMe3; phi = 0.02 for D = S, E = SiMe3; phi = 0.04 for D = NMe, E = SiMe3). The results of this effort are discussed in terms of how the relative energies of interconverting zwitterionic biradical intermediates and the energy barriers for their alpha-heterolytic fragmentation reactions influence the chemical yields and quantum efficiencies of SET promoted photocyclization reactions of acceptor-polydonor substrates.
The IHO S-100 is a standard on the universal hydorgraphic data model for supporting information services that integrate various data in maritime and provide proper information for safety of vessels. The S-100 is used to develop S-10x product specifications which are standards on guideline for creation and delivery of specific data set in maritime. The product specification for feature-based data such as ENC(Electronic Navigational Chart) data includes a feature catalogue that describes characteristics of features in that feature-based data. The feature catalogue is developed by domain experts with knowledge on data of the target domain. However, it is not feasible to develop a feature catalogue according to the XML schema by manual. In the IHO TSMAD committee meeting, needs of developing technology on building feature catalogue has been discussed. Therefore, we present a feature catalogue builder that is a GUI(Graphic User Interface) system supporting domain experts to build feature catalogues in XML. The feature catalogue builder is developed to connect with the FCD(Feature Concept Dictionary) register in the IHO(International Hydrographic Organization) GI(Geographic Information) registry. Also, it supports domain experts to select proper feature items based on the relationships between register items.
Although the various crime involved numerous digital evidence, the digital evidence is hard to be acknowledged as a evidence to proof the crime fact in court. We propose the method of verification for the legal admissibility of digital evidence using digital forensics ontology. In order to verify the legal admissibility of digital evidence, we will extend the digital ontology by standard digital forensics process from Digital Forensics Technical Manual defined by KNPA and set up the relation properties and the rule of property constraint to process class in the digital forensics ontology. It is possible for proposed ontology to utilize to plan the criminal investigation and to educate the digital forensics.
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