Zugl.: Stuttgart, Univ., Diss., 2008

To gain better understanding of the nature of the carbonmetal bonding in 3-neopentylallyl alkali metal (5,5-dimethyl- 2-hexenyl alkali metal) systems, an investigation is extended to 3-neopentylallylpotassium. In addition, pertinent data on the 3-neopentylallyl systems are re-examined in an attempt to understand the trends in the bonding habits, as affected by the solvent, the cation and the temperature.

京都大学 / 0048 / 新制・論文博士 / 博士(農学) / 乙第12936号 / 論農博第2816号 / 新制||農||1033(附属図書館) / 学位論文||H27||N4895(農学部図書室) / 32146 / (主査)教授 伏木 亨, 教授 保川 清, 教授 安達 修二 / 学位規則第4条第2項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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We give an overview of quantum chemical methods with a particular emphasis on the development of high-accuracy quantum chemical models. The reliability of these methods often hinges on whether enough electron correlation is included in the truncated wave function. As an example, we investigate the structures of m-benzyne and its fluorinated derivative, tetrafluoro-m-benzyne where the inclusion of triple excitations is paramount to correctly describe through-bond delocalization of the monocyclic form. At the CCSDT/6-31G** level of theory, the C1–C3 distance of the minimum energy form of m-benzyne is 2.0°A and the profile of the PES along the C1–C3 distance is that of an asymmetric, single-well, in agreement with previous density-functional theory and coupled cluster studies. In addition, the calculated CCSD(T) fundamental frequencies are in excellent agreement with the measured infrared frequencies, thus confirming the monocyclic form of m-benzyne. For tetrafluoro-m-benzyne, however, the increased eclipsing strain between the ring-external Câ X bonds stabilizes the bicyclo[3.1.0]hexatriene form: the C1–C3 distance is calculated at the CCSD(T)/cc-pVTZ level to be approximately 1.75 °A, which is in the range of elongated CC bonds. Computed harmonic vibrational frequencies compare reasonably well with the experimental neon-matrix difference spectrum and provide further evidence for the existence of a bicyclic form. We also report an extension of the coupled cluster iterative-triples model, CC3, to excited states of open-shell molecules, including radicals. We define the method for both spin-unrestricted Hartree-Fock (UHF) and spin-restricted open-shell Hartree-Fock (ROHF) reference determinants and discuss its efficient implementation in the PSI3 program package. The program is streamlined to use at most O(N7) computational steps and avoids storage of the triple-excitation amplitudes for both the ground-and excited-state calculations. The excitation-energy program makes use of a Lowdin projection formalism (comparable to that of earlier implementations) that allows computational reduction of the Davidson algorithm to only the single- and double-excitation space, but limits the calculation to only one excited state at a time. However, a root-following algorithm may be used to compute energies for multiple states of the same symmetry. Benchmark applications of the new methods to the lowest valence 2B1 state of the allyl radical, low-lying states of the CH and CO+ diatomics, and the nitromethyl radical show substantial improvement over ROHF- and UHF-based CCSD excitation energies for states with strong double-excitation character or cases suffering from significant spin contamination. For the allyl radical, CC3 adiabatic excitation energies differ from experiment by less than 0.02 eV, while for the 2§+ state of CH, significant errors of more than 0.4 eV remain. Finally, ground- and excited-state dipole moments are derived diagramatically and were recently developed within the PSI3 quantum chemistry package. However, convergence problems with computing the left-hand excited-state has prevented us from reporting any meaningful results. Thus, future work includes solving this convergence problem before the effects of triple excitations on one-electron properties can be reported with certainty. / Ph. D.

Since 2006 there have been four Salmonella enterica and one Listeria monocytogenes foodborne outbreaks linked to whole cantaloupe fruit. No post-harvest intervention to reduce potential contamination on cantaloupe currently exists. The complex surface topography of netted cantaloupes aids bacterial attachment. This research evaluates the use of allyl isothiocyanate (AITC; a natural antimicrobial) to reduce populations of S. enterica Michigan and L. monocytogenes on the surface of cantaloupe. Fifty μl of S. Michigan or L. monocytogenes was inoculated onto whole ‗Athena‘ or ‗Hales Best Jumbo‘ (‗HBJ‘) cantaloupe fruit in 22 mm diameter circles and allowed to dry for 90 min. resulting in 6.60 log CFU/g. Cantaloupe received either AITC liquid or vapor, sterile deionized water, 200 ppm sodium hypochlorite per circle, or no treatment. All cantaloupes were stored in separate sealed glass desiccators for 1 or 24 h at 25°C or 35°C. To enumerate the bacteria following treatment, 22 mm sections of the rind were removed, homogenized and plated onto appropriate agar. Headspace analysis using Gas Chromatography-Mass Spectrometry (GC-MS) quantified the concentration of each AITC vapor treatment. The texture quality of the pericarp tissue of whole cantaloupes was evaluated after 24 h treatments, followed by two weeks of storage at 4°C. The concentration of vapor ranged from 3.4 to 19.6 μl AITC/L inside the desiccators. The liquid treatment reduced (P < 0.05) S. Michigan populations on ‗Athena‘ (3 log CFU/g) and L. monocytogenes on ‗HBJ‘ (2.6 log CFU/g). The longer exposure time to the AITC vapor (24 h versus 1 h) resulted in a greater reduction of both S. Michigan and L. monocytogenes on ‗Athena‘ and treatments at 35°C reduced microbial populations up to 4.5 times greater (P < 0.05). The highest vapor concentration reduced (P < 0.05) both pathogens at least 3.0 log CFU/g on ‗Athena‘ at 25°C. Generally, bacterial pathogens from the surface of ‗Athena‘ cantaloupe were reduced more than pathogens inoculated on the surface of ‗HBJ.‘ The application of AITC liquid or vapor is a natural alternative post-harvest treatment to 200 ppm free chlorine to reduce the level of bacterial contamination on cantaloupe surfaces for certified organic production. / Ph. D.

This thesis describes attempts to synthesize 5-allyl-5-(2-thienyl)-barbituric acid as an improved anticonvulsant.

Parmi les analogues de sucres, les iminosucres constituent la classe la plus prometteuse au niveau biologique. En effet, leur structure, dans laquelle l'atome d'oxygène intracyclique est remplacé par un atome d'azote, leur confère des propriétés uniques d'inhibition de glycosidases et/ou glycosyltransférases, et en fait donc de très bons candidats thérapeutiques. L'introduction d'un substituant pseudo-anomérique carboné permet de mimer la partie aglycone du substrat de l'enzyme et d'accéder aux iminosucres C-glycosides, des composés chimiquement stables qui sont des inhibiteurs sélectifs et puissants des glycosidases.Afin d'accélérer la découverte de molécules d'intérêt thérapeutique, il est nécessaire de trouver des voies de synthèses conduisant à une plus grande diversité structurale. La méthodologie que nous avons mise au point est basée sur la débenzylation régiosélective de la position 2 de C-allyl glycosides exploitant une iodocyclisation. Cette dernière a été appliquée avec succès à la C-allyl-1-déoxynojirimycine puis étendue à plusieurs iminosucres de configurations variées en séries pipéridine et pyrrolidine.L'introduction de diversité moléculaire a été réalisée à partir de la C-allyl-1-déoxynojirimycine O-débenzylée régiosélectivement en position 2. Nous avons ainsi obtenu plusieurs iminosucres de configurations D-gluco- et D-manno- portant différentes fonctionnalités en position 2. La mise au point de cette synthèse a donc permis d'accéder à une grande variété de C-allyl iminosucres à partir d'un synthon unique. L'accès à des iminosucres bicycliques de structures inédites a également été possible en exploitant un C-allyl 2-céto iminosucre obtenu par notre méthodologie de débenzylation régiosélective. / Iminosugars constitute undoubtedly the most promising class of sugar analogues, their unique glycosidase and/or glycosyltransferase inhibition profile making them promising therapeutics. To generate more potent and selective inhibitors called C-glycoside iminosugars, introduction of a stable pseudoanomeric substituent is usually performed, the improved efficacy being attributed in part to the information brought by the aglycon moiety.The main challenge associated with this class of iminosugars C-glycosides is currently the design of efficient and general routes enabling introduction of structural diversity at a late stage from advanced synthons to accelerate the discovery of biologically relevant molecules. In this context, we have explored a strategy based on a regioselective debenzylation at C-2 and a stereocontrolled nucleophilic substitution assisted by the N-benzyl group. We have successfully applied this methodology on the C-allyl-1-deoxynojirimycin and extended it to several iminosugars in the piperidine and pyrrolidine series.The introduction of molecular diversity was performed from the C-allyl-1-deoxynojirimycin selectively O-debenzylated at position 2. We obtained several iminosugars in the D-gluco- and D-manno- series bearing various functionalities at position 2. This strategy allowed us to access a wide range of C-allyl iminosugars from one single synthon. We have also described the access to unknown bicyclic iminosugars starting from a C-allyl 2-keto iminosugar obtained by our regioselective debenzylative methodology.

The syntheses and characterization of the palladium complexes [Pd(accp)2] (7), [Pd(acch)2] (8), [Pd(η3-CH2CMeCH2)(accp)] (11), [Pd(η3-CH2CMeCH2)(acch)] (12), [Pd(η3-CH2CtBuCH2)(accp)] (13) and [Pd(η3-CH2CtBuCH2)(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na2[Pd2Cl6] forming 7 and 8 or with [(Pd(η3-CH2CRCH2)(μ-Cl))2] (9, R = Me; 10, R = tBu) forming 11–14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate β-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11–14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11–14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 °C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N2/H2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 °C were utilized. With 11–14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 °C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

A primeira parte desta Tese incluiu a funcionalização em solução de polietileno linear de média densidade (LMDPE) com alil glicidil éter (AGE), na presença de peróxido de benzoíla (BPO) como iniciador de reações radicalares. A caracterização foi feita por espectroscopia no infravermelho com transformada de Fourier (FTIR) e o grau de funcionalização (GF) foi estimado por meio de duas curvas de calibração. Foi observado efeito do tipo de solvente sobre o GF. A segunda parte consistiu na funcionalização superficial por radiação ultravioleta (UV). Como monômeros foram usados AGE, anidrido maléico (MAH) e anidrido tetraidroftálico (THFAH). Como iniciadores, BPO e benzofenona (BP). A caracterização das superfícies foi realizada por medidas de ângulo de contato. THFAH apresentou a melhor performance. A terceira tratou da funcionalização por processamento reativo do LMDPE com AGE, na presença de BPO. A caracterização se deu por FTIR e o GF foi estimado conforme descrito acima. A funcionalização foi confirmada (indiretamente) por calorimetria diferencial exploratória, que evidenciou a diminuição do grau de cristalinidade com a funcionalização. Não foi possível confirmar a funcionalização por meio de análise elementar, termogravimetria e difração de raios X. A fragmentação das cadeias do LMDPE funcionalizado do ensaio 13 (e 13A) foi evidenciada por decréscimo no torque e nas propriedades mecânicas. Contudo, o índice de fluidez, surpreendentemente, diminuiu. Os valores relativamente superiores de resistência à tração e módulo de Young dos compósitos e blendas obtidos com LMDPE funcionalizado, contra os obtidos com LMDPE virgem, evidenciaram a interação favorável entre os grupos epóxidos inseridos nas cadeias do LMDPE e os grupos hidroxilas presentes no polissacarídeo. O aumento da adesão entre a matriz polimérica e as fibras de celulose foi confirmado por microscopia eletrônica de varredura e, qualitativamente, por quantidades relativamente maiores de resíduos remanescentes após extração em xileno sob refluxo. / The first part of this work included the functionalization in solution of linear medium density polyethylene (LMDPE) with allyl glycidyl ether (AGE), in the presence of benzoyl peroxide (BPO) as free radical reaction initiator. The characterization was made by Fourier transform infrared spectroscopy (FTIR) and the degree of functionalization was estimated by means of two calibration curves. The type of solvent influenced the DF. The second part comprised the surface functionalization by ultraviolet (UV) radiation. AGE, maleic anhydride (MAH) and tetrahydrophthalic anhydride (THFAH) were used as monomers and BPO and benzophenone (BP) as initiators. Contact angle measurements were used to characterize the surfaces. THFAH showed the best performance. The third part dealt with the functionalization by reactive processing of LMDPE with AGE, in the presence of BPO. FTIR was used to characterize the samples and the degree of functionalization was estimated as described above. The functionalization was (indirectly) confirmed by differential scanning calorimetry. The degree of crystallinity decreased with the functionalization. The functionalization couldn?t be confirmed by elemental analysis, thermogravimetry and X-ray diffraction. The chain scissions of the chemical modified LMDPE of trial 13 (and 13A) were evidenced by reduction of torque and mechanical properties. However, the melt flow index diminished. The favorable interaction between epoxide groups inserted on LMDPE chains and hydroxyl groups present in polysaccharide caused the increase in tensile strength and Young?s modulus values for composites and blends in relation to those obtained with virgin LMDPE. The increase in adhesion between the polymeric matrix and cellulose fibers was also confirmed by scanning electron microscopy and, qualitatively, by relatively large amounts of remaining residues after extraction in refluxing xylene.