@article {TPJ:TPJ13294, title = {The composition of surface wax on trichomes of Arabidopsis thaliana differs from wax on other epidermal cells}, journal = {The Plant Journal}, year = {2016}, pages = {n/a{\textendash}n/a}, keywords = {Arabidopsis thaliana, cuticle, Epidermis, HYDROCARBONS, Pavement cells, trichomes, wax}, issn = {1365-313X}, doi = {10.1111/tpj.13294}, url = {http://dx.doi.org/10.1111/tpj.13294}, author = {Hegebarth, Daniela and Buschhaus, Christopher and Wu, May and Bird, David and Jetter, Reinhard} } @article {Rueda-Becerril2012, title = {Fluorine transfer to alkyl radicals.}, journal = {J. Am. Chem. Soc.}, volume = {134}, number = {9}, year = {2012}, month = {mar}, pages = {4026{\textendash}9}, abstract = {The development of new synthetic technologies for the selective fluorination of organic compounds has increased with the escalating importance of fluorine-containing pharmaceuticals. Traditional methods potentially applicable to drug synthesis rely on the use of ionic forms of fluorine (F(-) or F(+)). Radical methods, while potentially attractive as a complementary approach, are hindered by a paucity of safe sources of atomic fluorine (F({\textbullet})). A new approach to alkyl fluorination has been developed that utilizes the reagent N-fluorobenzenesulfonimide as a fluorine transfer agent to alkyl radicals. This approach is successful for a broad range of alkyl radicals, including primary, secondary, tertiary, benzylic, and heteroatom-stabilized radicals. Furthermore, calculations reveal that fluorine-containing ionic reagents are likely candidates for further expansion of this approach to polar reaction media. The use of these reagents in alkyl radical fluorination has the potential to enable powerful new transformations that otherwise would take multiple synthetic steps.}, keywords = {Fluorinated, Fluorinated: chemical synthesis, Fluorinated: chemistry, FLUORINE, Fluorine: chemistry, Free Radicals, Free Radicals: chemical synthesis, Free Radicals: chemistry, HYDROCARBONS, models, MOLECULAR, molecular structure, quantum theory}, issn = {1520-5126}, doi = {10.1021/ja211679v}, url = {http://www.ncbi.nlm.nih.gov/pubmed/22320293}, author = {Rueda-Becerril, Montserrat and Sazepin, Claire Chatalova and Leung, Joe Cho Tak and Okbinoglu, Tulin and Kennepohl, Pierre and Paquin, Jean-Fran{\c c}ois and Sammis, Glenn M} } @article {ISI:000270186500047, title = {Influence of oxygenation on the reactivity of ruthenium-thiolato bonds in arene anticancer complexes: insights from XAS and DFT.}, journal = {J. Am. Chem. Soc.}, volume = {131}, number = {37}, year = {2009}, month = {sep}, pages = {13355{\textendash}61}, publisher = {American Chemical Society}, abstract = {Thiolate ligand oxygenation is believed to activate cytotoxic half-sandwich [(eta(6)-arene)Ru(en)(SR)](+) complexes toward DNA binding. We have made detailed comparisons of the nature of the Ru-S bond in the parent thiolato complexes and mono- (sulfenato) and bis- (sulfinato) oxygenated species including the influence of substituents on the sulfur and arene. Sulfur K-edge XAS indicates that S(3p) donation into the Ru(4d) manifold depends strongly on the oxidation state of the sulfur atom, whereas Ru K-edge data suggest little change at the metal center. DFT results are in agreement with the experimental data and allow a more detailed analysis of the electronic contributions to the Ru-S bond. Overall, the total ligand charge donation to the metal center remains essentially unchanged upon ligand oxygenation, but the origin of the donation differs markedly. In sulfenato complexes, the terminal oxo group makes a large contribution to charge donation and even small electronic changes in the thiolato complexes are amplified upon ligand oxygenation, an observation which carries direct implications for the biological activity of this family of complexes. Details of Ru-S bonding in the mono-oxygenated complexes suggest that these should be most susceptible to ligand exchange, yet only if protonation of the terminal oxo group can occur. The potential consequences of these results for biological activation are discussed.}, keywords = {Antineoplastic Agents, Antineoplastic Agents: chemical synthesis, Antineoplastic Agents: chemistry, Antineoplastic Agents: metabolism, AROMATIC, Aromatic: chemistry, DFT, DNA, DNA: metabolism, Drug Design, ELECTRONS, HYDROCARBONS, LIGANDS, metal-based drugs, models, MOLECULAR, Molecular Conformation, ORGANOMETALLIC COMPOUNDS, Organometallic Compounds: chemical synthesis, Organometallic Compounds: chemistry, Organometallic Compounds: metabolism, OXYGEN, Oxygen: chemistry, quantum theory, ruthenium, Ruthenium: chemistry, Spectrum Analysis, Sulfhydryl Compounds, Sulfhydryl Compounds: chemistry, X-Rays, XAS}, issn = {1520-5126}, doi = {10.1021/ja903405z}, url = {http://www.ncbi.nlm.nih.gov/pubmed/19719101 http://dx.doi.org/10.1021/ja903405z}, author = {Sriskandakumar, Thamayanthy and Petzold, Holm and Bruijnincx, Pieter C A and Habtemariam, Abraha and Sadler, Peter J and Kennepohl, Pierre} } @article {2113, title = {Plant surface lipid biosynthetic pathways and their utility for metabolic engineering of waxes and hydrocarbon biofuels}, journal = {Plant Journal}, volume = {54}, number = {4}, year = {2008}, note = {ISI Document Delivery No.: 299KRTimes Cited: 12Cited Reference Count: 122Jetter, Reinhard Kunst, Ljerka}, month = {May}, pages = {670-683}, type = {Review}, abstract = {Due to their unique physical properties, waxes are high-value materials that are used in a variety of industrial applications. They are generated by chemical synthesis, extracted from fossil sources, or harvested from a small number of plant and animal species. As a result, the diversity of chemical structures in commercial waxes is low and so are their yields. These limitations can be overcome by engineering of wax biosynthetic pathways in the seeds of high-yielding oil crops to produce designer waxes for specific industrial end uses. In this review, we first summarize the current knowledge regarding the genes and enzymes generating the chemical diversity of cuticular waxes that accumulate at the surfaces of primary plant organs. We then consider the potential of cuticle biosynthetic genes for biotechnological wax production, focusing on selected examples of wax ester chain lengths and isomers. Finally, we discuss the genes/enzymes of cuticular alkane biosynthesis and their potential in future metabolic engineering of plants for the production of renewable hydrocarbon fuels.}, keywords = {ARABIDOPSIS-THALIANA, BRASSICA-OLERACEA, chain lengths, CONDENSING ENZYME, CUTICULAR WAX, cuticular waxes, ECERIFERUM MUTANTS, EPICUTICULAR WAX, ESTERS, fatty acid elongation, FATTY ACYL-COENZYME, HYDROCARBONS, industrial products, LEAVES PISUM-SATIVUM, MOLECULAR CHARACTERIZATION, SACCHAROMYCES-CEREVISIAE}, isbn = {0960-7412}, url = {://000255755000012}, author = {Jetter, R. and Kunst, L.} } @article {ISI:000251974000023, title = {An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands.}, journal = {J. Am. Chem. Soc.}, volume = {129}, number = {51}, year = {2007}, month = {dec}, pages = {15774{\textendash}6}, chapter = {15774}, abstract = {Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.}, keywords = {ALKENES, Alkenes: chemistry, BOND, carbenes, CATALYSTS, CL, DFT, ELECTRONS, Heterocyclic Compounds, Heterocyclic Compounds: chemistry, HYDROCARBONS, Hydrocarbons: chemistry, KINETICS, LIGANDS, MECHANISM, METHANE, Methane: analogs \& derivatives, Methane: chemistry, MOIETY, NHC LIGANDS, OLEFIN METATHESIS, phosphines, Phosphines: chemistry, RAY-ABSORPTION SPECTROSCOPY, ruthenium, Ruthenium: chemistry, TRANSITION-METAL-COMPLEXES, XAS}, isbn = {0002-7863}, issn = {1520-5126}, doi = {10.1021/ja0747674}, url = {://000251974000023 http://www.ncbi.nlm.nih.gov/pubmed/18047332}, author = {Getty, Kendra and Delgado-Jaime, Mario Ulises and Kennepohl, Pierre} } @article {766, title = {No "delayed" muonium-formation in organic liquids}, journal = {Journal of Chemical Physics}, volume = {118}, number = {7}, year = {2003}, note = {ISI Document Delivery No.: 640RVTimes Cited: 4Cited Reference Count: 19}, month = {Feb}, pages = {3233-3236}, type = {Article}, abstract = {Studies of the yields of muonium atoms and diamagnetic-species in hexane in the presence of added scavengers have shown, unequivocally, that muonium is not formed by the "delayed" (microsecond) mechanism proposed recently. Instead, the lifetimes evaluated show that if the combination reaction of mu(+)+e(-){\textendash}>Mu contributes to muonium formation in "chemically active" liquids, then it is complete within <10(-10) s. In fact the results are consistent only with the "hot" model, in which the initial distribution of muons between muonium atoms and diamagnetic molecules is determined at the epithermal level, as the last step of the muon{\textquoteright}s charge-exchangecycles and thermalization. (C) 2003 American Institute of Physics.}, keywords = {ELECTRONS, HYDROCARBONS}, isbn = {0021-9606}, url = {://000180702500029}, author = {Walker, D. C. and Karolczak, S. and Porter, G. B. and Gillis, H. A.} } @article {537, title = {Parallel modes of C-H bond activation initiated by Cp*Mo(NO)(CH2CMe3)(C6H5) at ambient temperatures}, journal = {Journal of the American Chemical Society}, volume = {124}, number = {33}, year = {2002}, note = {ISI Document Delivery No.: 584EVTimes Cited: 15Cited Reference Count: 32}, month = {Aug}, pages = {9680-9681}, type = {Article}, keywords = {ALKANES, ARYNE COMPLEXES, CHEMISTRY, HYDROCARBONS, INTERMEDIATE, METAL-COMPLEXES, MOLYBDENUM, REACTIVITY, THERMOLYSIS, TUNGSTEN ALKYLIDENE COMPLEXES}, isbn = {0002-7863}, url = {://000177455000012}, author = {Wada, K. and Pamplin, C. B. and Legzdins,Peter} } @article {4138, title = {Optical detection of yttrium dicarbide, a {\textquoteright}{\textquoteright}T-shaped{\textquoteright}{\textquoteright} molecule}, journal = {Journal of Chemical Physics}, volume = {106}, number = {6}, year = {1997}, note = {ISI Document Delivery No.: WG307Times Cited: 13Cited Reference Count: 28}, month = {Feb}, pages = {2060-2066}, type = {Article}, abstract = {The yttrium dicarbide molecule, YC2, has been identified in the reactions of laser-ablated yttrium with methane and other small hydrocarbons under supersonic jet-cooled expansion conditions. A parallel-polarized electronic band system with origin at 12889.5 cm(-1) has been tentatively identified as an A(1)-<(X)over tilde (2)A(1)> transition of a {\textquoteright}{\textquoteright}T-shaped{\textquoteright}{\textquoteright} isomer where the Y atom is bonded to the side of a C-2 molecule. Weak vibronically induced perpendicular bands, representing Delta upsilon(3)=odd transitions, are also present. Extensive vibrational progressions in the excitation and the resolved fluorescence spectra have been analyzed to give the two lowest vibrational frequencies of the two electronic states: (X) over tilde (2)A(1), nu(2) (a(1))=561.1(+/-2.8 cm(-1)), nu(3) (b(2))=369.6 (+/-1.7 cm(-1)); excited A(1), nu(2)=494.5(+/-5.0 cm(-1)), nu(3)=331.6(+/-2.2 cm(-1)). No bands involving the C-C stretching vibration (nu(1),a(1)) have been found. The frequency of the vibration in the ground state indicates that the barrier to internal rotation of the C-2 group against the Y atom is quite high, but large anharmonic coupling between the nu(2) and nu(3) vibrations suggests that internal rotation is facilitated by excitation of the Y-C-2 stretohing vibration. (C) 1997 American lnstitute of Physics.}, keywords = {ACTIVATION, C-C BONDS, CLUSTERS, HYDROCARBONS, JET-COOLED SIC2, SPECTROSCOPY, TRANSITION-METAL ATOMS, YC2}, isbn = {0021-9606}, url = {://A1997WG30700002}, author = {Steimle, T. C. and Marr, A. J. and Xin, J. and Merer, A. J. and Athanassenas, K. and Gillet, D.} } @article {3744, title = {Microbial degradation of pyrene and characterization of a metabolite}, journal = {Science of the Total Environment}, volume = {177}, year = {1996}, note = {ISI Document Delivery No.: TP870Times Cited: 10Cited Reference Count: 37}, month = {Jan}, pages = {17-29}, type = {Article}, abstract = {We report the degradation of pyrene by microorganisms present in sea water and sediment samples that were obtained from Kitimat Arm, BC, Canada, an environment that is highly contaminated by polycyclic aromatic hydrocarbons because of nearby aluminum smelting activity. The utilization of pyrene as sole carbon source by the microorganisms is demonstrated by monitoring the disappearance of pyrene and the production of its metabolite in the cultures. Pyrene (10 mu g) is degraded to an undetectable level after 120 h of incubation with 0.5 mi of the enriched culture and 10 ml of mineral salt medium. The extent of mineralization is also assessed by determining the radioactivity of the (CO2)-C-14 produced from the cultures containing C-14-labeled pyrene: up to 65\% of the pyrene is mineralized after 12 days of incubation. A metabolite that accumulates in the pyrene degradation cultures can be isolated. This metabolite is identified as cis-dihydrodiol pyrene, an initial ring oxidation product, on the basis of its chromatographic behavior, absorption spectrum, fluorescence excitation and emission spectra, and mass spectra.}, keywords = {BACTERIAL, BIODEGRADATION, bioremediation, cis-dihydrodiol pyrene, CONTAMINATED SOIL, HYDROCARBONS, METABOLITE, microbial degradation, MINERALIZATION, MYCOBACTERIUM SP, NAPHTHALENE, OXIDATION, PHENANTHRENE, polycyclic aromatic, POLYCYCLIC AROMATIC-HYDROCARBONS, PYRENE, SEDIMENT}, isbn = {0048-9697}, url = {://A1996TP87000003}, author = {Li, X. F. and Cullen, W. R. and Reimer, K. J. and Le, X. C.} } @article {7041, title = {EPITHERMAL MUONIUM PROCESSES IN METHANE AND PROPANE GASES}, journal = {Journal of Physical Chemistry}, volume = {95}, number = {19}, year = {1991}, note = {ISI Document Delivery No.: GG383Times Cited: 7Cited Reference Count: 90}, month = {Sep}, pages = {7338-7344}, type = {Article}, abstract = {Gas-phase mu-SR studies of dense methane up to 10 mol L-1 and of propane at low densities, up to 0.2 mol L-1, are reported. It is found that the diamagnetic polarization, P(D), increases in both gases with pressure, with a related decrease seen in the muonium polarization, P(Mu). The initial increase seen in P(D) at low densities is attributed to hot-atom (Mu*) abstraction and substitution reactions. Comparisons with both hot-tritium (T*) and epithermal H* reactions in the alkanes reveal substantial isotope effects. In the case of CH4, a continued increase in P(D) at higher densities is likely due to a proton-transfer reaction from the molecular ion CH4Mu+ in the radiolysis track, forming CH3Mu, rather than to hot-atom reactions. Extrapolation of the present trend with density gives agreement with the value of P(D) found in liquid CH4, indicating that the diamagnetic muon polarization in dense alkanes depends primarily on density rather than on temperature or phase.}, keywords = {CHARGE-EXCHANGE, CHEMISTRY, HOT-ATOM REACTIONS, HYDROCARBONS, HYDROGEN-ATOMS, LIQUIDS, POSITRONIUM, REACTION PROBABILITIES, THRESHOLD ENERGY, time}, isbn = {0022-3654}, url = {://A1991GG38300043}, author = {Kempton, J. R. and Arseneau, D. J. and Fleming, Donald G. and Senba, M. and Gonzalez, A. C. and Pan, J. J. and Tempelmann, A. and Garner, D. M.} }