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31.
Stahl SS 《Science (New York, N.Y.)》2005,309(5742):1824-1826
32.
Aromatic molecules are key constituents of many pharmaceuticals, electronic materials, and commodity plastics. The utility of these molecules directly reflects the identity and pattern of substituents on the aromatic ring. Here, we report a palladium(II) catalyst system, incorporating an unconventional ortho-dimethylaminopyridine ligand, for the conversion of substituted cyclohexanones to the corresponding phenols. The reaction proceeds via successive dehydrogenation of two saturated carbon-carbon bonds of the six-membered ring and uses molecular oxygen as the hydrogen acceptor. This reactivity demonstrates a versatile and efficient strategy for the synthesis of substituted aromatic molecules with fundamentally different selectivity constraints from the numerous known synthetic methods that rely on substitution of a preexisting aromatic ring. 相似文献
33.
Shannon RR Ceccon C Smith WS Metheny W Philbrick R 《Science (New York, N.Y.)》1979,206(4424):1267-1272
An experiment has been performed to measure directly the effect of atmospheric turbulence on spherical wave propagation of light on a vertical path. The results permit determination of the magnitude of the effect at a variety of locations and under different conditions. Agreement is found with the functional form predicted by the inertial theory of turbulence. General agreement is found with scattering data obtained by a low-frequency radar and with predictions of some turbulence profile models. The results also demonstrate some reasons for poor agreement with time integrating sensors. 相似文献
34.
Phototropins are light-activated kinases important for plant responses to blue light. Light initiates signaling in these proteins by generating a covalent protein-flavin mononucleotide (FMN) adduct within sensory Per-ARNT-Sim (PAS) domains. We characterized the light-dependent changes of a phototropin PAS domain by solution nuclear magnetic resonance spectroscopy and found that an alpha helix located outside the canonical domain plays a key role in this activation process. Although this helix associates with the PAS core in the dark, photoinduced changes in the domain structure disrupt this interaction. We propose that this mechanism couples light-dependent bond formation to kinase activation and identifies a signaling pathway conserved among PAS domains. 相似文献
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McBride JM Segmuller BE Hollingsworth MD Mills DE Weber BA 《Science (New York, N.Y.)》1986,234(4778):830-835
Organic single crystals provide an ideal model for studying the factors that influence chemical processes in structured media. Reaction trajectories are well defined and reveal the influence of spontaneous mechanical stresses equivalent to tens of thousands of atmospheres. Analysis of molecular and crystal structures helps to explain both local mechanical properties, which influence reactions, and bulk properties such as melting point, compressibility, and surface energy. 相似文献
38.
The herbicide bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) is a photosynthetic (photosystem II) inhibitor in plants. A gene, bxn, encoding a specific nitrilase that converts bromoxynil to its primary metabolite 3,5-dibromo-4-hydroxybenzoic acid, was cloned from the natural soil bacterium Klebsiella ozaenae. For expression in plants, the bxn gene was placed under control of a light-regulated tissue-specific promoter, the ribulose bisphosphate carboxylase small subunit. Transfer of this chimeric gene and expression of a bromoxynil-specific nitrilase in leaves of transgenic tobacco plants conferred resistance to high levels of a commercial formulation of bromoxynil. The results presented indicate a successful approach to obtain herbicide resistance by introducing a novel catabolic detoxification gene in plants. 相似文献
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Significant increases in pulping efficiency in C4H-F5H-transformed poplars: improved chemical savings and reduced environmental toxins 总被引:14,自引:0,他引:14
Huntley SK Ellis D Gilbert M Chapple C Mansfield SD 《Journal of agricultural and food chemistry》2003,51(21):6178-6183
The gene encoding ferulate 5-hydroxylase (F5H) was overexpressed in poplar (Populus tremula x Populus alba) using the cinnamate-4-hydroxylase (C4H) promoter to drive expression specifically in cells involved in the lignin biosynthetic pathway and was shown to significantly alter the mole percentage of syringyl subunits in the lignin, as determined by thioacidolysis. Analysis of poplar transformed with a C4H-F5H construct demonstrated significant increases in chemical (kraft) pulping efficiency from greenhouse-grown trees. Compared to wild-type wood, decreases of 23 kappa units and increases of >20 ISO brightness units were observed in trees exhibiting high syringyl monomer concentrations. These changes were associated with no significant modification in total lignin content and no observed phenotypic differences. C4H-F5H-transformed trees could increase pulp throughputs at mills by >60% while concurrently decreasing chemicals employed during processing (chemical pulping and bleaching) and, consequently, the amount of deleterious byproducts released into the environment. 相似文献