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31.
Benedikt S. Schreib Marlene Fadel Erick M. Carreira 《Angewandte Chemie (International ed. in English)》2020,59(20):7818-7822
Palladium‐catalyzed regio‐ and diastereoselective C?H functionalization with bromoalkynes and electronically unbiased olefins is reported. The picolinamide directing group enables the formation of putative 5 and 6‐exo‐metallacycles as intermediates to afford monoalkynylated products in up to 91 % yield in a stereospecific fashion. The systematic study reveals that substrates with a wide range of substituents on the olefin and bromoalkyne coupling partners are tolerated. Chemoselective transformations were demonstrated for the obtained amides, olefins, and alkynes. 相似文献
32.
Reina MC Boese R Ge M Ulic SE Beckers H Willner H Della Védova CO 《The journal of physical chemistry. A》2008,112(34):7939-7946
Trichloromethanesulfenyl acetate, CCl 3SOC(O)CH 3, belongs to the family of sulfenic esters. This molecule has been characterized by vibrational spectroscopy. The conformational and geometrical properties of this species have been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum chemical calculations. Geometry optimizations of the most stable forms were performed with ab initio (HF, MP2) and density functional theory (B3LYP) methods. According to our data, this compound results in a gauche-syn conformer with C 1 symmetry (gauche orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the most stable geometry, and trans-syn conformer with C s symmetry (trans orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in energy than the most stable C 1 form according to the matrix FTIR spectroscopy and MP2/6-31G* level of the theory, respectively). The crystalline solid (monoclinic, P2 1/ n, a = 8.0152(17) A, b = 5.7922(13) A, c = 17.429(4) A, alpha = gamma = 90 degrees , beta = 100.341(3) degrees ) consists exclusively of the main form. The geometrical parameters (X-ray diffraction) are d C-Cl = 1.767(19) A, d C-S = 1.797(2) A, d S-O = 1.663(14) A, d CO = 1.189(2) A, d O-C = 1.389(3) A, d C-C = 1.483(3) A, angles Cl-C-Cl = 110.3(11) degrees , Cl-C-S = 111.8(12) degrees , C-S-O = 97.4(8) degrees , S-O-C = 116.7(11) degrees , O-CO = 122.8(19) degrees , OC-C = 127.1(2) degrees , and the main torsion angles are delta(CSOC) = 105.9(15) degrees and delta(SOC(O)) = 7.6(3) degrees . The geometrical data calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data. 相似文献
33.
34.
Dipl.‐Chem. Vikas Aggarwal Dipl.‐Chem. Linus F. Reichenbach Dipl.‐Chem. Mirja Enders Dr. Thierry Muller Dipl.‐Ing. Simone Wolff Marlene Crone Prof. Dr.‐Ing. Michael Türk Prof. Dr. Stefan Bräse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12794-12799
The optimized synthesis of a range of cyclooctadiene‐stabilized Pt complexes that contained different perfluoro‐alkane chains, [Pt(cod)Me(CnF2n+1)], is presented. These metal–organic compounds were employed in the so‐called supercritical fluid reactive deposition (SFRD) in CO2 under reductive conditions to generate metallic nanoparticles on aluminum oxide as a porous support. Thus, Al2O3‐supported Pt nanoparticles with a narrow particle‐size distribution were obtained. At a reduction pressure of 15.5 MPa and a temperature of 353 K, particle diameters of d50=2.3–2.8 nm were generated. Decreasing the pressure during the reduction reaction led to slightly larger particles whilst decreasing the amount of organometallic precursor in CO2 yielded a decrease in the particle size from x50=3.2 nm to 2.6 nm and a particle‐size distribution of 2.2 nm. Furthermore, substitution of the CH3 end group by the CnF2n+1 end groups led to a significant drop in Pt loading of about 50 %. Within the series of perfluorinated end groups that were considered, the Pt complex that contained a branched perfluoro‐isopropyl group showed the most‐interesting results when compared to the control precursor, [Pt(cod)Me2] ( 1 ). 相似文献
35.
Fisher Douglas B. Espidel Joussef Huerta Marlene Randall Leslie Goldman Jon 《Transport in Porous Media》1999,35(2):189-204
The purpose of this work is to present the results of the phase behavior study for a live heavy oil during a pressure depletion process using magnetic resonance imaging (MRI) as a tool to characterize foamy oil phenomena. The experiments were carried out in the pressure range of 13.1 to 1.4MPa. Signal intensity images were obtained at each pressure and with respect to time, that is, approximately for a total time of 3h after each pressure change. It is possible to see a variation in intensity across the sample. These changes can be associated with changes in mobility as well as segregation of the oil. It was also possible to observe that what we trust is the formation of gas channels at the last two pressure values, as it comes out of solution. A correlation between the transverse relaxation time T2 and temperature was established with the aim of producing one between T2 and viscosity. In this way viscosity maps for the live oil were obtained as a function of pressure and time. It was observed that above the bubble point, the viscosity maps varied from low to high to low with respect to time for the same pressure. Below the bubble point the situation is reverse. The viscosity map changes from high to low to high with respect to time for the same pressure. The study shows the potential use of MRI to follow viscosity changes during pressure depletion test in a PVT MRI cell. 相似文献
36.
Yeast cells exposed to adverse conditions employ a number of defense mechanisms in order to respond effectively to the stress effects of reactive oxygen species. In this work, the cellular response of Yarrowia lipolytica and Pichia pastoris to the exposure to the ROS-inducing agents’ paraquat, hydrogen peroxide, and increased air pressure was analyzed. Yeast cells at exponential phase were exposed for 3 h to 1 mM paraquat, to 50 mM H2O2, or to increased air pressure of 3 or 5 bar. For both strains, the cellular viability loss and lipid peroxidation was lower for the cells exposed to increased air pressure than for those exposed to chemical oxidants. The glutathione induction occurred only in Y. lipolytica strain and reached the highest level as a response to PQ exposure. In general, antioxidant enzymes were more expressed in Y. lipolytica than in P. pastoris. The enzyme superoxide dismutase was induced in both strains under all the oxidant conditions but was dependent on the cellular growth phase, being undetectable in non-growing cells, whereas glutathione reductase was more induced in those conditions. Hydrogen peroxide was the most efficient inducer of catalase. Both yeast cultures underwent no cellular growth inhibition with increased air pressure, indicating that these yeast species were able to adapt to the oxidative stressful environment. 相似文献
37.
The electromechanical properties of thin tangentially polarized, stripe-electroded piezoceramic elements are considered. Theoretical analysis is made based on a piecewise linear approximation of the actual nonuniform electric field in the volume of the stripe-electroded cylinder design. Analytical expressions are derived for the electromechanical properties (including the effective coupling coefficient) of the tangentially polarized elements as a function of the geometry and electrode configuration (i.e., electrode width and spacing). The properties of stripe-electroded cylinders are calculated and compared with the ideal case of a uniform circumferential electric field, which may be realized in practice with segmented cylinders comprised of 33-polarized bar elements. The reasons for the reduction in the effective coupling coefficient of tangentially polarized stripe-electroded cylinders compared to the ideal coupling coefficient k(33) achievable with the segmented cylinder designs are discussed. The results of calculations of the electromechanical properties are in good agreement with experimentally obtained data on a variety of samples. 相似文献
38.
Katharina Buddrus-Schiemann Martin Rieger Marlene Mühlbauer Maria Vittoria Barbarossa Christina Kuttler Burkhard A. Hense Michael Rothballer Jenny Uhl Juliano R. Fonseca Philippe Schmitt-Kopplin Michael Schmid Anton Hartmann 《Analytical and bioanalytical chemistry》2014,406(25):6373-6383
In this interdisciplinary approach, the dynamics of production and degradation of the quorum sensing signal 3-oxo-decanoylhomoserine lactone were studied for continuous cultures of Pseudomonas putida IsoF. The signal concentrations were quantified over time by use of monoclonal antibodies and ELISA. The results were verified by use of ultra-high-performance liquid chromatography. By use of a mathematical model we derived quantitative values for non-induced and induced signal production rate per cell. It is worthy of note that we found rather constant values for different rates of dilution in the chemostat, and the values seemed close to those reported for batch cultures. Thus, the quorum-sensing system in P. putida IsoF is remarkably stable under different environmental conditions. In all chemostat experiments, the signal concentration decreased strongly after a peak, because emerging lactonase activity led to a lower concentration under steady-state conditions. This lactonase activity probably is quorum sensing-regulated. The potential ecological implication of such unique regulation is discussed. 相似文献
39.
Dipl.-Ing. Sabrina D. Püschmann Philipp Frühwirt Michael Pillinger Andreas Knöchl Marlene Mikusch Dr. Judith Radebner Dr. Ana Torvisco Prof. Roland C. Fischer Prof. Norbert Moszner Prof. Dr. Georg Gescheidt Dr. Michael Haas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3338-3347
Tetraacylgermanes are known as highly efficient photoinitiators. Herein, the synthesis of mixed tetraacylgermanes 4 a – c and 6 a – e with a nonsymmetric substitution pattern is presented. Germenolates are crucial intermediates of these new synthetic protocols. The synthesized compounds show increased solubility compared with symmetrically substituted tetraacylgermanes 1 a – d . Moreover, these mixed derivatives reveal broadened n–π* absorption bands, which enhance their photoactivity. Higher absorption of these new compounds at wavelengths above 450 nm causes efficient photobleaching when using an LED emitting at 470 nm. The quantum yields are in the range of 0.15–0.57, depending on the nature of the aroyl substituents. On the basis of these properties, mixed-functionalized tetraacylgermanes serve as ideal photoinitiators in various applications, especially in those requiring high penetration depth. The synthesized compounds were characterized by elemental analysis, IR spectroscopy, NMR and CIDNP spectroscopy, UV/Vis spectroscopy, photolysis experiments, and X-ray crystallography. The CIDNP data suggest that the germyl radicals generated from the new tetraacylgermanes preferentially add to the tail of the monomer butyl acrylate. In the case of 6 a – e only the mesitoyl groups are cleaved off, whereas for 4 a – c both the mesitoyl and the aroyl group are subject to α-cleavage. 相似文献
40.
Lipid nanotube formation from streptavidin-membrane binding 总被引:1,自引:0,他引:1
Liu H Bachand GD Kim H Hayden CC Abate EA Sasaki DY 《Langmuir : the ACS journal of surfaces and colloids》2008,24(8):3686-3689
A novel transformation of giant lipid vesicles to produce nanotubular structures was observed upon the binding of streptavidin to biotinylated membranes. Unlike membrane budding and tubulation processes caused by proteins involved with endocytosis and vesicle fusion, streptavidin is known to crystallize at near the isoelectric point (pI 5 to 6) into planar sheets against biotinylated films. We have found, however, that at neutral pH membranes of low bending rigidity (<10kT), such as 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), spontaneously produce tubular structures with widths ranging from micrometers to below the diffraction limit (<250 nm) and lengths spanning up to hundreds of micrometers. The nanotubes were typically held taut between surface-bound vesicles suggesting high membrane tension, yet the lipid nanotubes exhibited a fluidic nature that enabled the transport of entrained vesicles. Confocal microscopy confirmed the uniform coating of streptavidin over the vesicles and nanotubes. Giant vesicles composed of lipid membranes of higher bending energy exhibited only aggregation in the presence of streptavidin. Routes toward the development of these highly curved membrane structures are discussed in terms of general protein-membrane interactions. 相似文献