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881.
Theresa Julia Zielinski Masayuki Shibata Robert Rein 《International journal of quantum chemistry》1981,19(1):171-177
Ab initio STO -3G geometries and relative energies for uracil (U) and the tautomer 4-hydroxyuracil (U*) were obtained with the HONDO program utilizing the rapidly convergent method of Murtaugh and Sargent for geometry optimization. ΔE for U?U* is 6.61 kcal/mole. The reaction field continuum model for solvent effect indicates a preferential stabilization of U* by 1.0 kcal/mole. The calculated gas phase Kt and solution Kt for U?U* are 1.44×10?5 and 1.3×10?4, respectively. 相似文献
882.
Dissolved uranium is selectively removed from 11 of filtered, acidified water using a liquid anion exchange resin (Amberlite LA-1) dissolved in 10 ml of purified kerosene. The organic phase is then analyzed by a standard delayed neutron counting technique. Yields of removed uranium are consistently greater than 90 percent over a measured concentration range of 1.0 to 100 ppb uranium. The absolute detection limit based on 11 of water is 0.06 ppb. Elemental interferences are minimal and the results compare favorably with fluorometric analyses of natural waters. 相似文献
883.
Temporal control over supramolecular systems has great potential for the modulation of binding and assembly events, such as providing orthogonal control over protein activity. Especially light controlled triggering provides unique entries for supramolecular systems to interface in a controlled manner with enzymes. Here we report on the light-induced release of cucurbit[8]uril (CB[8]) from a bivalent cage molecule and its subsequent activation of a proteolytic enzyme, caspase-9, that itself is unresponsive to light. Central to the design is the bivalent binding of the cage with high affinity to CB[8], 100-fold stronger than the UV-inactivated products. The affinity switching occurs in the (sub-)micromolar concentration regime, matching the concentration characteristics required for dimerizing and activating caspase-9 by CB[8]. The light-responsive caged CB[8] concept presented offers a novel platform for tuning and application of switchable cucurbiturils and beyond.Photo-switchable supramolecular systems offer unique entries to control biomolecular process, as illustrated via the light-induced release of cucurbit[8]uril from a bivalent cage molecule and its subsequent activation of the caspase-9 enzyme. 相似文献
884.
885.
Tim Austin 《Israel Journal of Mathematics》2016,211(1):221-238
Let (X, d) be a compact metric space and µ a Borel probability on X. For each N ≥ 1 let d∞N be the ?∞-product on XN of copies of d, and consider 1-Lipschitz functions XN → ? for d∞N. 相似文献
886.
Joseph Zielinski 《Mathematical Logic Quarterly》2016,62(6):547-551
We observe that there is an example of an automorphism group of a model of an ω‐stable theory—in fact, the prime model of an uncountably categorical theory—that is not locally (OB), answering a question of Rosendal. 相似文献
887.
Tim Plath Philipp Amstutz Jörn Bödewadt Günter Brenner Nagitha Ekanayake Bart Faatz Kirsten Hacker Katja Honkavaara Leslie Lamberto Lazzarino Christoph Lechner Theophilos Maltezopoulos Matthias Scholz Siegfried Schreiber Mathias Vogt Johann Zemella Tim Laarmann 《Journal of synchrotron radiation》2016,23(5):1070-1075
Free‐electron lasers (FELs) generate femtosecond XUV and X‐ray pulses at peak powers in the gigawatt range. The FEL user facility FLASH at DESY (Hamburg, Germany) is driven by a superconducting linear accelerator with up to 8000 pulses per second. Since 2014, two parallel undulator beamlines, FLASH1 and FLASH2, have been in operation. In addition to the main undulator, the FLASH1 beamline is equipped with an undulator section, sFLASH, dedicated to research and development of fully coherent extreme ultraviolet photon pulses using external seed lasers. In this contribution, the first simultaneous lasing of the three FELs at 13.4 nm, 20 nm and 38.8 nm is presented. 相似文献
888.
Mirror‐Image Packing Provides a Molecular Basis for the Nanomolar Equipotency of Enantiomers of an Experimental Herbicide
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Dr. Claudine Bisson Dr. K. Linda Britton Dr. Svetlana E. Sedelnikova H. Fiona Rodgers Dr. Thomas C. Eadsforth Dr. Russell C. Viner Dr. Tim R. Hawkes Dr. Patrick J. Baker Prof. David W. Rice 《Angewandte Chemie (International ed. in English)》2016,55(43):13485-13489
Programs of drug discovery generally exploit one enantiomer of a chiral compound for lead development following the principle that enantiomer recognition is central to biological specificity. However, chiral promiscuity has been identified for a number of enzyme families, which have shown that mirror‐image packing can enable opposite enantiomers to be accommodated in an enzyme's active site. Reported here is a series of crystallographic studies of complexes between an enzyme and a potent experimental herbicide whose chiral center forms an essential part of the inhibitor pharmacophore. Initial studies with a racemate at 1.85 Å resolution failed to identify the chirality of the bound inhibitor, however, by extending the resolution to 1.1 Å and by analyzing high‐resolution complexes with the enantiopure compounds, we determined that both enantiomers make equivalent pseudosymmetric interactions in the active site, thus mimicking an achiral reaction intermediate. 相似文献
889.
Spectroscopic Monitoring of Mechanical Forces during Protein Folding by using Molecular Force Probes
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Detailed folding pathways of proteins are still largely unknown. Real‐time monitoring of mechanical forces acting in proteins during structural transitions would provide deep insights into these highly complex processes. Here, we propose two molecular force probes that can be incorporated into the protein backbone to gain insight into the magnitude and direction of mechanical forces acting in proteins during natural folding and unfolding through their optical spectroscopic response. In fact, changes in the infrared and Raman spectra are proportional to the mechanical force deforming the force probes, and the relevant bands can be intensified and shifted to a transparent window in the protein spectrum by isotopic substitution. As a result, the proposed molecular force probes can act as “force rulers”, allowing the spectroscopic observation and measurement of mechanical forces acting within the proteins under natural conditions without external perturbation. 相似文献
890.
Jeremias Schuermann Tim Huber Deborah LeCorre Gérard Mortha Mathieu Sellier Benoît Duchemin Mark P. Staiger 《Cellulose (London, England)》2016,23(2):1043-1050
Four sources of cellulose with different molecular weights were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate at 100 °C over a 10 h period. The solution densities were determined and these results were subsequently utilised to access the influence of dissolved cellulose on surface tension properties of cellulose/ionic liquid solutions. Surface tension measurements revealed increasing molecular weight and concentration reduced surface tension while temperature increases showed the opposite effect. These results are consistent with that of repulsive polymer-wall interactions near the interface in good solvent conditions. The semi-flexible nature of this carbohydrate in solution can help explain deviations of these results when compared to ideal flexible chains. 相似文献