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21.
Small molecule receptor-binding is dominated by weak, non-covalent interactions such as van-der-Waals hydrogen bonding or electrostatics. Calculating these non-covalent ligand-receptor interactions is a challenge to computational means in terms of accuracy and efficacy since the ligand may bind in a number of thermally accessible conformations. The conformational rotamer ensemble sampling tool (CREST) uses an iterative scheme to efficiently sample the conformational space and calculates energies using the semi-empirical ‘Geometry, Frequency, Noncovalent, eXtended Tight Binding’ (GFN2-xTB) method. This combined approach is applied to blind predictions of the modes and free energies of binding for a set of 10 drug molecule ligands to the cucurbit[n]urils CB[8] receptor from the recent ‘Statistical Assessment of the Modeling of Proteins and Ligands’ (SAMPL) challenge including morphine, hydromorphine, cocaine, fentanyl, and ketamine. For each system, the conformational space was sufficiently sampled for the free ligand and the ligand-receptor complexes using the quantum chemical Hamiltonian. A multitude of structures makes up the final conformer-rotamer ensemble, for which then free energies of binding are calculated. For those large and complex molecules, the results are in good agreement with experimental values with a mean error of 3 kcal/mol. The GFN2-xTB energies of binding are validated by advanced density functional theory calculations and found to be in good agreement. The efficacy of the automated QM sampling workflow allows the extension towards other complex molecular interaction scenarios. 相似文献
22.
The fracture strength of HF-etched samples was measured as a function of field-assisted K-Na ion exchange depth, as well as the severity of abrasion. As expected, the more severe the abrasion, the greater the depth required to make the strength insensitive to abrasion. An abrasion-independent weakening mechanism that increased with exchange depth was also found to be operative. 相似文献
23.
Karin Yaccato Alfred Hagemeyer Andreas Lesik Anthony Volpe Henry Weinberg 《Topics in Catalysis》2004,(1):127-132
High-throughput synthesis and screening methods have been developed for the discovery of highly active lead compounds for the selective catalytic reduction as well as direct decomposition of NO in the temperature range 200–300 °C. The discovery libraries for primary screening consisted of 16 × 16 catalyst arrays on 4in. square quartz wafers. Catalysts were prepared by robotic liquid dispensing techniques and screened for catalytic activity in Symyx' scanning mass spectrometer. The scanning mass spectrometer is a fast serial screening tool that uses flat wafer catalyst surfaces, local laser heating, a scanning/sniffing nozzle and a quadrupolar mass spectrometer to compare relative catalytic activities. The feed consisted of NO/NH3 mixtures with optional O2 cofeed and Kr as the internal standard in Ar carrier gas. QMS detection allowed for tracking of H2O, N2, NO, O2, N2O and Kr. Screening protocols for catalytic materials encompassed metal precursors and carriers for supported vanadia systems, extensive doping of V2O5/TiO2, and broad screening of mixed redox metal oxides and supported base and noble metal systems. More than 500 samples could be screened in a single day. Active hits (high NO consumption accompanied by corresponding N2 production) identified in discovery libraries were re-synthesized as focus libraries for lead confirmation and further optimization. These libraries used shallower compositional gradients, for example 56 points (compositions) per ternary, with four 56-point ternaries per 4in. wafer. Broad screening ternaries were generally 8 or 15 points. The focus libraries more clearly reveal the trends and provide guidelines for secondary screening and scale-up. High conversions were achieved in scanning mass spectrometer so the scalability risk is small for the short contact time reactions. 相似文献
24.
Zvi Mendel Lev Zegelman Alfred Hassner Fabienne Assael Miriam Harel Shlomo Tam Ezra Dunkelblum 《Journal of chemical ecology》1995,21(3):331-341
The active component of the sex pheromone ofMatsucoccus josephi is (2E,6E,8E)-5,7-dimethyl-2,6,8-decatrien-4-one; the chemical is also a powerful kairomone of adult males and females of the bugElatophilus hebraicus the principal predator ofM. josephi. The presence of theZ isomer (2E,6Z,8E)-5,7-dimethyl-2,6,8-decatrien-4-one does not interfere with the attractancy of the activeE component forM. josephi males or the bug. Our results show a clear dose-response between trap catch ofM. josephi males andE. hebraicus. Conversely, increasing amounts of theZ isomer in the mixture did not affect the attraction of the scale insect males or the bug. The catch ofM. josephi males did not differ significantly among traps of different color, and was significantly higher with traps attached to the tree trunk than those suspended between trees. Comparison of the catch ofM. josephi among the three forests and between pine species suggests that the level of infestation ofPinus halepepsis andPinus brutia ssp.brutia is similar, despite the fact that the latter pine is resistant to the scale insect. Both sexes ofE. hebraicus were trapped in much lower numbers at the more infested sites. This may be related to interference with the activity ofE. hebraicus due to deterioration and drying of parts of the tree crowns and heavy colonization by generalist predators in injured trees. 相似文献
25.
The reaction of H atoms (produced by nanosecond pulse radiolysis) with ferri-cytochrome-c in aqueous solution results in the second order formation of an absorption spectrum due to the addition of H atoms to the enzyme protein. This spectrum is not specific to the iron moiety. The rate constant of the addition is 1×1010M?1 sec?1. This is followed by two first order intramolecular processes with specific rates of ~ 1×105 sec?1 and ~ 2×104 sec?1. In these processes, specific spectra related to the α and β bands of ferro-cytochrome-c appear. The results are interpreted to show reduction equivalent transfer through the protein to the iron moiety. 相似文献
26.
W. Stein H. Weiß O. Koch P. Neuhausen H. Baumann 《European Journal of Lipid Science and Technology》1970,72(11):956-959
Preparation of Esters of α-Sulfo-Fatty Acids A process for the continuous α-sulfonation of saturated fatty acid esters with SO3 was worked out and a special bleaching process was developed for these products. The conversion, i. e. the degree of sulfonation is of the order of 95–99%. Solvents, further processing steps or purification operations for the separation of by-products are not required. 相似文献
27.
Various reactions occur between pyrite (FeS2) in coal and CaO to form CaS when a finely pulverized intimate mixture of coal and CaO is coked at 900 °C in an inert atmosphere. The effectiveness of lime and calcined dolomite (CaO.MgO) in promoting this reaction has been evaluated; calcined dolomite is somewhat more effective than lime over coal/ oxide weight ratios from 2.8 to 14. The degree of conversion of pyrite to calcium sulphide at a coal/calcined dolomite weight ratio of 7 has been determined as a function of time at 900 °C; coking time in excess of 2.5 h does not have a significant effect. It has been shown that the total sulphur lost on coking coal/lime mixtures decreases and the percentage of FeS, originating from the dissociation of pyrite, converted to CaS increases as the amount of lime added increases. But although the total sulphur content of coke produced in the presence of CaO is then higher than when the coal is coked without lime, the pyritic sulphur has been converted to CaS which is more amenable to chemical conversion to H2S. A method is outlined for determining CaS in the coked mixture in the presence of FeS. 相似文献
28.
29.
Alfred Hermida Seth C. Lewis Rodrigo Zamith 《Journal of Computer-Mediated Communication》2014,19(3):479-499
News sourcing practices are critical as they shape from whom journalists get their information and what information they obtain, mostly from elite sources. This study evaluates whether social media platforms expand the range of actors involved in the news through a quantitative content analysis of the sources cited by NPR's Andy Carvin on Twitter during the Arab Spring. Results show that, on balance, nonelite sources had a greater representation in the content than elite sources. Alternative actors accounted for nearly half of the messages. The study points to the innovative forms of production that can emerge with new communication technologies, with the journalist as a central node trusted to authenticate and interpret news flows on social awareness streams. 相似文献
30.
In principle, the oil milling process is straightforward. The wide variety of equipment in use reflects, however, a multiparametric
process. The main limiting parameters are kind of seed, oil content, particle strength, particle structure, temperature, moisture,
particle size, residence time, mechanical forces, etc. Additionally, the seed specific parameters vary not only between kinds
of seed but also for the same seed, due to different conditions in climate, soil, and harvesting. Therefore, equipment design
must be widely based on statistical averages of the limiting parameters. In other words, exact precalculation of the single
technological steps is impossible. As a consequence, for more than 5,000 years, the oil milling process has been in the stage
of being optimized. The acutal technical standard is very satisfying, but there is still a strong need for further research
and development. Currently, as in the past, the oil milling process seems to be not so much a science as an art. 相似文献