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21.
Bing-Yu Li Lauren Voets Ruben Van Lommel Fien Hoppenbrouwers Mercedes Alonso Steven H. L. Verhelst Wim M. De Borggraeve Joachim Demaerel 《Chemical science》2022,13(8):2270
Sulfur(vi) Fluoride Exchange (SuFEx) chemistry has emerged as a next-generation click reaction, designed to assemble functional molecules quickly and modularly. Here, we report the ex situ generation of trifluoromethanesulfonyl fluoride (CF3SO2F) gas in a two chamber system, and its use as a new SuFEx handle to efficiently synthesize triflates and triflamides. This broadly tolerated protocol lends itself to peptide modification or to telescoping into coupling reactions. Moreover, redesigning the SVI–F connector with a S O → S NR replacement furnished the analogous triflimidoyl fluorides as SuFEx electrophiles, which were engaged in the synthesis of rarely reported triflimidate esters. Notably, experiments showed H2O to be the key towards achieving chemoselective trifluoromethanesulfonation of phenols vs. amine groups, a phenomenon best explained—using ab initio metadynamics simulations—by a hydrogen bonded termolecular transition state for the CF3SO2F triflylation of amines.Triflyl fluoride gas (CF3SO2F) and its aza analogues are reported as new SuFEx activators. These SVI–F reagents react efficiently with a variety of nucleophiles, yet the presence of water grants complete chemoselectivity to phenols. 相似文献
22.
Clara Argerich Martín Ruben Ibáñez Pinillo Anais Barasinski Francisco Chinesta 《Comptes Rendus Mecanique》2019,347(11):754-761
The aim of this paper is to present a new classification and regression algorithm based on Artificial Intelligence. The main feature of this algorithm, which will be called Code2Vect, is the nature of the data to treat: qualitative or quantitative and continuous or discrete. Contrary to other artificial intelligence techniques based on the “Big-Data,” this new approach will enable working with a reduced amount of data, within the so-called “Smart Data” paradigm. Moreover, the main purpose of this algorithm is to enable the representation of high-dimensional data and more specifically grouping and visualizing this data according to a given target. For that purpose, the data will be projected into a vectorial space equipped with an appropriate metric, able to group data according to their affinity (with respect to a given output of interest). Furthermore, another application of this algorithm lies on its prediction capability. As it occurs with most common data-mining techniques such as regression trees, by giving an input the output will be inferred, in this case considering the nature of the data formerly described. In order to illustrate its potentialities, two different applications will be addressed, one concerning the representation of high-dimensional and categorical data and another featuring the prediction capabilities of the algorithm. 相似文献
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A method is described to couple sterically-hindered electron-poor anilines to the 4-position of the pyrimidine core using a pyrimidine-2,4-bis(trifluoromethanesulfonate). 相似文献
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We review our recent work in the implementation of optical single-sideband (OSSB) modulation and in the application of this modulation format to microwave photonics and optical testing systems. We have developed an enhanced OSSB modulator for wide-band operation, the so-called bidirectional OSSB modulator, and a simplification of this scheme for narrow-band applications. These OSSB modulators are based on the use of a standard single-electrode Mach-Zehnder electro-optic modulator (MZ-EOM) and passive fiber-optic components. In both designs, the OSSB operation is shown to be independent of the MZ-EOM bias. Therefore, the optical modulation depth at the output of the device can be enhanced using minimum transmission biasing to provide suppression of the optical carrier. Finally, we demonstrate the application of OSSB modulators to the improvement of microwave/millimeter-wave subcarrier multiplexing fiber-optic links and to narrow-band fiber radio systems. In addition, we analyzed the feasibility and the limitations of an optical vector network analysis technique based on OSSB modulation that can provide sub-picometer wavelength resolution. 相似文献
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An analytic formulation is given for the total potential in atomic and molecular systems, based on the electrostatic approach from the Hellmann-Feynman theorem. The potential function is obtained from the analytic solution of the Poisson equation using charge densities expressed as a superposition of gaussian functions. The method is independent of the specific LCAO approximation used for the calculation of the charge distribution function. The calculation of the potential and its derivatives to a rapid algorithm form, which can be used for the evaluation of various electronic properties and the treatment of experimental situation, even for large molecular systems. 相似文献
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Nathaniel Cain Alexander Haywood George Roberts Douglas Kiserow Ruben Carbonell 《Journal of Polymer Science.Polymer Physics》2011,49(15):1093-1100
The influence of dissolved propane (up to 31.2 wt %) on the phase equilibria of 5 wt % polystyrene (PS) dissolved in 66/34 wt % trans/cis‐decahydronaphthalene (DHN) was measured over the temperature range of 323–423 K. A suitable temperature, pressure, and propane composition operating space was defined to measure intrinsic viscosities of a single fluid phase. Intrinsic viscosities of PS in cosolvent mixtures of propane and trans/cis‐DHN were measured between 323 and 423 K and between 70 and 208 bar. The addition of propane to the isomeric mixture of DHN resulted in a decreased solvent quality for PS, causing a contraction of the PS coil. The most dramatic decrease in solvent quality with the addition of propane occurred at 323 K and 70 bar with approximately a 36% reduction in the viscometric radius with the addition of 45 mol % propane to DHN. At 423 K, the solvent quality was less sensitive to the addition of propane and only a 13% reduction in the viscometric radius was observed at 70 bar and 45 mol % propane in DHN. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 相似文献