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31.
Niels Van Herck Diederick Maes Kamil Unal Marc Guerre Johan M. Winne Filip E. Du Prez 《Angewandte Chemie (International ed. in English)》2020,59(9):3609-3617
The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross‐linkers for thiols. The click‐like thiol–yne cross‐linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross‐linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne‐based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross‐linker. 相似文献
32.
Two protonated forms of chlorine nitrate, HClONO+ 2 and ClONO2H+, are treated ab initio by the Hartree-Fock and the second order Møller-Plesset perturbation approach with the standard 6–31G* basis set. Both minimum energy structures are planar (C 3 symmetry) and their structural, energy, and vibrational parameters are reported. The computations conclude that the proton attacks the chlorine nitrate at its central, not end, oxygen atom. The protonation causes a considerable elongation of the central ON bond which becomes most probable place of cleavage. The dissociation should yield the neutral HOCl and NO+ 2. These quantum-chemical findings well agree with the previous experimental indications. 相似文献
33.
In this paper, we present several methods for the construction of elliptic curves with large torsion group and positive rank over number fields of small degree. We also discuss potential applications of such curves in the elliptic curve factorization method (ECM). 相似文献
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36.
Vajda S Lupulescu C Merli A Budzyn F Wöste L Hartmann M Pittner J Bonacić-Koutecký V 《Physical review letters》2002,89(21):213404
We present two-color fs pump-probe spectra of Na2F which were recorded by employing excitation wavelengths around 1208 nm (pump) and ionization wavelengths around 405 nm (probe). The observed oscillatory structure of the signal with a period of 185 fs shows an excellent agreement with our simulated spectra. The employed ab initio Wigner distribution approach provides clear evidence that this observation is caused by photoinduced metal bond breaking followed by a butterfly-type periodic geometric rearrangement. 相似文献
37.
Filip X Tripon C Filip C 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,176(2):239-243
A new heteronuclear decoupling mechanism under fast magic-angle spinning MAS is introduced. It is based on refocusing the coherences responsible for the dephase of low-gamma nuclei ((13)C, (15)N) transverse spin-polarization in the presence of strongly dipolar-coupled protons, and has the advantage that can be implemented by pulsed techniques, with all the benefits resulting from a reduced duty cycle compared with conventional decoupling by continuous rf irradiation. The decoupling efficiency of a simple rotor-synchronized Hahn-echo pulse train is analyzed both theoretically and experimentally. It was found that a substantial improvement in sensitivity and resolution can be achieved in compounds with small (1)H chemical shielding parameters even at moderate sample spinning, and some interesting applications are shown. It is also shown that much faster spinning frequencies, or alternative refocusing sequences, are needed for applications on rigid organic solids, i.e., in systems with larger (1)H chemical shifts. 相似文献
38.
Continuous separation of lipid particles from erythrocytes by means of laminar flow and acoustic standing wave forces 总被引:1,自引:0,他引:1
Improved continuous acoustic particle separation (separation efficiency close to 100%) and separation of erythrocytes (red blood cells) from lipid microemboli in whole blood is reported. 相似文献
39.
Trzaskowski B Leonarski F Leś A Adamowicz L 《The journal of physical chemistry. B》2005,109(37):17734-17742
A theoretical study of protein docking to self-assembled monolayers using a new approach is presented. Docking experiments based on space complementarity implemented in FTDock software were performed for three different proteins: tubulin dimer, cytochrome c, and lysozyme. The proteins were adsorbed on alkanethiol surfaces with different terminating groups and 50,000 best orientations of each protein were analyzed. For all systems three filters based on different chemical and biological approaches were applied. Correctly docked proteins for the cytochrome c and lysozyme systems were found in a list of the first 12 results after applying the geometrical and grouping filter and in a list of the first 3 results after applying the biological filter. We have found that alkanethiol monolayers with odd and even numbers of -CH2- groups have similar properties in terms of interactions with the two proteins. Docking of the tubulin dimer revealed that the orientation favored from the applicational point of view can be found in a list of the first 14 results for monolayers with different terminating groups and that there may be a noticeable difference in tubulin dimer interactions with alkanethiol chains of various length. The results for tubulin dimer docking combined with microtubules ability of reversible assembly suggest that these biological structures may become good candidates to serve as templates for fabrication of nanowires and other nanoscale electronic devices. The new method of theoretical docking presented may be used as a fast and reliable tool complementing other theoretical and experimental techniques of exploring other protein-surface interfaces. 相似文献
40.
The fluid of two-dimensional hard disks is investigated over a range of densities by Monte Carlo simulations in order to detect and characterize structural changes which take place when the condition of freezing and melting is approached. A novel method is proposed based on the use of the Voronoi tessellation and a certain shape factor which turns out to be a clear indicator of the presence of different underlying substructures (domains). Close to the freezing condition the probability distribution of the shape factor develops a second distinct maximum corresponding to a predominant presence of near-regular hexagons, whereas the original peak, having its origin primarily in pentagons and distorted hexagons, diminishes and disappears at melting density. 相似文献