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Mechanistic features of the cationic copolymerization of lactones with cyclic ethers are studied for β-propiolactone (PL) with tetrahydrofuran (THF) and ?-caprolactone (CL) with THF. It is shown that, in the PL-THF system at [THF]0 > [THF]e, the copolymer is considerably enriched with the more basic THF whereas at [THF]0 < [THF]e anomalous enrichment of the copolymer with the less basic PL is observed. The mechanism of this phenomenon, which is applicable to many other cases and causes the formation of block copolymers from some heterocyclic monomers, is considered. At concentrations below equilibrium, THF is incorporated in the copolymer as pairs of units due to the effect of the penultimate unit on the thermodynamics of its addition. 相似文献
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Fryklund Fredrik Klinteberg Ludvig af Tornberg Anna-Karin 《Advances in Computational Mathematics》2022,48(2):1-35
Advances in Computational Mathematics - It is well known in the literature that standard hierarchical matrix ( ${\mathscr{H}}$ -matrix)-based methods, although very efficient for asymptotically... 相似文献
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p-Carborane has been vinylated on the 2-B-atom in high yields using the Heck reaction. Thus, the reaction between 2-iodo-p-carborane and various styrenes [4-H-, 4-C(6)H(4)-, 4-Cl-, 4-Br-, 4-NO(2)-, 4-CH(3)O-, and 4-CH(3)-] resulted in the production of the corresponding trans-beta-(2-B-p-carboranyl)styrene in DMF solution when reacted in the presence of silver phosphate and the palladacycle Herrmann's catalyst. 相似文献
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Xin-ping Duan Tianyi Chen Tianxiang Chen Lele Huang Li Ye Benedict T. W. Lo Youzhu Yuan Shik Chi Edman Tsang 《Chemical science》2021,12(25):8791
Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts. However, owing to their low melting point, poor thermal stability remains a major obstacle towards their application under reaction conditions. It is a common practice to use porous inorganic templates such as mesoporous silica SBA-15 to disperse Ag nanoparticles (NPs) against aggregation but their stability is far from satisfactory. Here, we show that the catalytic activity for hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) over Ag NPs dispersed on SBA-15 silica can be further promoted by incorporation of alkali metal ions at small loading, which follows the inverse order of their cationic size: Li+ > Na+ > K+ > Rb+. Among these, 5Ag1–Li0.05/SBA-15 can double the MG yield compared to pristine 5Ag/SBA-15 under identical conditions with superior thermal stability. Akin to the effect of an ionic surfactant on stabilization of a micro-emulsion, the cationic charge of an alkali metal ion can maintain dispersion and modulate the surface valence of Ag NPs. Interstitial Li in the octahedral holes of the face center packed Ag lattice is for the first time confirmed by X-ray pair distribution function and electron ptychography. It is believed that this interstitial-stabilization of coinage metal nanoparticles could be broadly applicable to multi-metallic nanomaterials for a broad range of C–O bond activating catalytic reactions of esters.Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts. 相似文献
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Spectroscopic characterization of bacteriorhodopsin's L-intermediate in 3D crystals cooled to 170 K.
A Royant K Edman T Ursby E Pebay-Peyroula E M Landau R Neutze 《Photochemistry and photobiology》2001,74(6):794-804
Spectra are presented from a single 3D microcrystal of bacteriorhodopsin (bR) cooled to 170 K under various illumination conditions. This set is necessary and sufficient to assign the relevant crystal reference spectra. A spectral decomposition of the difference spectrum obtained following the trapping protocol of Royant et al. (2000) (Nature 406, 645-648) is given, confirming that the low temperature L-intermediate was the species that dominated the structural rearrangements previously reported. Smaller contributions from the K and M spectral intermediates are also quantified. Mechanistic insights derived from the X-ray structures of the early bR intermediates are discussed. 相似文献
7.
Michael T. Pottiger John C. Coburn James R. Edman 《Journal of Polymer Science.Polymer Physics》1994,32(5):825-837
The anisotropy of the thermal expansion of polyimide films was investigated . Out-of-plane or thickness direction coefficients of linear thermal expansion (CTE) were calculated from the difference between the coefficient of volumetric expansion (CVE) and the sum of the in-plane or film direction coefficients of linear thermal expansion for commercial and spin-coated PMDA//ODA and BPDA//PPD films and spin coated BTDA//ODA/MPD films. The CVEs were obtained from a pressure-volume-temperature (PVT) technique based on Bridgeman bellows. The CVE was shown to be essentially constant, independent of molecular orientation and thickness. A decrease in the in-plane CTEs therefore occurs at the expense of an increase in the out-of-plane CTE. In all cases the calculated out-of-plane CTE was higher than the measured in-plane CTE. The ratio of the out-of-plane CTE to the in-plane CTE was 1.2, 3.8, and 49.3 for the spin-coated BTDA//ODA/MPD, PMDA//ODA, and BPDA//PPD films, respectively. © 1994 John Wiley & Sons, Inc. 相似文献
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We review and introduce a generalized reaction-diffusion approach to epidemic spreading in a metapopulation modeled as a complex network. The metapopulation consists of susceptible and infected individuals that are grouped in subpopulations symbolizing cities and villages that are coupled by human travel in a transportation network. By analytic methods and numerical simulations we calculate the fraction of infected people in the metapopulation in the long time limit, as well as the relevant parameters characterizing the epidemic threshold that separates an epidemic from a non-epidemic phase. Within this model, we investigate the effect of a heterogeneous network topology and a heterogeneous subpopulation size distribution. Such a system is suited for epidemic modeling where small villages and big cities exist simultaneously in the metapopulation. We find that the heterogeneous conditions cause the epidemic threshold to be a non-trivial function of the reaction rates (local parameters), the network’s topology (global parameters) and the cross-over population size that separates “village dynamics” from “city dynamics”. 相似文献
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Anna Peterson Mari-Liis Ludvig Jevgenija Martõnova Sandra Kaabel Paul Kerner Merle Uudsemaa 《Supramolecular chemistry》2020,32(5):313-319
ABSTRACT We demonstrate that Ullman fragment-coupling can be used to synthesise an oxacalix[4]arene monocarboxylic acid, which provides easy access to its water-soluble carboxylato derivatives. Crystallographic and computational data suggest that the new carboxyl-substituted oxacalix[4]arene adopts a 1,3-alternate conformation both in the solid-state and in methanol solution. Its water-soluble tetrabutylammonium derivate can detect the herbicide paraquat at neutral pH in aqueous media (K a = 111 ± 3 M–1) and in methanol (K a = 2020 ± 70 M–1). 相似文献
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Dr. Shi Tang Dr. Zhi Wang Yanzi Xu Huili Ma Dr. Jia Wang Dr. Christian Larsen Prof. Dongfeng Dang Prof. Ergang Wang Prof. Ludvig Edman 《Angewandte Chemie (International ed. in English)》2023,62(23):e202302874
The emission efficiency of organic semiconductors (OSCs) often suffers from aggregation caused quenching (ACQ). An elegant solution is aggregation-induced emission (AIE), which constitutes the design of the OSC so that its morphology inhibits quenching π–π interactions and non-radiative motional deactivation. The light-emitting electrochemical cell (LEC) can be sustainably fabricated, but its function depends on motion of bulky ions in proximity of the OSC. It is therefore questionable whether the AIE morphology can be retained during LEC operation. Here, we synthesize two structurally similar OSCs, which are distinguished by that 1 features ACQ while 2 delivers AIE. Interestingly, we find that the AIE-LEC significantly outperforms the ACQ-LEC. We rationalize our finding by showing that the AIE morphology remains intact during LEC operation, and that it can feature appropriately sized free-volume voids for facile ion transport and suppressed non-radiative excitonic deactivation. 相似文献