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941.
Gabriel Jaramillo‐Soto M. Luz Castellanos‐Crdenas Pedro R. García‐Morn Eduardo Vivaldo‐Lima Gabriel Luna‐Brcenas Alexander Penlidis 《Macromolecular theory and simulations》2008,17(6):280-289
The RAFT radical polymerization of vinyl monomers in supercritical carbon dioxide was modeled using the Predici® simulation package. The sensitivity of polymerization responses on formulation and process variables was analyzed. The simulations were carried out using kinetic and physical parameters corresponding to the polymerization of methyl methacrylate in supercritical carbon dioxide, using AIBN as initiator, at 65 °C and 200 bar, and using values of the addition and fragmentation kinetic rate constants of a “typical” RAFT agent, as reference conditions. This is the first report in the literature addressing the modeling or simulation of RAFT polymerization in supercritical carbon dioxide.
942.
ZHENG Yun-Hong RUAN Yu-Zhong YU Yan WU Ren-Ping 《结构化学》2007,26(6):659-663
Mg-Al spinel is synthesized by using industrial waste-residue and basic magnesium carbonate in the aluminum factory as the main raw materials. The influence of V2O5 and Fe2O3 mineralizers on the structure, cell parameters and microscopic morphology of synthesized Mg-Al spinel has been discussed. The Mg-Al spinel is characterized by using XRD, SEM and relevant analytical software, such as Philips plus, Rietveld quantification and so on. The experimental results show that certain amounts of V2O5 and Fe2O3 are beneficial to the formation of Mg-Al spinel, and the optimum addition of V2O5 and Fe2O3 is respectively 2wt% and 3wt%. V2O5 has few effects on cell parameters of Mg-Al spinel; but Fe2O3 can form solid solution with Mg-Al spinel in which Mg-Fe spinel can also dissolve to form continuous solid solution. Therefore, with the increase of Fe2O3 content, the cell parameters of Mg-Al approximately present linear increase. 相似文献
943.
Lingui Zhu Chuanfa Ni Petr Beier G.K. Surya Prakash George A. Olah 《Journal of fluorine chemistry》2007,128(10):1241-1247
We have successfully achieved nucleophilic (phenylsulfinyl)difluoromethylation of both enolizable and non-enolizable aldehydes and ketones by using difluoromethyl phenyl sulfone (1) as the fluoroalkylating agent. Although the chemical yields of the reactions are good to excellent, the observed diastereoselectivity is poor (dr = 1:1.04-2.03). The present synthetic methodology provides a convenient alternative for the preparation of α-(phenylsulfinyl)difluoromethylated carbinols that were previously synthesized via a two-step procedure. 相似文献
944.
Wei Jiang Shujing Li Haitao Liu Guo Lu Fawei Zheng Ping Zhang 《Physics letters. A》2019,383(8):754-758
CrI3 monolayer has recently drawn much attention due to its two-dimensional long range ferromagnetic order. We find that CrI3 nanoribbons, which are strips of CrI3 monolayer, can be used as building blocks of nanodevices. In this paper, we studied the atomic and electronic structures of CrI3 zigzag nanoribbons by using first-principles calculations. CrI3 zigzag nanoribbons are also ferromagnet. Interestingly, edge states exist in the system and play an important role in their electronic structures. They dominate the band structures around Fermi level and can be tuned by edge atomic structures. The intrinsic ferromagnetism and rich electronic structures enable CrI3 zigzag nanoribbons a group of promising candidate materials for spintronics. 相似文献
945.
Vuagnoux-d'Augustin M Alexakis A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(34):9647-9662
Me3Al, Et3Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)4]BF4 or [CuOTf]2C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions. 相似文献
946.
947.
Antonio García Martínez Santiago de la Moya Cerero Beatriz Lora Maroto 《Tetrahedron》2005,61(12):3055-3064
An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed. 相似文献
948.
Nicholas E. Leadbeater Sharon J. Pillsbury Erik Shanahan Victoria A. Williams 《Tetrahedron》2005,61(14):3565-3585
In the light of the controversy in the area and since reports using simultaneous cooling in conjunction with microwave heating are appearing in the literature, we were keen to assess the methodology, looking at temperature measurement issues as well as the use of the technique in three classes of reaction, namely a Heck coupling, a Diels-Alder cycloaddition and a Michael addition. We present our initial findings here. 相似文献
949.
Konstantin L. Ivanov Anna A. Kravtsova Elena A. Kirillova Mikhail Ya. Melnikov Ekaterina M. Budynina 《Tetrahedron letters》2019,60(30):1952-1955
A convenient synthetic strategy for the diastereoselective assembly of spiro[azepane-4,3′-oxindoles] was developed via a Staudinger/Michael/aza-Wittig/reduction/N-deprotection reaction sequence starting from PMB-protected oxindole-substituted ethylazides. The key step of the method is a domino self-catalytic Michael/aza-Wittig reaction wherein the phosphazene moiety acts first as the catalyst and then as the reactant, resulting in the formation of a seven-membered N-heterocycle. 相似文献
950.
Pfisterer A Eisele K Chen X Wagner M Müllen K Weil T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9697-9707
Iodo- and ethynyl-containing bisalkylating bioconjugation agents 5 and 8 were achieved and allow the introduction of reactive unnatural substituents into proteins and peptides whilst the bioactive 3D structure is retained. Derivatives of the peptide hormone somatostatin bearing a single iodo or ethynyl group were prepared through intercalation into the disulfide bridge. For the first time, the exact reaction mechanism of the intercalation was elucidated by applying 2D NMR experiments and it was shown that, during the reaction, somatostatin diastereomers were formed. Site-directed modification of the ethynyl-modified peptide with a coumarin chromophore was achieved through a [1,3] dipolar Huisgen cycloaddition reaction; this suggests that such a derivative could serve as an attractive platform to prepare artificial somatostatin compound libraries. The biological activity and specificity of a representative modified somatostatin derivative was demonstrated and efficient receptor-mediated cell uptake occurred in a dose-dependent manner into receptor positive cells only. The iodo and ethynyl bioconjugation reagents presented herein could be applied for introducing such substituents into alternative peptides and proteins and, in principle, could facilitate the efficient design of a broad variety of artificial protein and peptide analogues with previously unknown bioactivities. 相似文献