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201.
J. A. Tenon M. Carles J. P. Aycard 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(5):568-569
The molecular structure of 1‐methylpyrrolidine‐2,5‐dione, C5H7NO2, corresponds to the dicarbonyl tautomer with an envelope ring conformation. The packing is stabilized by weak intermolecular hydrogen bonds and presents push–pull nucleophile–electrophile interactions of the carbonyl groups. 相似文献
202.
Marta Giamberini Jos Antonio Reina Joan Carles Ronda 《Journal of polymer science. Part A, Polymer chemistry》2006,44(5):1722-1733
A family of mono‐, di‐, and trisubstituted benzylglycidylether derivatives with 4‐dodecyloxybenzyloxy groups at the 4‐, 3,5‐, and 3,4,5‐ position of the aromatic ring was synthesized and characterized. These monomers were subsequently polymerized with an aluminum‐based ionic‐coordinative initiator, [(CH3)2CHO]2Al? O? Zn? O? Al[OCH(CH3)2]2 (the Teyssie' catalyst) or an anionic initiator, potassium t‐butoxide. Polymerizations by potassium t‐butoxide gave rise to conversions below 50% in all cases and relatively low molecular weights. The resulting polymers exhibited liquid crystalline phases, which were smectic for the calamitic monomer and columnar for the tapered monomers. When the ionic‐coordinative Teyssie' catalyst was used, the conversion of monomer was almost quantitative according to the higher activity of this type of initiators. The molecular weights and degree of stereoregularity were higher. The results of mesophase characterization, by DSC, XRD, and POM suggested that higher molecular weights and stereoregularity increase the stability of the mesophase and give rise to more compact structures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1722–1733, 2006 相似文献
203.
Carmen A. Mak Sara Ranjbar Paola Riente Carles Rodríguez-Escrich Miquel A. Pericàs 《Tetrahedron》2014
Two hybrid magnetic materials have been prepared from κ-carrageenan and Fe3O4 nanoparticles and tested as catalysts for the Michael addition of aldehydes to nitroalkenes. Remarkably, the material prepared from unmodified κ-carrageenan showed catalytic activity in the reaction of choice, while the individual components were inactive. This points out to a synergistic effect between the MNPs and κ-carrageenan. The second catalyst, bearing a diphenylprolinol silyl ether moiety, was also shown to promote the reaction, giving rise to the corresponding adducts in excellent ees. After the reaction is complete, the catalysts can be conveniently retrieved by simple magnetic decantation. 相似文献
204.
Enantioselective Continuous‐Flow Production of 3‐Indolylmethanamines Mediated by an Immobilized Phosphoric Acid Catalyst
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Laura Osorio‐Planes Dr. Carles Rodríguez‐Escrich Prof. Dr. Miquel A. Pericàs 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2367-2372
A polystyrene‐supported 1,1’‐bi‐2‐naphthol derived phosphoric acid has been synthesized and applied in the enantioselective Friedel–Crafts reaction of indoles and sulfonylimines. The immobilized catalyst was highly active and selective, and gave rise to a broad range of 3‐indolylmethanamines (19 examples) in high yields and excellent enantioselectivities (up to 98 % enantiomeric excess) after short reaction times under very convenient reaction conditions (RT in dichloromethane). Moreover, repeated recycling (14 cycles) was possible with no substantial loss in catalytic performance and the system could be adapted to a continuous‐flow operation (6 h). Finally, the applicability of the system was further confirmed by rapid access to a library of compounds with three points of diversity in a single continuous‐flow experiment that involved sequential pumping of different substrate combinations. 相似文献
205.
Joan Carles Ronda Jos Antonio Reina Marta Giamberini 《Journal of polymer science. Part A, Polymer chemistry》2004,42(2):326-340
A set of high‐molecular‐weight, new, side‐chain liquid‐crystalline polyethers was obtained by chemical modification of poly(epichlorohydrin) with potassium 3,4,5‐tris[4‐(n‐dodecan‐1‐yloxy)benzyloxy]benzoate. The degree of modification depended on the reaction conditions and ranged from 39 to 58%. The highest value was an apparent modification plateau. NMR characterization indicated no side reactions of any kind (e.g., deshydrohalogenation). All random‐grafted copolymers had hexagonal columnar mesophases with the exception of the least modified copolymer, which had a nematic columnar mesophase. X‐ray diffraction experiments performed on mechanically oriented samples showed that tapered groups were tilted with respect to the column axes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 326–340, 2004 相似文献
206.
David Sanchez‐Garcia Salvador Borros Santi Nonell Jose I. Borrell Carles Colominas Jordi Teixido 《Journal of heterocyclic chemistry》2002,39(4):733-735
Treatment of the benzyl and (trimethylsilylethoxymethyl) SEM protected 2,2′‐biimidazoles, 2a and 2b , with 2 equivalents of N‐bromosuccinimide (NBS) allows obtaining the 5,5′‐dibromo and 4,4′‐dibromo substituted biimidazoles, 3a and 5b respectively. The use of 4 equivalents of NBS, followed by treatment of the corresponding tetrabromoderivatives 4a and 5b with butyl lithium (BuLi), yields the 4,4′‐dibromoderiva‐tives 5a (G=Bn) and 5b (G=SEM). 相似文献
207.
Reyes-Chilpa R Berkov S Hernández-Ortega S Jankowski CK Arseneau S Clotet-Codina I Esté JA Codina C Viladomat F Bastida J 《Molecules (Basel, Switzerland)》2011,16(11):9520-9533
The bulbs and aerial parts of Zephyranthes concolor (Lindl.) Benth. & Hook. f. (Amaryllidaceae), an endemic species to Mexico, were found to contain the alkaloids chlidanthine, galanthamine, galanthamine N-oxide, lycorine, galwesine, and epinorgalanthamine. Since currently only partial and low resolution (1)H-NMR data for chlidanthine acetate are available, and none for chlidanthine, its 1D and 2D high resolution (1)H- and (13)C-NMR spectra were recorded. Unambiguous assignations were achieved with HMBC, and HSQC experiments, and its structure was corroborated by X-ray diffraction. Minimum energy conformation for structures of chlidanthine, and its positional isomer galanthamine, were calculated by molecular modelling. Galanthamine is a well known acetylcholinesterase inhibitor; therefore, the isolated alkaloids were tested for this activity. Chlidanthine and galanthamine N-oxide inhibited electric eel acetylcholinesterase (2.4 and 2.6 × 10(-5) M, respectively), indicating they are about five times less potent than galanthamine, while galwesine was inactive at 10(-3) M. Inhibitory activity of HIV-1 replication, and cytotoxicity of the isolated alkaloids were evaluated in human MT-4 cells; however, the alkaloids showed poor activity as compared with standard anti-HIV drugs, but most of them were not cytotoxic. 相似文献
208.
209.
Photosynthetic light-harvesting is tuned by the heterogeneous polarizable environment of the protein
Curutchet C Kongsted J Muñoz-Losa A Hossein-Nejad H Scholes GD Mennucci B 《Journal of the American Chemical Society》2011,133(9):3078-3084
In photosynthesis, special antenna proteins that contain multiple light-absorbing molecules (chromophores) are able to capture sunlight and transfer the excitation energy to reaction centers with almost 100% quantum efficiencies. The critical role of the protein scaffold in holding the appropriate arrangement of the chromophores is well established and can be intuitively understood given the need to keep optimal dipole-dipole interactions between the energy-transferring chromophores, as described by Fo?rster theory more than 60 years ago. However, the question whether the protein structure can also play an active role by tuning such dipole-dipole interactions has not been answered so far, its effect being rather crudely described by simple screening factors related to the refractive index properties of the system. Here, we present a combined quantum chemical/molecular mechanical approach to compute electronic couplings that accounts for the heterogeneous dielectric nature of the protein-solvent environment in atomic detail. We apply the method to study the effect of dielectric heterogeneity in the energy migration properties of the PE545 principal light-harvesting antenna of the cryptomonad Rhodomonas CS24. We find that dielectric heterogeneity can profoundly tune by a factor up to ~4 the energy migration rates between chromophore sites compared to the average continuum dielectric view that has historically been assumed. Our results indicate that engineering of the local dielectric environment can potentially be used to optimize artificial light-harvesting antenna systems. 相似文献
210.
We propose an infinitesimal dispersion index for Markov counting processes. We show that, under standard moment existence conditions, a process is infinitesimally (over-)equi-dispersed if, and only if, it is simple (compound), i.e. it increases in jumps of one (or more) unit(s), even though infinitesimally equi-dispersed processes might be under-, equi- or over-dispersed using previously studied indices. Compound processes arise, for example, when introducing continuous-time white noise to the rates of simple processes resulting in Lévy-driven SDEs. We construct multivariate infinitesimally over-dispersed compartment models and queuing networks, suitable for applications where moment constraints inherent to simple processes do not hold. 相似文献