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31.
The N-arylation of aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, has been accomplished using a simple and cheap copper catalytic system. The corresponding tertiary acyclic amides, which can be found in numerous biologically active compounds, have been obtained in good to excellent yields. 相似文献
32.
The mechanism of the copper-mediated disproportionation of aromatic imine disulfides to benzothiazoles in the gas phase is investigated by experimental and theoretical methods. Application of infrared multiphoton dissociation and hydrogen/deuterium exchange experiments combined with density functional theory (DFT) calculations of the relevant molecular structures and the associated infrared spectra allows the identification of the observed ionic intermediates. The theoretical investigation of the possible reaction pathways supported by collision-induced dissociation experiments provides a consistent mechanistic picture of the reaction catalyzed by a single copper(I) ion. Activation of the substrate proceeds via homolytic sulfur-sulfur bond cleavage, yielding metal complexes in the formal +3 oxidation state; carbon-sulfur coupling and hydrogen-atom transfer complete the transformation to the products. Exploratory studies demonstrate that in the gas phase, the disproportionation of the imine disulfide can also be mediated by other metal ions via different either homo- or heterolytic mechanisms without involving high-valent intermediates. 相似文献
33.
Mercey G Verdelet T Saint-André G Gillon E Wagner A Baati R Jean L Nachon F Renard PY 《Chemical communications (Cambridge, England)》2011,47(18):5295-5297
Nerve agents are highly toxic organophosphorus compounds with strong inhibition potency against acetylcholinesterase (AChE). Herein, we describe two first extremely promising uncharged reactivators for poisoned human AChE with a superior or similar in vitro ability to reactivate the enzyme as compared to that of HI-6, obidoxime, TMB-4 and HL?-7. 相似文献
34.
Unger EL Morandeira A Persson M Zietz B Ripaud E Leriche P Roncali J Hagfeldt A Boschloo G 《Physical chemistry chemical physics : PCCP》2011,13(45):20172-20177
The hole transporting medium in solid-state dye-sensitized solar cells can be utilized to harvest sunlight. Herein we demonstrate that a triphenylamine-based dye, used as hole-transporting medium, contributes to the photocurrent in a squaraine-sensitized solid-state dye-sensitized solar cell. Steady-state photoluminescence measurements have been used to distinguish between electron transfer and energy transfer processes leading to energy conversion upon light absorption in the hole-transporting dye. 相似文献
35.
Klecha E Arfaoui I Richardi J Ingert D Pileni MP 《Physical chemistry chemical physics : PCCP》2011,13(7):2953-2962
Here, 5 nm Ag nanocrystals are deposited, using the same procedure, on various substrates differing by their rms roughness, wetting properties and nanoparticle-substrate interactions leading, consequently, to different nanocrystal orderings. Theoretical calculations are carried out to understand how these parameters influence the size of the nanocrystal organizations on the substrate surface. When these nanocrystal arrays are subjected to an oxygen plasma treatment, the nanocrystals perfectly assembled in hexagonal networks remain intact, while the nanocrystals that are not well-packed coalesce to form larger particles independently on the used substrate. This phenomenon is observed on the entire substrate surface. This procedure gives an innovative way of using oxygen plasma generated by the reactive ion etching technique, as a new method to reveal defects in 2D Ag nanocrystal self-assemblies. 相似文献
36.
Emilie Groison Salim Adjili Alice Ferrand Frdric Lortie Daniel Portinha Nathalie Sintes‐Zydowicz 《Macromolecular rapid communications》2011,32(6):491-496
This contribution presents a new strategy for preparing nanocapsules with a shell made of a supramolecular polymer which repeating units are held together by reversible interactions rather than covalent bonds. These nanocapsules were prepared in classical miniemulsion through interfacial addition reaction of a diisocyanate (IPDI) and a monoamine (iBA), forming low‐molecular weight bis‐ureas moieties which are strong self‐complementary interacting molecules through hydrogen‐bonding. The nanocapsules present a diameter around 100 nm, and MALDI‐TOF MS and 1H NMR analyses confirm the expected molecular characteristics for the shell. This strategy opens the scope of a new type of nanomaterials exhibiting stimuli‐responsiveness due to the reversible interaction linking the repeating units.
37.
We theoretically introduce a mesoscopic pendulum from a triple dot. The pendulum is fastened through a singly occupied dot (spin qubit). Two other strongly capacitively coupled islands form a double-dot charge qubit with one electron in excess oscillating between the two low-energy charge states (1,0) and (0,1). The triple dot is placed between two superconducting leads. Under realistic conditions, the main proximity effect stems from the injection of resonating singlet (valence) bonds on the triple dot. This gives rise to a Josephson current that is charge- and spin-dependent and, as a consequence, exhibits a distinct resonance as a function of the superconducting phase difference. 相似文献
38.
Multidentate phosphines were readily obtained by reaction of chiral multidentate amines, prepared via ring opening of (S)-N-tosyl-2-isopropylaziridine with ammonia, primary, and secondary amines, with achiral phosphorus containing building blocks. The phosphines were used in palladium-catalyzed alkylation of rac-3-cyclohexenyl and cyclopentenyl carbonates. The enantioselectivity and reactivity were largely dependent on the structure of the amine core of the ligands. Up to 88% ee was observed in reactions with the six-membered substrate. 相似文献
39.
40.
Cindy Jong Joseph J. Pedulla Emilie Mitescu Reagan Yves Salomon‐Fernandez Marilyn Cochran‐Smith 《School science and mathematics》2010,110(6):309-326
This study examined the classroom practices of beginning elementary school teachers' instruction of mathematics and how it connected to their pupils' learning. The Reformed Teaching Observation Protocol (RTOP) was used to measure the extent to which beginning teachers used reformed teaching practices. As a measure of pupil learning, we utilized assessment scores specific to the mathematics unit observed and correlated them with teachers' RTOP scores. We found that beginning teachers who implemented reformed teaching practices tended to have pupils who scored higher on the district mathematics test with a statistically significant correlation of 0.56 (p < .05). Implications of these findings and others are discussed in terms of using the RTOP to improve practice at the elementary school level and for future school‐based research. 相似文献