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Egle M. Beccalli Prof. Elena Borsini Stefano Brenna Dr. Simona Galli Dr. Micol Rigamonti Gianluigi Broggini Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1670-1678
The isolation of σ‐alkylpalladium Heck intermediates, possible when β‐hydride elimination is inhibited, is a rather rare event. Performing intramolecular Heck reactions on N‐allyl‐2‐halobenzylamines in the presence of [Pd(PPh3)4], we isolated and characterized a series of stable bridged palladacycles containing an iodine or bromine atom on the palladium atom. Indolyl substrates were also tested for isolation of the corresponding complexes. X‐ray crystallographic analysis of one of the indolyl derivatives revealed the presence of a five‐membered palladacycle with the metal center bearing a PPh3 ligand and an iodine atom in a cis position with respect to the nitrogen atom. The stability of the σ‐alkylpalladium complexes is probably a consequence of the strong constraint resulting from the bridged junction that hampers the cisoid conformation essential for β‐hydride elimination. Subsequently, the thus obtained bridged five‐membered palladacycles were proven to be effective precatalysts in Heck reactions as well as in cross‐coupling processes such as Suzuki and Stille reactions. 相似文献
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Peruzzo D Zanderigo F Bertoldo A Pillonetto G Cosottini M Cobelli C 《Magnetic resonance imaging》2011,29(7):927-936
Dynamic susceptibility contrast magnetic resonance imaging (DSC-MRI) allows the noninvasive assessment of brain hemodynamics alterations by quantifying, via deconvolution, the cerebral blood flow (CBF) and mean transit time (MTT). Singular value decomposition (SVD) and block-circulant SVD (cSVD) are the most widely adopted deconvolution method, although they bear some limitations, including unphysiological oscillations in the residue function and bias in the presence of delay and dispersion between the tissue and the arterial input function. A nonlinear stochastic regularization (NSR) has been proposed, which performs better than SVD and cSVD on simulated data both in the presence and absence of dispersion. Moreover, NSR allows to quantify the dispersion level. Here, cSVD and NSR are compared for the first time on a group of nine patients with severe atherosclerotic unilateral stenosis of internal carotid artery before and after carotid stenting to investigate the effect of arterial dispersion. According to region of interest-based analysis, NSR characterizes the pathologic tissue more accurately than cSVD, thus improving the quality of the information provided to physicians for diagnosis. In fact, in 7 (78%) of the 9 subjects, CBF and MTT maps provided by NSR allow to correctly identify the pathologic hemisphere to the physician. Moreover, by emphasizing the difference between pathologic and healthy tissues, NSR may be successfully used to monitor the subject's recovery after the treatment and/or surgery. NSR also generates dispersion level and non-dispersed CBF and MTT maps. The dispersion level provides information on CBF and MTT estimates reliability and may also be used as a clinical indicator of pathological tissue state complementary to CBF and MTT, thus increasing the clinical information provided by DSC-MRI analysis. 相似文献
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Chiara Dall'asta Gianluigi Ingletto Roberto Corradini Gianni Galaverna Rosangela Marchelli 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):257-263
Cyclodextrins have been used as fluorescence enhancers in HPLC to improve thedetection limits of aflatoxins, cancerogens which can be found in severalfoodstuffs. In this work, a screening of several cyclodextrins has been performedin order to find the factors affecting the fluorescence enhancement. Evidence for formationof a 1 : 1 AF-CD inclusion complex has been achieved by titration and competitiveexperiments with adamantanecarboxylic acid and by fluorescence quenching by KI.Stability constants of the AF-CD complexes were evaluated. 相似文献
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Observed and calculated LEED intensity spectra for the p(2 × 2) pattern given by the adsorption of hydrogen on Ni(111) at 173 K are reported. Among the several model geometries tried that with the hydrogen atoms adsorbed in one of the two possible hollow sites seems to be the most probable. 相似文献
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