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31.
32.
Laure Gouriou Štěpán Vysko?il Pavel Ko?ovský 《Journal of organometallic chemistry》2003,687(2):525-537
The reaction of iso-cinnamyl acetate with NaC(Me)(CO2Me)2, catalysed by Pd-‘MOP’ (MOP=2-methoxy-2′-diphenylphosphino-1,1′-binaphthalene) is known to proceed with a regiochemical memory effect that results in the predominant generation of the branched alkylation product. The analogous reaction employing ‘MAP’ as ligand (MAP=2-N,N-dimethylamino-2′-diphenylphosphino-1,1′-binaphthalene) proceeds with ‘normal’ regioselectivity to generate predominantly the linear isomer of product. A 2H-NMR based analysis, employing quadrupolar coupling in a chiral liquid crystal matrix, has been developed to facilitate the simultaneous study of the regiochemical and stereochemical outcome of the reaction of both enantiomers of iso-cinnamyl ester substrates in 2H-labelled but racemic samples. The analysis allows the comparison of relative rates of two competing isomerisation processes occurring in the π-allyl intermediates in the Pd-catalysed reaction, one of which facilitates asymmetric induction, the other resulting in loss of regiochemical memory. It is demonstrated that the two processes are partially coupled and that this then limits the attainment of high global enantiomeric excess in the branched product to reactions that proceed with low regiochemical retention. A key factor for the observation of high regiochemical memory is found to be the nucleophilicity of the malonate anion and the electrophilicity of the Pd-π-allyl intermediate with reduction in the reactivity of either partner resulting in the onset of substantial loss of memory. 相似文献
33.
Certain haloanisoles present at trace levels cause a large part of earthy-musty off-flavor problems in drinking water. These potent odorous chemicals come mainly through biomethylation of their corresponding halopenols. To enable the investigation of both families of compounds, a method involving solid-phase microextraction (SPME) was developed and the main parameters governing SPME were optimized. This method allows the simultaneous quantification of haloanisoles and halophenols at levels ranging from 1 to 100 or 250 ng/l, with detection limits of about 0.5 ng/l and could be applied to potable as well as raw surface waters. 相似文献
34.
Lejeune C Coelho C Bonhomme-Coury L Azaïs T Maquet J Bonhomme C 《Solid state nuclear magnetic resonance》2005,27(4):242-246
We show that it is possible to efficiently transfer magnetization from 31P to 29Si, using variable amplitude CP MAS experiment. This experiment is demonstrated by using Si5O(PO4)6, the synthesis protocol of which is described. From the obtained results, we show that the experiment allows the spectral edition of 29Si spectra from 31P→29Si CP, enabling the studies of derivatives involving Si–O–P linkages, such as phosphosilicate glasses, microporous silicoaluminophosphates (SAPO) and bioactive phosphosilicates. 相似文献
35.
Le Gal J Latapie L Gressier M Coulais Y Dartiguenave M Benoist E 《Organic & biomolecular chemistry》2004,2(6):876-883
Synthetic pathways to a range of novel semi-rigid tetradentate ligands, with sulfur, amido or amino donor groups, designed to coordinate technetium 99m have been developed. The technetium-99m complexes have been prepared and their stabilities in serum and by metathesis reaction via cysteine exchange reactions were compared. HPLC comparison of two (99m)Tc-complexes and their rhenium analogues led to the first proof of the nature of our radioactive complexes. 相似文献
36.
The efficiency of conventional diffractive optical elements with échelette-type profiles drops rapidly as the illumination wavelength departs from the blaze wavelength. We use high dispersion of artificial materials to synthesize diffractive optical elements that are blazed over a broad spectral range (approximately 1 octave) or for two different wavelengths. 相似文献
37.
Elayaraja Muthuswamy S. Sree Ramadevi H.N. Vasan Cécile Garcia Laure Noé Marc Verelst 《Journal of nanoparticle research》2007,9(4):561-567
A novel synthesis of inorganic–organic hybrid films containing well dispersed and almost uniform size Ag nanoparticles in
agar-agar matrix has been reported. The films are found to be highly stable for more than a year. The colloidal particles
of Ag can be obtained in large quantities in the form of a film or in the gel form when dispersed in agar-agar or by dissolving
in a suitable solvent as solution. Characterization has been done by UV–visible spectroscopy and TEM. The hybrid may be of
interest to study third-order non-linear susceptibility. 相似文献
38.
Putkunz CT D'Alfonso AJ Morgan AJ Weyland M Dwyer C Bourgeois L Etheridge J Roberts A Scholten RE Nugent KA Allen LJ 《Physical review letters》2012,108(7):073901
Ptychographic coherent diffractive imaging (CDI) has been extensively applied using both x rays and electrons. The extension to atomic resolution has been elusive. This Letter demonstrates ptychographic electron diffractive imaging at atomic resolution, permitting identification of structure in a boron nitride helical cone at a resolution of order 1 ?, beyond that of comparative Z-contrast images. A scanning transmission electron microscope is used to create a diverging illumination in a defocused Fresnel CDI geometry, providing a robust strategy leading to a unique solution. 相似文献
39.
Dr. Christophe André Dr. Baptiste Legrand Laure Moulat Emmanuel Wenger Dr. Claude Didierjean Dr. Emmanuel Aubert Dr. Marie Christine Averlant‐Petit Prof. Jean Martinez Dr. Muriel Amblard Dr. Monique Calmes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):16963-16971
The combination of a non‐functionalized constrained bicyclo[2.2.2]octane motif along with urea linkages allowed the formation of a highly rigid 2.512/14 helical system both in solution and the solid state. In this work, we aimed at developing stable and functionalized systems as promising materials for biological applications in investigating the impact of this constrained motif and its configuration on homo and heterochiral mixed‐oligourea helix formation. Di‐, tetra‐, hexa‐, and octa‐oligoureas alternating the highly constrained bicyclic motif of (R) or (S) configuration with acyclic (S)‐β3‐amino acid derivatives were constructed. Circular dichroism (CD), NMR experiments, and the X‐ray crystal structure of the octamer unequivocally proved that the alternating heterochiral R/S sequences form a stable left‐handed 2.5‐helix in contrast to the mixed (S/S)‐oligoureas, which did not adopt any defined secondary structure. We observed that the (?)‐synclinal conformation around the Cα? Cβ bond of the acyclic residues, although sterically less favorable than the (+)‐synclinal conformation, was imposed by the (R)‐bicyclic amino carbamoyl (BAC) residue. This highlighted the strong ability of the BAC residue to drive helical folding in heterochiral compounds. The role of the stereochemistry of the BAC unit was assessed and a model was proposed to explain the misfolding of the S/S sequences. 相似文献
40.
Imaging the Magnetic Reversal of Isolated and Organized Molecular‐Based Nanoparticles using Magnetic Force Microscopy 下载免费PDF全文
Elena Pinilla‐Cienfuegos Samuel Mañas‐Valero Josep Canet‐Ferrer Laure Catala Talal Mallah Alicia Forment‐Aliaga Eugenio Coronado 《Particle & Particle Systems Characterization》2015,32(6):693-700
In the race towards miniaturization in nanoelectronics, magnetic nanoparticles (MNPs) have emerged as potential candidates for their integration in ultrahigh‐density recording media. Molecular‐based materials open the possibility to design new tailor‐made MNPs with variable composition and sizes, which benefit from the intrinsic properties of these materials. Before their implementation in real devices is reached, a precise organization on surfaces and a reliable characterization and manipulation of their individual magnetic behavior are required. In this paper, it is demonstrated how molecular‐based MNPs are accurately organized on surfaces and how the magnetic properties of the individual MNPs are detected and tuned by means of low‐temperature magnetic force microscopy (LT‐MFM) with variable magnetic field. The magnetization reversal on isolated and organized MNPs is investigated; in addition, the temperature dependence of their magnetic response is evaluated. 相似文献