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71.
The Pd-catalysed Suzuki homocoupling of boronic acids was successfully carried out in water under high-intensity ultrasound (HIU). Heterogeneous catalysis with Pd/C, facilitating work up and purification, could be used without adding phosphine ligands. Reaction rates and yields were strongly influenced by the oxidant employed; excellent results were obtained using either molecular oxygen or 3-bromo-4-hydroxycoumarin. 3-Arylation of the latter with the Suzuki procedure had failed, exclusively affording the homocoupling products, symmetric biaryls. Besides offering a number of operational advantages, the use of HIU broadens the field of application for the Suzuki reaction. 相似文献
72.
Chitosan (CTS), a biocompatible, biodegradable, non-toxic polymer, dissolves in water only if pH is lowered under 6.5, when a substantial fraction of the amino groups is protonated. Its range of application has been much extended by partially depolymerising it or converting it to water-soluble derivatives. Working under high-intensity ultrasound at 17.8-18.5 kHz, using either a simple horn or a cup horn, we achieved a controlled depolymerization of CTS, also prepared in high yields several derivatives that can be useful intermediates for further chemical modification, as well as several water-soluble derivatives that lend themselves to a host of industrial applications. Compared to conventional methods, all these reactions went to completion in considerably shorter times at lower temperatures. 相似文献
73.
Benettin Giancarlo Fasso Francesco Guzzo Massimiliano 《Communications in Mathematical Physics》2004,250(1):133-160
We study the long term stability of the proper rotations of the perturbed Euler rigid body, in the framework of Nekhoroshev theory. For simplicity we treat here in detail only the kinetically symmetric case (the potential needs not to be symmetric), but we indicate how to extend the results to the triaxial case. We show that the proper rotations around the symmetry axis are Nekhoroshev stable: more precisely, if the initial datum is sufficiently close to a proper rotation, then for a very long time it remains such, and the tip of the unit vector parallel to the angular momentum precesses, up to a small noise, along the level curves of a regular function on the unit sphere. If the proper rotations are resonant, chaotic motions with positive Lyapunov exponents are possible, but chaos (unlike the case of ordinary motions, that is motions not close to proper rotations) is always localized, and does not affect in an essential way the motion of the angular momentum in space. Preliminary numerical results indicate that the theory is, in many aspects, optimal, although in some points it can still be improved. 相似文献
74.
Pilla O Cunsolo A Fontana A Masciovecchio C Monaco G Montagna M Ruocco G Scopigno T Sette F 《Physical review letters》2000,84(10):2136-2139
Spontaneous emission in photonic crystals with anisotropic three-dimensional dispersion relation is studied. If the upper level is below a characteristic frequency omega(1), or above omega(2), or between omega(1) and omega(2), the radiation is a localized field with a frequency in the band gap, or a propagating field with a frquency in the band, or a diffusion field, respectively. An analytical expression for the Lamb shift is obtained. The Lamb shift for the current case is small compared to that in an ordinary vacuum or in one- or two-dimensional photonic crystals due to lower density of states. 相似文献
75.
Giancarlo Marconi Sandra Monti Francesco Manoli Stefano Ottani 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):279-282
The Induced Circular Dichroism of the complex formed by inclusion of Licochalcone-A (a powerful antimalarian of natural origin)
and β-cyclodextrin was measured and calculated. The association constant was determined by titration experiments of ICD and
fluorescence. The lowest energy conformations of the complex were obtained through docking procedures and their Circular Dichroism
was evaluated within the Tinoco framework. The geometry of the complex was found to be consistent with the main experimental
features. 相似文献
76.
The bis- and tris-pyrylium and thiopyrylium cations 1-4 were prepared in gram scale by heterocyclization of the corresponding bis- and tris-1,5-pentanediones 6 and 8. Their reaction with CD3ONa in CD3OD was studied by 1H NMR at -40 degrees C and at +25 degrees C. At low temperature, kinetically controlled mixtures of 2H and/or 4H adducts were detected, whereas at room temperature the mixtures equilibrated to yield, in all of the cases, the more stable 2H adducts exclusively. A spectrophotometric study of the reactions with sodium methoxide in methanol was carried out at 25.0 degrees C with the aim of determining the stepwise equilibrium constants for the addition of MeO- at the alpha position of the heteroaromatic rings. The obtained equilibrium constants allowed the evaluation of the electronic effects of chalcogenopyrylium and 2H-chalcogenopyran subunits as substituents. Despite the different sensitivity to electronic effects, pyrylium and thiopyrylium rings have a similar electron-withdrawing effect with a sigma(+)p approximately 0.8 and a sigma(+)m approximately 0.5. Apart from the expected importance of the inductive effect due to the positive charge, the difference between these two values remarks the importance of the resonance contribution. In contrast both the neutral 2H-pyranyl and thiopyranyl rings have a negligible effect as substituents, independently of the position, para or meta, they occupy. 相似文献
77.
Bacchi Alessia Pelizzi Giancarlo Minardi Giovannina Pistuddi Angelo M. Solinas Costantino Chelucci Giorgio 《Transition Metal Chemistry》2002,27(3):274-278
Metal complexes of general formula M(L)X2 and M(L)X3 [L = (4S,5S)-2,2-dimethyl-4,5-bis{6-[(4,5-dihydro-4-(S)-(1-methylethyl)oxazol-2-yl)pyridin-2-yl]}-1,3-dioxolane] were obtained by reacting, respectively, CoII, CuII, NiII, and ZnII nitrate salts and the RhIII chloride salt, with a chiral C2-symmetric bis(oxazolinylpyridinyl)dioxolane (L) ligand, in MeOH/CHCl3 solution. A single crystal X-ray analysis was carried out on [Ni(L)(OH2)2](NO3)2 · 2H2O and the molecular structure of L was also determined. In the free ligand the two symmetric arms are essentially planar and oriented nearly perpendicular to the dioxolane average plane. In the Ni complex one seven-membered and two five-membered chelation rings are formed. The metal atom also lies on the C2 axis, and two symmetry-related water molecules complete the octahedral coordination environment. Both compounds crystallize in chiral space groups; the ligand crystallizes in orthorhombic system, space group C 2 2 21, Z = 4; the nickel complex crystallizes in tetragonal system, space group P 43 21 2, Z = 4. 相似文献
78.
We propose a method for the digital reconstruction of an object whose diffraction pattern has been recorded on a hologram. The fractional Fourier transform is used for the object reconstruction. To determine the position of the object, the fractional order is scanned. The fractional cosine and fractional Hartley transforms are also employed for object reconstruction. These two transforms are real valued and allow the reconstruction to be done with lower computing complexity. Simulations and experimental results are presented. 相似文献
79.
Franco Cataldo Giancarlo Angelini Donatella Capitani Marco Gobbino Ornella Ursini Fabrizio Forlini 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):839-849
This paper is dedicated to the memory of our friend and colleague Annalaura Segre. The chemical structure of a series of β (-)-pinene polymers (PBP) obtained by radiation-induced polymerization, free radical initiation, cationic polymerization over a Friedel-Craft catalyst and by coordinative polymerization over a Ziegler-Natta catalyst has been fully elucidated by 1H and 13C-NMR spectroscopy. 2D NMR techniques have been applied in order to assign all the NMR resonances to the structures of the PBP investigated. The NMR spectra show that the most regular PBP structure is obtained by radiation-induced polymerization followed by the free radical initiated polymerization. The most defective structure has been observed in the case of PBP prepared by cationic mechanism over a Friedel-Crafts catalyst. The discussion accounts for different types of defects and cross-links present in the PBPs investigated whose fundamental structure is based on the p-menthene repeating unit. NMR self-diffusion measurements have been performed to evaluate the molecular weight of all the PBP investigated. The highest molecular weight (2600 Dalton) was found in the case of PBP prepared by Ziegler-Natta catalyst, while the lowest molecular weight was found in the case of PBP prepared by radiation-induced polymerization (about 1000 Dalton). 相似文献
80.
This paper reports voltammetric sequential determination of Pt(II), Pd(II), and Rh(III), by square-wave adsorption stripping voltammetry (SWAdSV), and Pb(II), by square-wave anodic stripping voltammetry (SWASV), in vegetable environmental matrices. Analytical procedures were verified by the analysis of the standard reference materials: Olive Leaves BCR-CRM 062 and Tomato Leaves NIST-SRM 1573a. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were always less than 6% and the limits of detection (LOD) for each element were below 0.096 g g–1. Once set up on the standard reference materials, the analytical procedure was transferred and applied to laurel leaves sampled in proximity to a superhighway and in the Po river mouth area. A critical comparison with spectroscopic measurements is discussed. 相似文献