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41.
[reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction. 相似文献
42.
Develay S Tripier R Le Baccon M Patinec V Serratrice G Handel H 《Dalton transactions (Cambridge, England : 2003)》2005,(18):3016-3024
The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions and four cyclen based bis-macrocycles ligands possessing ortho-(BOC), meta-(BMC), para-xylenyl (BPC) or 2,6-pyridinyl (BPyC) linker was investigated by potentiometric measurements and NMR spectroscopy. Each ligand gave protonated species in aqueous solution that further formed ternary complexes after binding with anions; these complexes were analyzed as a result of hydrogen bond formation and Coulombic attraction between the organic host and the inorganic guest. The equilibrium constants for all the detected species are reported and the selectivity, illustrated with species distribution diagrams, is discussed. The results unambiguously showed the importance of the distance between the two cyclen cores and underlined, especially for the triphosphate species, the contribution of the nitrogen atom of the pyridinyl spacer as a supplementary anchoring point in acidic medium. 相似文献
43.
Raphaël Trouillon Zachary Combs Bhavik Anil Patel Danny O’Hare 《Electrochemistry communications》2009,11(7):1409-1413
Stability of sensors in biosamples is a critical issue and can be mitigated by membranes. The effect of different membranes (Nafion, cellulose acetate, chitosan, fibronectin, PSS/PL) on the electrochemistry of an outer-sphere redox couple (ruthenium II/III hexaammine) and on the electrocatalytic reduction of dissolved oxygen are described. Biofouling has been induced by albumin solutions. Results demonstrate good performances of fibronectin in all situations investigated. Other membranes do not provide a satisfactory protection from biofouling and some of them, PSS/PL in particular, seriously disturb electrochemical mechanisms. 相似文献
44.
Jean-François Morfin Raphaël Tripier Michel Le Baccon Henri Handel 《Polyhedron》2009,28(17):3691-3698
The synthesis of new cyclam and cyclen derivatives (respectively L1 and L2), able to efficiently coordinate to Bi(III) are presented here. The two ligands bearing two different pendant arms (two-pycolyl and two (2-(2-hydroxyethoxy)ethyl)-2-aminoacetamide in trans position) were synthesized in the aim to obtain stable and water soluble complexes. The thermodynamic and kinetic of the formation of the corresponding complexes in aqueous solution were studied by means of NMR and potentiometric investigations. The fast kinetic of complexation and the high stability of the complexes are encouraging for further application with the alpha-emitting 213Bi isotope. 相似文献
45.
We consider a simplified model arising in radiation hydrodynamics which is based on the barotropic Navier–Stokes system describing the macroscopic fluid motion and a P1-approximation (see below) of the transport equation modeling the propagation of radiative intensity. We establish global-in-time existence of strong solutions for the associated Cauchy problem when initial data are close to a stable radiative equilibrium and local existence for large data with no vacuum. All our results are stated in the so-called critical Besov spaces. 相似文献
46.
Raphaël Danchin 《偏微分方程通讯》2017,42(1):68-99
Our main aim is to investigate the temperature patch problem for the two-dimensional incompressible Boussinesq system with partial viscosity: the initial temperature is the characteristic function of some simply connected domain with 𝒞1,𝜀 Hölder regularity. Although recent results ensure that the 𝒞1 regularity of the patch persists for all time, whether higher order regularity is preserved has remained an open question. In the present paper, we give a positive answer to that issue. We also study the higher dimensional case, after prescribing an additional smallness condition involving critical Lebesgue or weak-Lebesgue norms of the data, so as to get a global-in-time statement. All our results stem from general properties of persistence of geometrical structures (of independent interest), that we establish in the first part of the paper. 相似文献
47.
48.
Raphaël Robidas Dominik L. Reinhard Prof. Stefan M. Huber Prof. Claude Y. Legault 《Chemphyschem》2023,24(1):e202200634
Cyclic diaryliodonium compounds like iodolium derivatives have increasingly found use as noncovalent Lewis acids in the last years. They are more stable toward nucleophilic substitution than acyclic systems and are markedly more Lewis acidic. Herein, this higher Lewis acidity is analyzed and explained via quantum-chemical calculations and energy decomposition analyses. Its key origin is the change in energy levels and hybridization of iodine's orbitals, leading to both more favorable electrostatic interaction and better charge transfer. Both of the latter seem to contribute in similar fashion, while hydrogen bonding as well as steric repulsion with the phenyl rings play at best a minor role. In comparison to iodolium, bromolium and chlorolium are less Lewis acidic the lighter the halogen, which is predominantly based on less favorable charge-transfer interactions. 相似文献
49.
Birkel CS Kieslich G Bessas D Claudio T Branscheid R Kolb U Panthöfer M Hermann RP Tremel W 《Inorganic chemistry》2011,50(22):11807-11812
Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C. 相似文献
50.
Raphaël Côte Claudio Muñoz Didier Pilod Gideon Simpson 《Archive for Rational Mechanics and Analysis》2016,220(2):639-710
We prove that solitons (or solitary waves) of the Zakharov–Kuznetsov (ZK) equation, a physically relevant high dimensional generalization of the Korteweg–de Vries (KdV) equation appearing in Plasma Physics, and having mixed KdV and nonlinear Schrödinger (NLS) dynamics, are strongly asymptotically stable in the energy space. We also prove that the sum of well-arranged solitons is stable in the same space. Orbital stability of ZK solitons is well-known since the work of de Bouard [Proc R Soc Edinburgh 126:89–112, 1996]. Our proofs follow the ideas of Martel [SIAM J Math Anal 157:759–781, 2006] and Martel and Merle [Math Ann 341:391–427, 2008], applied for generalized KdV equations in one dimension. In particular, we extend to the high dimensional case several monotonicity properties for suitable half-portions of mass and energy; we also prove a new Liouville type property that characterizes ZK solitons, and a key Virial identity for the linear and nonlinear part of the ZK dynamics, obtained independently of the mixed KdV–NLS dynamics. This last Virial identity relies on a simple sign condition which is numerically tested for the two and three dimensional cases with no additional spectral assumptions required. Possible extensions to higher dimensions and different nonlinearities could be obtained after a suitable local well-posedness theory in the energy space, and the verification of a corresponding sign condition. 相似文献