The pentamethylcyclopentadienyl N-heterocyclic carbene nickel complex [Ni(η5-C5Me5)Cl(IMes)] (IMes=1,3-dimesitylimidazol-2-ylidene) efficiently catalyses the anti-Markovnikov hydroboration of alkenes with catecholborane in the presence of a catalytic amount of potassium tert-butoxide, and joins the very exclusive club of nickel catalysts for this important transformation. Interestingly, the regioselectivity can be reversed in some cases by using pinacolborane instead of catecholborane. Mechanistic investigations involving control experiments, 1H and 11B NMR spectroscopy, cyclic voltammetry, piezometric measurements and DFT calculations suggest an initial reduction of the NiII precursor to a NiI active species with the concomitant release of H2. The crucial role of the alkoxo-catecholato-borohydride species resulting from the reaction of potassium tert-butoxide with catecholborane in the formation of an intermediate nickel-hydride species that would then be reduced to the NiI active species, is highlighted. 相似文献
First-in-class CuII and AuIII metaled phosphorus dendrons were synthesized and showed significant antiproliferative activity against several aggressive breast cancer cell lines. The data suggest that the cytotoxicity increases with reducing length of the alkyl chains, whereas the replacement of CuII with AuIII considerably increases the antiproliferative activity of metaled phosphorus dendrons. Very interestingly, we found that the cell death pathway is related to the nature of the metal complexed by the plain dendrons. CuII metaled dendrons showed a potent caspase-independent cell death pathway, whereas AuIII metaled dendrons displayed a caspase-dependent apoptotic pathway. The complexation of plain dendrons with AuIII increased the cellular lethality versus dendrons with CuII and promoted the translocation of Bax into the mitochondria and the release of Cytochrome C (Cyto C). 相似文献
Journal of Solution Chemistry - Choline-based ionic liquids, involving various alkyl chains lengths and carboxylates derived from biobased acids, have been synthetized with high yields through a... 相似文献
A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2PO(OEt)2, iodonium salts and a copper salt provided a straightforward manifold to reach these highly relevant products. The reaction proved to be highly functional group tolerant and proceeded under mild conditions, giving the corresponding products in good to excellent yields. This method represents the first general synthetic route to this important class of fluorinated scaffolds, which are well‐recognized as in vivo stable phosphate surrogates. 相似文献
In this paper, the effects of functionalization with terpenes on two new liquid-crystalline stationary phases for gas chromatography (GC) are described. Citronellol was used as the terminal group in the first material, and tetrahydrogeraniol was used with a second material. Inverse GC showed that the new materials have wide liquid-crystalline ranges (mesophases), 371–500 and 395–501 K, respectively. Moreover, they show good thermal stability up to 523 K and good potential as stationary phases for capillary GC. To clarify the effects of the liquid crystal structures and functional groups on retention and separation, the chromatographic behaviors of the two stationary phases were compared by eluting alkylbenzenes, polycyclic aromatic hydrocarbons, aromatic compounds, and terpenoids. The selectivities for a wide range of analytes achieved using the citronellol column were significantly better than those obtained using the tetrahydrogeraniol column. The columns showed different retention behaviors and fine resolutions for some of the main constituents of essential oils. Introduction of the double bond of citronellol greatly improved the polarization interactions involved in the shape recognition of the liquid-crystalline state for isomers. The new citronellol liquid-crystalline stationary phase, therefore, has a high affinity for natural compounds.
Let \(\mathcal S\) be an abelian group of automorphisms of a probability space \((X, {\mathcal A}, \mu )\) with a finite system of generators \((A_1, \ldots , A_d).\) Let \(A^{{\underline{\ell }}}\) denote \(A_1^{\ell _1} \ldots A_d^{\ell _d}\), for \({{\underline{\ell }}}= (\ell _1, \ldots , \ell _d).\) If \((Z_k)\) is a random walk on \({\mathbb {Z}}^d\), one can study the asymptotic distribution of the sums \(\sum _{k=0}^{n-1} \, f \circ A^{\,{Z_k(\omega )}}\) and \(\sum _{{\underline{\ell }}\in {\mathbb {Z}}^d} {\mathbb {P}}(Z_n= {\underline{\ell }}) \, A^{\underline{\ell }}f\), for a function f on X. In particular, given a random walk on commuting matrices in \(SL(\rho , {\mathbb {Z}})\) or in \({\mathcal M}^*(\rho , {\mathbb {Z}})\) acting on the torus \({\mathbb {T}}^\rho \), \(\rho \ge 1\), what is the asymptotic distribution of the associated ergodic sums along the random walk for a smooth function on \({\mathbb {T}}^\rho \) after normalization? In this paper, we prove a central limit theorem when X is a compact abelian connected group G endowed with its Haar measure (e.g., a torus or a connected extension of a torus), \(\mathcal S\) a totally ergodic d-dimensional group of commuting algebraic automorphisms of G and f a regular function on G. The proof is based on the cumulant method and on preliminary results on random walks. 相似文献
The main purpose of this paper is to generalize the celebrated L~2 extension theorem of Ohsawa and Takegoshi in several directions: The holomorphic sections to extend are taken in a possibly singular hermitian line bundle, the subvariety from which the extension is performed may be non reduced, the ambient manifold is K¨ahler and holomorphically convex, but not necessarily compact. 相似文献
In this paper, we derive a necessary condition for a best approximation by piecewise polynomial functions of varying degree from one interval to another. Based on these results, we obtain a characterization theorem for the polynomial splines with fixed tails, that is the value of the spline is fixed in one or more knots (external or internal). We apply nonsmooth nonconvex analysis to obtain this result, which is also a necessary and sufficient condition for inf-stationarity in the sense of Demyanov–Rubinov. This paper is an extension of a paper where similar conditions were obtained for free tails splines. The main results of this paper are essential for the development of a Remez-type algorithm for free knot spline approximation. 相似文献
Anselm of Cantorbery wrote Proslogion (1077–1078), where is formulated the famous ‘Unum argumentum’ about the existence of God. This argument was been disputed and criticized by numerous logicians from an extensional view point. The classical predicate logic is not able to give a formal frame to develop an adequate analysis of this argument. According to us, this argument is not an ontological proof; it analyses the meaning of the “quo nihil maius cogitari posit”, a characterization of God, and establish, by absurd, that “quod non posit cogitare non esse” by using the hypothesis: “to think in re” is taller than “to think in solo intelectu”. We discuss this relation and the difference between the meanings of the elementary predicates ‘to be in re’, ‘to be in intellectu’ and ‘to be in solo intellectu’. We propose a new logical approach of this ‘Unum argumentum’ of Anselm by using Curry’s Combinatory Logic (1958, 1973). Indeed, Combinatory Logic is an abstract applicative formalism of operators applied to operands; in this formalism, the predicates, viewed as specific operators, can be composed and can be transformed, by an intrinsic way, into more complex predicates, by means of abstract operators, called “combinators”, studied by Combinatory Logic. We show that this formalism is a logical frame where it becomes possible to discuss and to formulate cognitive representations of the meanings of predicates used inside of the ‘Unum argumentum’ and to explain how the argument runs. 相似文献