Dissolution of Cellulose and Lignin with Biobased Ionic Liquids

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...     

Hydroboration of Alkenes Catalysed by a Nickel N-Heterocyclic Carbene Complex: Reaction and Mechanistic Aspects

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 Ni^II precursor to a Ni^I 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 Ni^I active species, is highlighted.     

Potent Anticancer Efficacy of First-In-Class CuII and AuIII Metaled Phosphorus Dendrons with Distinct Cell Death Pathways

First-in-class Cu^II and Au^III 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 Cu^II with Au^III 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. Cu^II metaled dendrons showed a potent caspase-independent cell death pathway, whereas Au^III metaled dendrons displayed a caspase-dependent apoptotic pathway. The complexation of plain dendrons with Au^III increased the cellular lethality versus dendrons with Cu^II and promoted the translocation of Bax into the mitochondria and the release of Cytochrome C (Cyto C).     

Characterization Theorem for Best Polynomial Spline Approximation with Free Knots,Variable Degree and Fixed Tails

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.     

CLT for Random Walks of Commuting Endomorphisms on Compact Abelian Groups

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.     

A Logical Analysis of the Anselm’s Unum Argumentum (from <Emphasis Type="BoldItalic">Proslogion</Emphasis>)

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.     

A general extension theorem for cohomology classes on non reduced analytic subspaces

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.     

A time-reversal method for an acoustical pulse propagating in randomly layered media

In the recent years a considerable amount of mathematical work has been devoted to the study of reflected signals obtained by the propagation of pulses in randomly layered media. We refer to [M. Asch, W. Kohler, G. Papanicolaou, M. Postel and B. White, “Frequency content of randomly scattered signals”, SIAM Review 33 (4), 519–625 (1991)] for an extensive survey and applications to inverse problems. The analysis is based on separation of scales between the correlation scale of the inhomogeneities present in the medium, the typical wavelengths of the pulse and the macroscopic variations of the medium. On the other hand, in the context of ultrasounds, time-reversal mirrors have been developed and their effects have been studied experimentally by Mathias Fink and his team at the Laboratoire Ondes et Acoustique (ESPCI-Paris). We refer to: [M. Fink, “Time reversal mirrors”, J. Phys. D: Appl. Phys. 26, 1333–1350 (1993)]. Our goal is to present a mathematical analysis of a time-reversal method for analyzing reflected signals in the model described in [M. Asch, W. Kohler, G. Papanicolaou, M. Postel and B. White, “Frequency content of randomly scattered signals”, SIAM Review 33(4), 519–625 (1991)]. We restrict our analysis to the one-dimensional case, the three-dimensional layered case being the content of a forthcoming paper. It is noticeable that we do not introduce new mathematics in the problem but simply put together an already existing mathematical theory and a new device, the time-reversal mirror.