Toward reactant encapsulation for substrate-selectivity

A synthetic tris-(bis-(aminomethyl)pyridine) receptor was prepared in excellent yields via reversible imine condensation strategy. Catalytic activity in Henry reactions of the corresponding copper(II) complex was studied. Capitalizing on previous works by Anslyn with related receptors, the dramatic increase in basicity induced by this type of complex on diketo-derivatives was used to perform a nucleophilic addition of a deprotonated substrate onto an electrophile within the cavity. Hence, a Lewis acid stabilized nitronate was reacted with various aldehydes. A notable preference for small reactants easily accommodated in the cavity over encumbered ones was observed, thus representing an example of substrate-selectivity.     

Design of metal oxide nanoparticles: Control of size,shape, crystalline structure and functionalization by aqueous chemistry

The aim of this paper is to show that a very simple but well controlled chemistry in an aqueous medium allows one to efficiently control the main characteristics of oxide nanoparticles. Examples concerning titania, alumina, iron and manganese oxides are discussed to illustrate various effects on the control of size, shape and structure of nanoparticles. Some examples of functionalization of these particles are also illustrated. Experimental data, procedures and detailed references can be found in the cited literature.     

Analytical approach for CRLH-based antennas design

This paper presents an analytical model for CRLH (Composite Right-Left Handed) antennas preliminary design. The objective of this work is to develop a tool to estimate quickly the scattering and radiating characteristics of these CRLH-based structures. The analytical model provides thus a set of parameters which roughly fulfill desired requirements. Afterwards, the antenna designer can refine the CRLH-based antenna performances with full 3D electromagnetic simulation software.     

Approximations simultanées de nombres algébriques de Q p par des rationnels

 In this paper, we prove that if β₁,…, β _n are p-adic numbers belonging to an algebraic number field K of degree n + 1 over Q such that 1, β₁,…,β _n are linearly independent over Z, there exist infinitely many sets of integers (q ₀,…, q _n ), with q ₀ ≠ 0 and

Irreducibility, Brill-Noether loci, and Vojta's inequality

This paper deals with generalizations of Hilbert's irreducibility theorem. The classical Hilbert irreducibility theorem states that for any cover of the projective line defined over a number field , there exist infinitely many -rational points on the projective line such that the fiber of over is irreducible over . In this paper, we consider similar statements about algebraic points of higher degree on curves of any genus. We prove that Hilbert's irreducibility theorem admits a natural generalization to rational points on an elliptic curve and thus, via a theorem of Abramovich and Harris, to points of degree 3 or less on any curve. We also present examples that show that this generalization does not hold for points of degree 4 or more. These examples come from an earlier geometric construction of Debarre and Fahlaoui; some additional necessary facts about this construction can be found in the appendix provided by Debarre. We exhibit a connection between these irreducibility questions and the sharpness of Vojta's inequality for algebraic points on curves. In particular, we show that Vojta's inequality is not sharp for the algebraic points arising in our examples.

     

Spin densities in a ferromagnetic bimetallic chain compound: polarized neutron diffraction and DFT calculations

The spin population distribution in the ferromagnetically coupled hetero-bimetallic chain compound [MnNi(NO(2))(4)(en)(2)] (en = 1,2-ethanediamine) has been investigated by means of polarized neutron diffraction experiments, and the results compared with those from theoretical estimates obtained via calculations based on density functional theory on dinuclear molecular models of the chain. The spin distributions obtained from experiment and from theory are consistent and reflect a larger spin delocalization from the Ni atom due to the more covalent character of the Ni-N bonds compared to the Mn-O ones. Also a nearly isotropic spin distribution is observed for the more ionic d(5) Mn(2+) ion and a clearly anisotropic distribution for the d(8) Ni(2+) ion. The use of dinuclear molecular models for the calculation of the exchange coupling constant between Ni and Mn provide upper and lower limits (+17.6 and -4.2 cm(-)(1)) for the experimentally determined value (+1.3 cm(-)(1)), depending on how the missing part of the chain is simulated, but yield essentially the same spin distribution. The Mn(II)-Ni(II) weak ferromagnetic coupling in the chain is interpreted in a spin delocalization mechanism as resulting from the weakness of the overlap between the magnetic orbitals centered on nickel and those centered on manganese which are only weakly delocalized on the ligands.     

Synthesis of a potent antagonist of E-selectin

A synthesis of an antagonist of E-selectin previously reported by a group at Novartis Pharma in Basel is described. An important feature involves the formation of an ether linkage based on a Rh(II)-catalyzed reaction. Stereocontrolled glycosylations rely on the anomeric activation of 2-pyridylthio carbonate as leaving group for the attachment of beta-D-galactopyranosyl and alpha-L-fucopyranosyl units on a common 1,5-anhydro D-glucitol scaffold.