Lanthanide SMMs Based on Belt Macrocycles: Recent Advances and General Trends

Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.     

PTML modeling for peptide discovery: in silico design of non-hemolytic peptides with antihypertensive activity

Molecular Diversity - Hypertension is a medical condition that affects millions of people worldwide. Despite the high efficacy of the current antihypertensive drugs, they are associated with...     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Prediction problem in quantum mechanics is intractable (NP-Hard)

It is proved that both the prediction problem and the problem of reconstructing the state from the observations in quantum mechanics are NP-hard.     

Some new topological cardinal inequalities

In this paper we make use of the Pol-Šapirovski?'s technique to prove several cardinal inequalities, which generalize other well-known inequalities.     

Risk-neutral valuation with infinitely many trading dates

The first Fundamental Theorem of Asset Pricing establishes the equivalence between the absence of arbitrage in financial markets and the existence of Equivalent Martingale Measures, if appropriate conditions hold. Since the theorem may fail when dealing with infinitely many trading dates, this paper draws on the A.A. Lyapunov Theorem in order to retrieve the equivalence for complete markets such that the Sharpe Ratio is adequately bounded.     

An elementary proof of the uniqueness of invariant product measures for some infinite dimensional processesUne preuve élémentaire de l'unicité des mesures invariantes produits pour certains processus en dimension infinie

Consider an infinite dimensional diffusion process with state space , where T is the circle, and defined by an infinitesimal generator L which acts on local functions f as . Suppose that the coefficients a_i and b_i are smooth, bounded, of finite range, have uniformly bounded second order partial derivatives, that a_i are uniformly bounded from below by some strictly positive constant, and that a_i is a function only of η_i. Suppose that there is a product measure ν which is invariant. Then if ν is the Lebesgue measure or if d=1,2, it is the unique invariant measure. Furthermore, if ν is translation invariant, it is the unique invariant, translation invariant measure. The proofs are elementary. Similar results can be proved in the context of an interacting particle system with state space , with uniformly positive bounded flip rates which are finite range. To cite this article: A.F. Ram??rez, C. R. Acad. Sci. Paris, Ser. I 334 (2002) 139–144     

Microperforated insertion units: An alternative strategy to design microperforated panels

Microperforated panels (MPPs) coupled to a rigid wall have been proposed recently as an alternative to porous absorbers in situations having concerns with bacterial contamination and small particles discharge, like food, pharmaceutical and microelectronic industries. There exists also an increasing interest for MPP absorbers in the transportation industry and civil engineering. In general, an optimally designed MPP with good broadband absorption requires many submillimetric holes distributed over a panel of also submillimetric thickness. Such thin plates or foils become so fragile that they need to be protected from mechanical damage. In this paper, an alternative strategy is investigated which allows the design of MPPs with panels of millimetric thickness while maintaining their acoustic performance. These absorbers, named microperforated insertion units (MIUs), avoid the structural problems of the classical MPPs. An assessment of the sound absorption properties of these structures is presented. Comparisons between calculations and measurements are also made under two experimental conditions: plane waves at normal incidence (impedance tube) and free field (anechoic room).