Contrasting effects of exterior and interior hydrophobic moieties in the complexation of amino acid functionalized gold clusters with alpha-chymotrypsin

[chemical structure: see text]. A series of L-amino acid functionalized gold nanoparticles with oligo(ethylene glycol) (OEG) tethers of varying length are prepared. These studies show that the hydrophobic side chains of amino acids facilitate the structural retention of alpha-chymotrypsin (ChT) but the interior alkyl chains promote its denaturation. An 80-fold range of denaturation rate constants were obtained for ChT in the presence of various nanoparticles. Thus, the tunable denaturation of protein could be achieved by rational combination of amino acid side chains and OEG tethers.     

An artificial siderophore for the detection of iron(III)

An artificial siderophore in the form of a squaraine dye (1) has been synthesized. The bidentate ligand chelates to Fe(III) between the deprotonated hydroxyl group on the ortho position of the ring adjacent to the carbonyl group of the cyclobutadiene ring. The optical response is due to a subtle geometry change of 1 on chelation to Fe(III). This artificial siderophore forms a 2 ratio 1 ligand ratio metal complex, as indicated by a sigmoidal isotherm (K(a)= 10(7) M(-1)). The optical response on the addition of Fe(III) is observed at low concentrations in comparison to other metal salts. The X-ray crystal structure and calculated structures of dye (1) are also included, and will be discussed.     

A cubic Hénon-like map in the unfolding of degenerate homoclinic orbit with resonance

In this Note, we study the unfolding of a vector field that possesses a degenerate homoclinic (of inclination-flip type) to a hyperbolic equilibrium point where its linear part possesses a resonance. For the unperturbed system, the resonant term associated with the resonance vanishes. After suitable rescaling, the Poincaré return map is a cubic Hénon-like map. We deduce the existence of a strange attractor which persists in the Lebesgue measure sense. We also show the presence of an attractor with topological entropy close to $\log 3$. To cite this article: M. Martens et al., C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

Counting and enumeration complexity with application to multicriteria scheduling

In this paper we tackle an important point of combinatorial optimisation: that of complexity theory when dealing with the counting or enumeration of optimal solutions. Complexity theory has been initially designed for decision problems and evolved over the years, for instance, to tackle particular features in optimisation problems. It has also evolved, more or less recently, towards the complexity of counting and enumeration problems and several complexity classes, which we review in this paper, have emerged in the literature. This kind of problems makes sense, notably, in the case of multicriteria optimisation where the aim is often to enumerate the set of the so-called Pareto optima. In the second part of this paper we review the complexity of multicriteria scheduling problems in the light of the previous complexity results.Received: November 2004 / Received version: March 2005MSC classification: 90B40, 90C29, 68Q15     

Coherent combining in an Yb-doped double-core fiber laser

Coherent combining is demonstrated in a clad-pumped Yb-doped double-core fiber laser. A slope efficiency of more than 70% is achieved with 96% of the total output power in the fundamental mode of one of the two cores. This high combining efficiency is obtained when both cores are coupled via a biconical fused taper in a Michelson interferometer configuration.     

Relationships between mastication conditions and rheological behavior of a natural rubber

The mastication of natural rubber results in the shortening of the long molecular chains, which affects the viscosity of the material. Mechanical and thermo-oxidative breakdowns are the two major factors that interfere during mastication and processing of natural rubber. In an attempt to characterize the viscous behavior of a such product during processing, rheological properties of unvulcanized rubber are studied with a capillary rheometer and a parallel plate rheometer, in small amplitude oscillatory shear. An investigation is carried out with an internal mixer to determine the effect of mastication and temperature on the rheological properties. The influence of thermomechanical effect is quantified as a function of the specific energy and mastication temperature. Depending on mastication conditions, the variation of viscosity may be important and its decrease is quantified by integrating the specific energy and the mastication temperature in a Carreau-Yasuda model.     

Dynamic kinetic resolution of atropisomeric amides

[reaction: see text] Using L-proline as catalyst in the asymmetric aldol reaction and a series of benzamides and naphthamides, we have accomplished a dynamic kinetic resolution that simultaneously establishes the stereochemistry of the atropisomeric amide's chiral axis and a stereogenic center. The enantioselectivities ranged from 82% to 95% and the diastereoselectivities from 2.1:1 to 7.0:1.     

Theoretical and Empirical Relationships Between the Redox Potentials and <Superscript>1</Superscript>(<Emphasis Type="Italic">δ</Emphasis>→<Emphasis Type="Italic">δ</Emphasis>*) Transition Energies of Quadruply Bonded Complexes

An analysis of the available electrochemical and electronic-sectroscopic data for quadruply metal–metal bonded complexes reveals that the ¹(*) transition energy is an approximately linear function of the difference between the electrode potentials at which they are reduced and oxidized to the bond-order 3. 5 complexes. A theoretical framework for interpreting this correlation is provided by extending to the redox potentials a simple zero-differential-overlap model previously applied to ¹(*) transition energies. It is suggested on the basis of this model that the simplicity of the empirical relationship between ¹(*) energies and redox potentials is a consequence of the particular one- and two-electron energy terms that characterize these complexes; a linear relationship is not required by theory.