Wavefront sensing issues in MCAO

The problematic of wavefront sensing in Multiconjugate Adaptive Optics (MCAO) is addressed in this article. We first focus on the sky coverage estimation which drives, in particular, the choice between natural and laser guide stars and therefore has a major impact on wavefront sensor design. Then a comparison between star oriented and layer oriented concepts is proposed. Analytical developments and optimization of the concepts are derived in the simplest MCAO case: the ground layer AO system. From this study, advantages and drawbacks of each concept are highlighted. To cite this article: T. Fusco et al., C. R. Physique 6 (2005).     

Chemistry of the versatile (hydroxymethyl)phosphinyl P(O)CH2OH functional group

(Hydroxymethyl)phosphorus compounds are well-known and valuable compounds in general; however the use of (hydroxymethyl)phosphinates R(1)P(O)(OR(2))CH(2)OH in particular has been much more limited. The potential of this functionality has not yet been fully realized because the mild unmasking of the hydroxymethyl group was not available. The mild oxidative conversion of R(1)P(O)(OR(2))CH(2)OH into R(1)P(O)(OR(2))H using the Corey-Kim oxidation is described. Other reactions preserving the methylene carbon are also reported.     

Closely stacked oligo(phenylene ethynylene)s: effect of π-stacking on the electronic properties of conjugated chromophores

In this work, a bicyclo[4.4.1]undecane scaffold is used to hold oligo(phenylene ethynylene) units in a cofacially stacked arrangement along the entire length of the conjugated units. We study the impact that the resulting strong interchain interactions have on the photophysical properties. The length of the individual oligomer branches was varied from three to five rings to investigate the effect of conjugation on the electronic properties of the stacked segments. Absorption and fluorescence spectra were recorded and compared to those of the corresponding unstacked analogues. Time-dependent density functional theory calculations were carried out and helped to rationalize the low-energy features present in the fluorescence spectra of the stacked systems. The calculations indicate that the low-energy emissions are due to the presence of excimer-like states. The stronger intensity of the low-energy fluorescence band observed in the five-ring stacked system compared to the three-ring analogue is attributed to the smaller activation barrier that separates the local intrachain state and the excimer-like state in the former compound.     

First steps toward spatially resolved OSL dating with electron multiplying charge-coupled devices (EMCCDs): System design and image analysis

Spatially resolved OSL (SR-OSL) measurements are made with a scanning or imaging system that records luminescence emissions from known sources within a sample. This work is a first step toward the development of an SR-OSL methodology based on the imaging of ultraviolet OSL emissions with an EMCCD camera. We present UV OSL images of natural quartz extracts, OSL/TL/IR images of sandstone, image-based OSL measurements from aluminum oxide grains, and dose recovery experiments on aluminum oxide and Risø calibration quartz. Camera sensitivity and quantitative reproducibility indicate that EMCCD-based OSL dating is feasible. Further experimentation is necessary to adequately define the error sources and measurement limitations of EMCCDs in the OSL regime.     

Preussianone, a new flavanone-chromone biflavonoid from Garcinia preussii Engl

A new flavanone-chromone biflavonoid, preussianone (1), has been isolated from the leaves of Garcinia preussii, along with four known biflavonoids. The absolute stereostructures were elucidated by chemical, spectroscopic, and chiroptical methods. The biological properties of the new biflavonoid against several bacterial strains were evaluated.     

Photoinduced Damage to Cellular DNA: Direct and Photosensitized Reactions(†)

The survey focuses on recent aspects of photochemical reactions to cellular DNA that are implicated through the predominant formation of mostly bipyrimidine photoproducts in deleterious effects of human exposure to sunlight. Recent developments in analytical methods have allowed accurate and quantitative measurements of the main DNA photoproducts in cells and human skin. Highly mutagenic CC and CT bipyrimidine photoproducts, including cyclobutane pyrimidine dimers and pyrimidine (6-4) pyrimidone photoproducts (6-4PPs) are generated in low yields with respect to TT and TC photoproducts. Another striking finding deals with the formation of Dewar valence isomers, the third class of bipyrimidine photoproducts that is accounted for by UVA-mediated isomerization of initially UVB generated 6-4PPs. Cyclobutadithymine (T<>T) has been unambiguously shown to be involved in the genotoxicity of UVA radiation. Thus, T<>T is formed in UVA-irradiated cellular DNA according to a direct excitation mechanism with a higher efficiency than oxidatively generated DNA damage that arises mostly through the Type II photosensitization mechanism. C<>C and C<>T are repaired at rates intermediate between those of T<>T and 6-4TT. Evidence has been also provided for the occurrence of photosensitized reactions mediated by exogenous agents that act either in an independent way or through photodynamic effects.     

Synthesis of a new family of acyclic nucleoside phosphonates, analogues of TPases transition states

A 6-step procedure was developed for the synthesis of a new family of acyclic nucleoside phosphonates (ANPs), "PHEEPA" [(2-pyrimidinyl-2-(2-hydroxyethoxy)ethyl)phosphonic acids] in overall yields ranging from 4.5% to 32%. These compounds, which possess on one side a hydroxy function and on the other side a phosphonate group, can be considered either as potential antiviral agents or as transition state analogues of nucleoside phosphorylases such as thymidine phosphorylase.     

Effectiveness of multilayer viscoelastic insulators to prevent occurrences of brake squeal: A numerical study

The purpose of this publication is to give an overview of the actual role of multi-layered viscoelastic parts, so called “shims”, to prevent squeal noises of automotive brake systems. Since shear stress is usually used to damp thin structures in their bending modes it is commonly believed to be the largest underwent by shims. To check this assumption and considering that stresses underwent by shims cannot be measured experimentally, the authors have computed them with the help of a detailed and realistic finite element model. Contrary to what shims manufacturers say, this study exhibits the fact that shims are almost uniquely solicited in their normal direction in brake systems. Secondly, the study focuses on the added damping and stiffening induced by the viscoelastic materials. In order to take into account these materials, a realistic frequency dependent viscoelastic behavior has been integrated in the simulations. Finally, the study shows certains eigenmodes for which the viscoelastic behavior of the shims reveals instabilities that would not exist without it. It is shown that this is due to coalescence phenomenon.     

The influence of captodative effect on the dienophilicity of olefins. The easy diels-alder reaction of α-methylthioacrylonitrile with cyclohexadiene

We show that the cycloaddition of α-methylthioacrylonitrile to cyclohexadiene is faster than that of acrylonitrile. This indicates that the captodative substitution exerts an accelerating effect on the Diels-Alder reaction despite the larger steric bulk of the methylthio group compared to hydrogen.