Statistical approach of the effects of roughness on the polarization of light scattered by dust grains

In order to study the effect of shape on the optical properties of dust grains, we statistically analyze the linear polarized scattered light. We start by examining a homogeneous spherical grain using the discrete dipole approximation (DDA) Draine (Astrophys J 1988;333:848). Using a uniform law we remove elements of matter on the surface of the grain to describe a random roughness. Then, for various scattering angles, the linear polarization P_l is calculated. We successively repeat the simulation in order to obtain a sample of random variables constituting the values P_l of the linear polarization. The analysis of the results is then achieved through a Gaussian kernel method which provides the probability density function of P_l for each scattering angle. We present the results for a typical interstellar grain of water–ice with radius a comparable to the incident wavelength λ so that the parameter size x≡2πa/λ1. We apply this method for two wavelengths in the near IR, when water–ice is transparent at 1.9 μm, and, when water–ice is absorbing at 3.1 μm. We find that the shape of the density function of the linear polarization is asymmetric to the mean value of the density function and non-unimodal for several scattering angles. This allows us to separate the effects of roughness from those of volume. When water–ice is absorbing, we also observe a significant shift of the polarization peak toward greater scattering angles.     

Predictable stereoselective and chemoselective hydroxylations and epoxidations with P450 3A4

Enantioselective hydroxylation of one specific methylene in the presence of many similar groups is debatably the most challenging chemical transformation. Although chemists have recently made progress toward the hydroxylation of inactivated C-H bonds, enzymes such as P450s (CYPs) remain unsurpassed in specificity and scope. The substrate promiscuity of many P450s is desirable for synthetic applications; however, the inability to predict the products of these enzymatic reactions is impeding advancement. We demonstrate here the utility of a chemical auxiliary to control the selectivity of CYP3A4 reactions. When linked to substrates, inexpensive, achiral theobromine directs the reaction to produce hydroxylation or epoxidation at the fourth carbon from the auxiliary with pro-R facial selectivity. This strategy provides a versatile yet controllable system for regio-, chemo-, and stereoselective oxidations at inactivated C-H bonds and demonstrates the utility of chemical auxiliaries to mediate the activity of highly promiscuous enzymes.     

Dramatic increase of quench efficiency in "spacerless" dimaleimide fluorogens

In this post-genomic era, new techniques are needed to cope with the task of assigning functional roles to the huge number of identified putative gene products. We have developed a minimalist labelling strategy based on the use of synthetic fluorogenic probe reagents that fluoresce only after their reaction with a target peptide sequence. The probe reagents have fluorescent cores and bear two maleimide groups, such that their latent fluorescence is quenched by a photoinduced electron transfer (PET) to the pendant maleimide groups, until both of these groups undergo a specific thiol addition reaction. The efficiency of the fluorescence quenching is critical to the practicality of this labelling method, and has been predicted to be related to the intramolecular distance between the fluorophore and the maleimide groups. We have conducted the first direct test of this hypothesis by preparing a series of novel fluorogens that differ only by the spacer moiety separating their coumarin fluorophore and their dimaleimide fragment. A striking correlation was observed between intramolecular distance and the fluorescence enhancement (FE) observed after reaction with two equivalents of thiol. Guided by this observation, we then designed 'spacerless' fluorogens, of which a dansyl derivative shows an FE ratio of >300, the largest recorded for dimaleimide fluorogens. The trends observed herein provide valuable lessons for subsequent fluorogen design, and the novel fluorogens developed in the course of this study are currently being applied to protein labelling applications.     

Synthesis and growth regulatory activity of pyrazolesulfanyl‐ and isoxazolesulfanyl‐1H‐[1,2,4]triazoles and their azinyl derivatives

By cyclocondensation of 3‐(1H‐[1,2,4]triazol‐3‐ylsulfanyl)‐pentane‐2,4‐dion with hydroxylamine, hydrazine, methylhidrazine, and arylsulfonyl‐hydrazides, the 3‐(3,5‐dimethyl‐isoxazol‐4‐ylsulfanyl)‐1H‐[1,2,4]triazole ( 2 ) and 3‐(3,5‐dimethyl‐1‐R‐pyrazol‐4‐ylsulfanyl)‐1H‐[1,2,4]triazoles ( 3a , 3b , 3c , 3d ) are synthesized. Under the action of quaternary ammonium salts of azines with limited heating in acetone they form a series of compounds ( 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h ), which molecules simultaneously contain three different heterocyclic rings. Structures of compounds were confirmed by ¹H and ¹³C NMR, MS, and elemental analysis. The plants growth regulatory activities of compounds 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h were investigated. Data of biological tests testify that these compounds can be of interest to search for new growth stimulators. J. Heterocyclic Chem., (2010).     

Phase separation of micellar solutions at extreme dilution: A study of polystyrene-b-poly(sodium acrylate) micelles in aqueous NaCl solutions

Micellar solutions of polystyrene-b-poly(sodium acrylate) copolymers in aqueous NaCl were studied by static light scattering (SLS). It was found that micellar solutions of the copolymer, at concentrations of NaCl at, or above, 2.0 mol dm⁻³, became turbid on dilution at constant salt concentration and at constant temperature. Turbidity arose from highly dilute solutions (typically at a concentration three orders of magnitude lower than the overlap concentration of the micelle, C*), but at concentrations above the expected critical micellization concentrations (c.m.c.s). The observed turbidity was attributed to the phase separation of the micellar phase. A systematic investigation of the phase separation phenomenon was performed. The effects of various parameters on the solution behavior of the micellar solutions were studied, including the effect of the concentration of NaCl, the effect of temperature, and the effect of the length of the hydrophilic, corona-forming poly(sodium acrylate) block. Phase separation was attributed to the presence of a very large excess of NaCl in the dilute micellar solutions. It was proposed that phase separation arose because of the reduced hydration of the polyion, the decreased electrostatic repulsion between the micelles, and the increase in the amount of ion binding, which occur in highly dilute salt solutions. © 1996 John Wiley & Sons, Inc.     

Modeling of (vapor + liquid) equilibrium and enthalpy of solution of carbon dioxide (CO2) in aqueous methyldiethanolamine (MDEA) solutions

A thermodynamic model was used to estimate enthalpy of solution of carbon dioxide (CO₂) in methyldiethanolamine (MDEA) aqueous solutions. The model was based on a set of equations for chemical equilibria, phase equilibria, charge, and mass balances. Non-ideality in the liquid phase was taken into account by interaction parameters fitted to (vapor + liquid) equilibrium data.The enthalpies of solution of CO₂ were derived from the model using classical thermodynamic relations and were compared to experimental values obtained in previous works.     

Ruthenium-catalyzed [2+2] cycloadditions of bicyclic alkenes and ynamides

Ruthenium-catalyzed [2+2] cycloadditions between bicyclic alkenes and ynamides were investigated. The ynamide moiety was found to be compatible with the ruthenium-catalyzed cycloaddition conditions giving the corresponding cyclobutene cycloadducts in moderate to good yields (up to 97%). Diastereoselective cycloaddition utilizing chiral cyclic ynamides were also examined and a low to moderate level of asymmetric induction was observed.     

Wetting of Alkanes on Water from a Cahn-Type Theory: Effects of Long-Range Forces

We apply the phenomenological wetting theory of Cahn to fluids with van der Waals forces, and in particular to the wetting of pentane on water. Taking into account explicitly the long-range substrate–adsorbate interaction allows us to reproduce the experimentally observed critical wetting transition, which arises from the vanishing of the Hamaker constant at T53°C. This transition is preceded by a first-order transition between a thin and a thick film at a (much) lower temperature. If long-range forces are neglected, this thin–thick transition is the only wetting transition and critical wetting is missed. Our study focuses on the development of useful theoretical tools, such as phase portraits and interface potentials adapted to systems with van der Waals forces.     

Concise Synthesis of the Antiplasmodial Isocyanoterpene 7,20‐Diisocyanoadociane

The flagship member of the antiplasmodial isocyanoterpenes, 7,20‐diisocyanoadociane (DICA), was synthesized from dehydrocryptone in 10 steps, and in 13 steps from commercially available material. Our previous formal synthesis was reengineered, leveraging only productive transformations to deliver DICA in fewer than half the number of steps of our original effort. Important contributions, in addition to the particularly concise strategy, include a solution to the problem of axial nucleophilic methylation of a late‐stage cyclohexanone, and the first selective synthesis and antiplasmodial evaluation of the DICA stereoisomer with both isonitriles equatorial.     

Représentations de Gelfand–Graev pour les groupes réductifs non connexesGelfand–Graev representations for non connected reductive groups

Let G be a connected reductive group defined over $\text{F}{}_{\mathrm{q}}$ and let F be the corresponding Frobenius endomorphism. Let σ be a quasi-central rational automorphism of G. We define in this article Gelfand–Graev representations of the group $\text{G}{}^{\mathrm{F}}\text{=G}{}^{\mathrm{F}}\text{.〈σ〉}$ when σ is unipotent and when it is semi-simple. We show that they have similar properties to Gelfand–Graev representations of the group G^F. To cite this article: K Sorlin, C. R. Acad. Sci. Paris, Ser. I 334 (2002) 179–184.