Synthesis of para-substituted styrenes

Using double Stille cross-coupling reaction bromo (or chloro)benzylbromide is easily transformed into substituted styrene monomers bearing a wide range of substituents in para position     

Stereo- and Regiochemical Effect of N,N-Dialkylamide Extractants on the Speciation of Pu Complexes

The relationship between extractant stereochemistry and their extraction performance has only poorly been established. In order to address a part of this concern, we investigated the Pu(IV) liquid-liquid extraction (LLE) by using the N,N-di-(2-ethylhexyl)butyramide (DEHBA), as well as those of its position isomers. DEHBA (ββ-isomer) and N-(2-ethylhexyl)-N-(oct-3-yl)butyramide (EHOBA or αβ-isomer) were synthesized as a mixture of stereoisomer or stereoenriched (R,S)- and (S,S)-diastereoisomers, and were all assessed for Pu^IV LLE. The results showed that both the position and the stereoisomerism of the aliphatic substituents affect Pu^IV complexation and extraction. We found that Pu extraction is lowered by factor 2 to 4 when the ethyl branching group is closer to the complexing site. UV-vis spectroscopy showed that this extraction decrease was affected by steric hindrance inducing a deprivation of Pu inner sphere complex. Effect of stereoisomerism is highlighted for branching closer to the complexing site (α-position). Enantiopure DEHBA stereoisomers provided similar Pu extraction, whereas a slight decrease could be noticed for the more cluttered stereoenriched (αβ)-isomers, which was also concomitant with a smaller population of inner sphere complex. In contrast, the stereoisomers mixture led to a strong decrease of Pu extraction because of an antagonistic association in the mixed complexes.     

Quantification of curium isotopes in environmental samples: drawbacks,speciation and specific tracer

Journal of Radioanalytical and Nuclear Chemistry - In this study, drawbacks of the use of 243Am as a tracer in order to quantify curium isotopes during a complex chemical procedure were...     

Functional and site-specific macromolecular micelles as high potential drug carriers

Since several years, macromolecular micelles based on amphiphilic block copolymers have attracted much interest as drug carriers. These micelles show a long term blood circulation time resulting from their small diameter and the steric repulsion created by the poly(ethylene oxide) chains which constitute micelle corona, as well as from their high thermodynamic stability. Besides this long term blood circulation time generating a passive targeting, an active targeting, chemical or physical affinity targeting, might allow the preparation of more efficient drug carriers. In order to obtain such double targeting properties, we have prepared two kinds of macromolecular micelles. The first one is based on amphiphilic poly(ethylene oxide)/poly(β-benzyl -aspartate) ---PEO/PBLA--- block copolymers having hydroxy groups at the free end of PEO chains. As a result of their structure, such micelles have hydroxy groups on their outer-shell which can be further modified in order to introduce a targeting moiety (sugar, etc.). The characteristics (diameter, critical micellar concentration (cmc), drug loading capacity) have been determined. Moreover, doxorubicin loaded -hydroxy PEO/PBLA micelles have been shown to be slightly more cytotoxic than the corresponding -methoxy PEO/PBLA micelles. The second type of micelles is based on thermosensitive amphiphilic poly(N-isopropyl acrylamide)/polystyrene ---PIPAAm/PSt--- block copolymers. Such micelles have a small diameter and a low cmc in addition to thermosensitivity properties which are similar to those of PIPAAm.     

N-3 alkylation of uracils with unprotected amino alcohols using the Mitsunobu reaction

During our search for novel CGRP antagonists, we had great difficulty in accessing one of our key motifs. Herein, we communicate how we solved the problem by an unprecedented Mitsunobu alkylation using unprotected amino alcohols.     

Glycosyl‐Substituted Dicarboxylates as Detergents for the Extraction,Overstabilization, and Crystallization of Membrane Proteins

To tackle the problems associated with membrane protein (MP) instability in detergent solutions, we designed a series of glycosyl‐substituted dicarboxylate detergents (DCODs) in which we optimized the polar head to clamp the membrane domain by including, on one side, two carboxyl groups that form salt bridges with basic residues abundant at the membrane–cytoplasm interface of MPs and, on the other side, a sugar to form hydrogen bonds. Upon extraction, the DCODs 8 b , 8 c , and 9 b preserved the ATPase function of BmrA, an ATP‐binding cassette pump, much more efficiently than reference or recently designed detergents. The DCODs 8 a , 8 b , 8 f , 9 a , and 9 b induced thermal shifts of 20 to 29 °C for BmrA and of 13 to 21 °C for the native version of the G‐protein‐coupled adenosine receptor A_2AR. Compounds 8 f and 8 g improved the diffraction resolution of BmrA crystals from 6 to 4 Å. DCODs are therefore considered to be promising and powerful tools for the structural biology of MPs.     

Limit process of stationary TASEP near the characteristic line

The totally asymmetric simple exclusion process (TASEP) on\input amssym ${\Bbb Z}$ with the Bernoulli‐ρ measure as an initial condition, 0 < ρ < 1, is stationary. It is known that along the characteristic line, the current fluctuates at an order of t^1/3. The limiting distribution has also been obtained explicitly. In this paper we determine the limiting multipoint distribution of the current fluctuations moving away from the characteristics by the order t^2/3. The main tool is the analysis of a related directed last percolation model. We also discuss the process limit in tandem queues in equilibrium. © 2010 Wiley Periodicals, Inc.     

Observation of size-dependent thermalization in CdSe nanocrystals using time-resolved photoluminescence spectroscopy

We report heat dissipation times in semiconductor nanocrystals of CdSe. Specifically, a previously unresolved, subnanosecond decay component in the low-temperature photoluminescence decay dynamics exhibits longer decay lifetimes (tens to hundreds of picoseconds) for larger nanocrystals as well as a size-independent, ~25-meV spectral shift. We attribute the fast relaxation to transient phonon-mediated relaxation arising from nonequilibrium acoustic phonons. Following acoustic phonon dissipation, the dark exciton state recombines more slowly via LO-phonon assistance resulting in the observed spectral shift. The measured relaxation time scales agree with classical calculations of thermal diffusion, indicating that interfacial thermal conductivity does not limit thermal transport in these semiconductor nanocrystal dispersions.     

Efficient functionalizations of a pyranosido-pyrimidine scaffold

Efficient reaction conditions have been developed to prepare highly functionalized chiral pyranosido-pyrimidine by regioselective alkylation of the pyranoside ring and palladium-catalyzed cross-coupling reaction on the pyrimidine ring under microwave activation. Such scaffold contains three different functions suitable for selective derivatization and could find applications in the design of peptidomimetics.