Synthesis of isomerically pure anti-anthradithiophene derivatives

The regiospecific total synthesis and characterization of anti-isomers of 2,8-dialkylanthradithiophenes are described. The "anti" structure of the ADT derivatives is demonstrated by (13)C NMR as well as single crystal X-ray diffraction.     

Palladium-catalyzed regioselective C-S bond cleavage of thiophenes

Herein, a Pd-catalyzed reaction of simple and diverse bromothiophenes with alkynes via regioselective C-S bond activation is reported. This provides a new approach to prepare sulfur-based heterocycles and fulvenes.     

Folding of a supramolecular framework based on a tetrametallic clip driven by π-π interactions

Supramolecular extended frameworks based on a rotational molecular clip and having the same "primary structure" can exhibit either an unfolded or a folded framework. This process is driven by intramolecular π-π interactions, resulting in the formation of an infinite π-stacked column within the folded supramolecular framework.     

Influence of montmorillonite tactoid size on Na-Ca cation exchange reactions

The spatial organisation of swelling clay platelets in a suspension depends on the chemical composition of the equilibration solution. Individual clay platelets can be well dispersed, with surfaces entirely in contact with the external solution, or be stacked in tactoids, where part of the surfaces forms parallel alignments embedding interlayer water and cations. External and interlayer surfaces do not exhibit similar affinities for cations having different hydration and charge properties and the clay platelet stacking arrangement influences the clay affinity for these cations. This paper aims to establish the link between exchange properties and clay tactoid size and organisation for Na-Ca exchange on montmorillonite. Different montmorillonite samples behave differently with regards to Na-Ca exchange, from ideal to non-ideal exchange behaviour. A simple model coupling the tactoid stacking size to different Na/Ca relative affinities of the external and interlayer clay surfaces enables these differences to be reproduced.     

Optical Emission Spectroscopy Measurements and Simulation of Radioelement Volatility During Radioactive Waste Treatment by Plasma

An optical emission spectroscopy (OES) method has been used to measure the concentration above the melt of some radioelements, ¹³⁷Cs, ⁶⁰Co and ¹⁰⁶Ru during the vitrification of radioactive wastes by thermal plasma. This method allows the study of non homogeneous optically thin plasmas exhibiting a symmetry plane without sophisticated tomographic systems. Local plasma temperatures above the melt have been evaluated using measured relative intensities of spectral lines of the plasma-forming gas. Radioelement concentrations in the plasma are deduced from the intensity ratio of the radioelement–gas spectral lines. A computer model is used to simulate the volatility of ¹³⁷Cs, ⁶⁰Co and ¹⁰⁶Ru, during the treatment of radioactive wastes by thermal plasma. This model is based on the calculation of system composition using the free enthalpy minimization method, coupled with the equation of mass transfer at the reactional interface. In this study, the OES measurements and the computer model allowed the determination of this radioelement volatility depending on the parameters like plasma current, and the nature of atmosphere furnace. The results of the model are compared to those obtained by OES measurements.     

β-Cyclodextrin-based polycationic amphiphilic "click" clusters: effect of structural modifications in their DNA complexing and delivery properties

Monodisperse facial amphiphiles consisting of a β-cyclodextrin (βCD) platform exposing a multivalent display of cationic groups at the primary rim and bearing hydrophobic chains at the secondary oxygens have been prepared by implementing two very robust "click" methodologies, namely cuprous cation-catalyzed azide-alkyne cycloaddition (CuAAC) and thiourea-forming reaction. Most interestingly, the use of solid-supported Cu(I) catalysts was found to be very well suited for multiple CuAAC while facilitating purification of the C(7)-symmetric macromolecular triazole adducts. The strategy is compatible with molecular diversity-oriented approaches, which has been exploited to generate a small library of click polycationic amphiphilic CDs (paCDs) for assessing the influence of structural modifications in the ability to complex, compact, and protect pDNA and the efficiency of the resulting paCD:pDNA nanocomplexes (CDplexes) to deliver DNA into cells and promote transfection. The results indicate that fine-tuning the hydrophilic/hydrophobic balance is critical to achieve optimal self-assembling properties and stability of the resulting CDplexes in saline- and serum-containing media. Triazole-type paCDs were, in general, less efficient in promoting gene transfection than thiourea-type derivatives. Nevertheless, the current body of results support that the "dual click" approach implying sequential CuAAC and thiourea-forming reactions represents a versatile strategy to optimize the gene delivery capabilities of cyclodextrin-based facial amphiphiles.     

Photoinduced pH drops in water

A 2-hydroxyazobenzene platform has been evaluated to photorelease protons in aqueous solutions. Three different systems relying on molecular, supramolecular and polymeric strategies have been investigated in order to tune the water solubility and the thermodynamic and kinetic properties. This paper first reports on the syntheses and the physico chemical analyses for each system. Subsequently, we show that the three strategies are appropriate to reversibly photo-generate tunable pH drops in water up to one pH unit amplitude and at the 10-100 s timescale, upon transient illumination at 365 nm.