Cyclic organohydroborate complexes of metallocenes: VIII. Triphenylsiloxy derivatives of Group IV organometallic systems, Cp2M(OSiPh3)X (M=Ti, Zr, Hf; X=Cl, {(μ-H)2BC8H14})

Group IV metallocene triphenylsiloxy chlorides, Cp₂MCl(OSiPh₃) (1, M=Ti; 2, M=Zr; 3, M=Hf), and cyclic organohydroborates, Cp₂M(OSiPh₃){(μ-H)₂BC₈H₁₄} (4, M=Zr; 5, M=Hf), were synthesized and characterized. The new hafnocene chloride derivative 3 was obtained by treating Cp₂HfCl₂ with triphenylsilanol and piperidine. The 18-electron cyclic organohydroborates 4 and 5 were afforded by reacting 2 and 3 with K[H₂BC₈H₁₄], the potassium salt of the 9-BBN dimer. Reaction of 1 with K[H₂BC₈H₁₄] causes reduction of the Ti(IV) center and produces the well-known Ti(III), 17-electron, paramagnetic dimer [Cp₂Ti(μ-Cl)₂TiCp₂] (6). Single-crystal X-ray diffraction structures of 3, 4, 5, and 6 were determined.     

Noncovalent functionalization of multi-walled carbon nanotubes by pyrene containing polymers

Multi-walled carbon nanotubes (MWNTs) have been solubilized in water and in various organic solvents by noncovalent side-wall functionalization by pyrene containing polymers.     

Sensitive determination of diuron on zinc oxide nanoparticles modified carbon paste electrode in soil and water samples

An electrochemical sensor based on Zinc oxide nanoparticles (ZnONPs) modified carbon paste electrode was designed for the toxic diuron pesticide detection. The ZnONPs were synthesized through the hydrothermal route and their structural properties were investigated via scanning electron microscopy (SEM) and X-ray diffraction powder (XRD). The designed ZnONPs-modified carbon paste electrode (ZnONPs-CPE) was characterized using cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly enhanced sensitivity on the diuron oxidation peak current, compared to the bare carbon paste electrode. Qualitative and quantitative analysis were performed using cyclic voltammetry (CV) and square wave voltammetry (SWV). Experimental parameters such as pH, amount of ZnONPs and frequency were evaluated and the optimized conditions were obtained with 0.1 M phosphate buffer solution at pH=8, a frequency of 50 Hz and a quantity of 5 mg of ZnONPs. Under these conditions, linear responses ranging from 1.3 to 7.7 μM and 8.6 to 30 μM of diuron were obtained, with correlation coefficients of R²=0.994 and 0.996 respectively. Detection and quantification limits of 0.22 μM and 0.84 μM (S/N=3) were respectively achieved based on the 3σ method. The interference of some ions on the oxidation peak of diuron on ZnONPs-CPE was also evaluated and no interference was observed, therefore demonstrating the selectivity of the sensor. The proposed sensor, designed with ecofriendly materials, is sensitive, selective and was effectively used for diuron determination in soils and water samples with recoveries ranging from 98 % to 101.5 %.     

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.     

Polymethylmethacrylate derivatives Eudragit E100 and L100: Interactions and complexation with surfactants

Precipitation or coprecipitation of polyelectrolytes has been largely investigated. However, the precipitation of polyelectrolytes via addition of charged and non‐charged surfactants has not been systematically studied and reported. Consequently, the aim of this work is to investigate the effect of different surfactants (anionic, cationic, non‐charged and zwitterionic) on the precipitation of cationic and anionic polymethylmethacrylate polymers (Eudragit). The surfactants effect has been investigated as a function of their concentration. Special attention has been dedicated to the CMC range and to the colloidal characterization of the formed dispersions. Moreover, the effect of salt (NaCl) and pH was also addressed. It is pointed out that non‐ionic and zwitterionic surfactants do not interact with charged Eudragit E100 and L100. For oppositely charged Eudragit E100/SDS and Eudragit L100/CTAB, precipitation occurs, and the obtained dispersions have been characterized in terms of particle size distribution and zeta potential. It was established that the binding of SDS molecules to Eudragit E100 polymer chains is made through the negative charges of the surfactant heads under the CMC value whereas binding of CTAB to Eudragit L100 chains is made at a CTAB concentration 5 times above its CMC. For Eudragit E100/SDS system, a more acidic medium induces aggregation. A same result was observed for the Eudragit L100/CTAB at a more basic pH. Moreover, it was observed that increasing salt concentration (higher than 100 mM) led to aggregation as generally observed for polycations/anionic surfactant systems.     

A Bistable Microelectromechanical System Actuated by Spin-Crossover Molecules

We report on a bistable MEMS device actuated by spin-crossover molecules. The device consists of a freestanding silicon microcantilever with an integrated piezoresistive detection system, which was coated with a 140 nm thick film of the [Fe(HB(tz)₃)₂] (tz=1,2,4-triazol-1-yl) molecular spin-crossover complex. Switching from the low-spin to the high-spin state of the ferrous ions at 338 K led to a reversible upward bending of the cantilever in agreement with the change in the lattice parameters of the complex. The strong mechanical coupling was also evidenced by the decrease of approximately 66 Hz in the resonance frequency in the high-spin state as well as by the drop in the quality factor around the spin transition.     

A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.     

Effective atom volumes for implicit solvent models: comparison between Voronoi volumes and minimum fluctuation volumes

An essential element of implicit solvent models, such as the generalized Born method, is a knowledge of the volume associated with the individual atoms of the solute. Two approaches for determining atomic volumes for the generalized Born model are described; one is based on Voronoi polyhedra and the other, on minimizing the fluctuations in the overall volume of the solute. Volumes to be used with various parameter sets for protein and nucleic acids in the CHARMM force field are determined from a large set of known structures. The volumes resulting from the two different approaches are compared with respect to various parameters, including the size and solvent accessibility of the structures from which they are determined. The question of whether to include hydrogens in the atomic representation of the solute volume is examined. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1857-1879, 2001     

Dispersive estimates and the 2D cubic NLS equation

We prove that the initial value problem for the 2D cubic semi-linear Schrödinger equation is well-posed in the Besov space B _0, ^∞2 (?²). For this, we rely on some new dispersive inequalities derived from bilinear restriction theorems.