Modulating the framework negative charge density in the system [BDT-TTP*+]/[Re6S5Cl9(1-)]/[Re6(S/Se)6Cl8(2-)]/[Re6S7Cl7(3-)]: templating by isosteric cluster anions of identical symmetry and shape, variations of incommensurate band filling, and electronic structure in 2D metals

A series of 2D metals, beta-(BDT-TTP)6[Re6Se6Cl8] x (CHCl2-CHCl2)2, 2; beta-(ST-TTP)6[Re6S6Cl8] x (CH2Cl-CHCl2)2, 3; beta-(BDT-TTP)7[Re6S6Cl8]0.5[Re6S7Cl7]0.5 x (CH2Cl2), 4; beta-(BDT-TTP)7[Re6Se6Cl8]0.5[Re6S7Cl7]0.5 x (CH2Cl2), 5; beta-(BDT-TTP)8[Re6S7Cl7] x (CH2Cl2)4, 6 (BDT-TTP and ST-TTP are 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene and 2-(1,3-diselenol-2-ylidene)-5(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene, respectively) is reported to have one single beta-slab layered topology despite successive increases of the cluster anion negative charge. The charge density within the templating composite inorganic-neutral molecule slab is shown to remain above a threshold of ca. one negative charge per square nanometer, that is, for cluster anions with two negative charges and higher. Conversely, discrete stacks are shown to be stabilized instead in the semiconducting salts (BDT-TTP)2[Re6S5Cl9], 1 where the cluster anion bears one negative charge only. The electronic structure of salts 2-6 is shown to be very stable and kept almost intact across the series. The templating strategy is shown to fulfill its anticipated potential for deliberate installment of incommensurate band fillings in molecular metals. The deliberate admixture of the 6:1 and 8:1 structures yields novel phases with a 7:1 stoichiometry with the anticipated crystal and electronic structures. The action at the organic-inorganic interface triggered by changing the anion charge yet keeping its shape and volume identical, which ultimately governs the shape of the unit cell, is of paramount importance in defining the Fermi surface of these metallic salts. The present BDT-TTP salts thus provide a series of materials with strongly related but subtly different Fermi surfaces worthy of many physical studies. Shubnikov-de Haas measurements are expected to be particularly interesting since they are especially sensitive to the details of the Fermi surface.     

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.     

High-throughput simultaneous detection of point mutations and large-scale rearrangements by CE

The detection of unknown mutations is important both in population genetics research and in diagnosis. At present, two different methods must be used to detect either point mutations or large-scale genetic rearrangements, which is costly and time-consuming. We describe here a new method for the simultaneous detection of these two types of mutations. It is based on electrophoretic heteroduplex analysis (HDA) using enhanced mismatch mutation analysis (EMMA) and semiquantitative multiplexed PCR conditions. The use of such conditions allows the simultaneous search of any kind of mutation in up to five different fragments per capillary, in a single or multi-CE system. The method was validated on patient samples with mutations in the breast predisposition gene BRCA1. It leads to highly reliable and high-throughput mutation detection at low cost, as compared with classical methods.     

Rheological characterisation of bis-urea based viscoelastic solutions in an apolar solvent

The rheological properties of hydrogen bonded reversible aggregates in apolar solvent have been investigated. The zero shear viscosity, the plateau modulus and the terminal viscoelastic relaxation time exhibit power laws dependencies with the concentration that have been compared with the behaviours expected for reversible polymers. It appears that the dynamics originate from scission/recombination mechanisms. Moreover, the growth of the aggregates with concentration follows the laws observed and predicted for worm-like micelles at low concentrations allowing the length of the aggregates to be estimated 500 nm at 3 g L(-1). However, at the highest concentrations investigated, deviations from the power laws suggest the presence of some intrinsic chain stopper poisons in the solutions.     

Interactions between poloxamers in aqueous solutions: micellization and gelation studied by differential scanning calorimetry, small angle X-ray scattering, and rheology

Poloxamers F88 (EO97PO39EO97) and P85 (EO27PO39EO27) are triblock copolymers of ethylene oxide (EO) and propylene oxide (PO), which have the same hydrophobic PO block. We studied aqueous solutions of these two copolymers by the conjoint use of differential scanning calorimetry (DSC), rheology, and small-angle X-ray scattering (SAXS). The results showed that the temperature-induced micellization of aqueous solutions of F88 and P85 was a progressive process followed by gelation for sufficiently concentrated samples. Gelation was due to the ordered packing of micelles under a hexagonal compact (HC) structure for P85 and a body-centered cubic (BCC) phase for F88. Importantly, the phase diagram of F88/P85 mixtures in water was elucidated and showed the destabilization of the HC phase upon addition of small amounts of F88.     

Determination of real-time predictors of the wind turbine wake meandering

The present work proposes an experimental methodology to characterize the unsteady properties of a wind turbine wake, called meandering, and particularly its ability to follow the large-scale motions induced by large turbulent eddies contained in the approach flow. The measurements were made in an atmospheric boundary layer wind tunnel. The wind turbine model is based on the actuator disc concept. One part of the work has been dedicated to the development of a methodology for horizontal wake tracking by mean of a transverse hot wire rake, whose dynamic response is adequate for spectral analysis. Spectral coherence analysis shows that the horizontal position of the wake correlates well with the upstream transverse velocity, especially for wavelength larger than three times the diameter of the disc but less so for smaller scales. Therefore, it is concluded that the wake is actually a rather passive tracer of the large surrounding turbulent structures. The influence of the rotor size and downstream distance on the wake meandering is studied. The fluctuations of the lateral force and the yawing torque affecting the wind turbine model are also measured and correlated with the wake meandering. Two approach flow configurations are then tested: an undisturbed incoming flow (modelled atmospheric boundary layer) and a disturbed incoming flow, with a wind turbine model located upstream. Results showed that the meandering process is amplified by the presence of the upstream wake. It is shown that the coherence between the lateral force fluctuations and the horizontal wake position is significant up to length scales larger than twice the wind turbine model diameter. This leads to the conclusion that the lateral force is a better candidate than the upstream transverse velocity to predict in real time the meandering process, for either undisturbed (wake free) or disturbed incoming atmospheric flows.     

EPR, NMR, and Thermodynamic Evidences for Forced Nuclear Spin–Electron Spin Interactions in the Case of 1-Phenyl-2-Methylpropyl-1,1-Dimethyl-2-Nitroxide (TIPNO) Attached to Permethylated β-Cyclodextrin

In a recent paper (Bardelang et al. in J Org Chem 71:7657–7667, 2006), the deep inclusion of the TIPNO (1-phenyl-2-methylpropyl-1,1-dimethylethyl-2-nitroxide) free radical attached to a permethylated β-cyclodextrin (TRIMEB) into its cavity was questioned. In the present paper it is shown that the results of X-band and W-band electron paramagnetic resonance (EPR) and ¹H nuclear magnetic resonance (NMR) studies of the TIPNO–TRIMEB in the presence of competitors of complexation (1-adamantanol, methyl orange and 1-adamantylamine) are consistent with a situation where the nitroxide is capping the small cavity entrance. The inclusion of the incoming guest was proven by ¹H NMR, whereas no changes in EPR spectra were noticed whatever the competitors’ concentrations. These observations are rationalized in terms of an equilibrium between a nitroxide-capped cyclodextrin (weak complex) and a non-self included form, both species involving competitors’ inclusion without significant EPR spectral changes. These results not only confirm our preliminary findings, but also point out to the peculiar role of the cyclodextrin methoxy crown of the primary rim stabilizing the appended guest by means of weak interactions.     

A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction

Mono-, di-, tri- and tetra-functional organotin compounds were easily prepared in a sonicated Barbier reaction using ultrasound technology via coupling reaction of organo halides with tin halides (Bu₃SnCl, Bu₂SnCl₂, BuSnCl₃, SnCl₄) mediated by magnesium metal. The di- and tri-functional organotin compounds were tested in a Stille cross-coupling reaction in order to ascertain how many groups were transferred.     

MIL-96, a porous aluminum trimesate 3D structure constructed from a hexagonal network of 18-membered rings and mu3-oxo-centered trinuclear units

A new aluminum trimesate Al12O(OH)18(H2O)3(Al2(OH)4)[btc]6.24H2O, denominated MIL-96, was synthesized under mild hydrothermal conditions (210 degrees C, 24 h) in the presence of 1,3,5-benzenetricarboxylic acid (trimesic acid or H3btc) in water. Hexagonal crystals, allowing a single-crystal XRD analysis, are grown from a mixture of trimethyl 1,3,5-benzenetricarboxylate (Me3btc), HF, and TEOS. The MIL-96 structure exhibits a three-dimensional (3D) framework containing isolated trinuclear mu3-oxo-bridged aluminum clusters and infinite chains of AlO4(OH)2 and AlO2(OH)4 octahedra forming a honeycomb lattice based on 18-membered rings. The two types of aluminum groups are connected to each other through the trimesate species, which induce corrugated chains of aluminum octahedra, linked via mu2-hydroxo bonds with the specific -cis-cis-trans- sequence. The 3D framework of MIL-96 reveals three types of cages. Two of them, centered at the special positions 0 0 0 and 2/3 1/3 1/4, have estimated pore volumes of 417 and 635 A3, respectively, and encapsulate free water molecules. The third one has a smaller pore volume and contains disordered aluminum octahedral species (Al(OH)6). The solid-state NMR characterization is consistent with crystal structure and elemental and thermal analyses. The four aluminum crystallographic sites are resolved by means of 27Al 3QMAS technique. This product is able to sorb both carbon dioxide and methane at room temperature (4.4 mmol.g(-1) for CO2 and 1.95 mmol.g(-1) for CH4 at 10 bar) and hydrogen at 77 K (1.91 wt % under 3 bar).