Pressure solution at the molecular scale

The topological evolution of the cleavage surface of a gypsum single crystal during its dissolution in a flowing undersaturated aqueous solution has been observed with an atomic force microscope. The matter transfer from solid to liquid proceeds through the migration of atomic steps. The step velocity has been measured and appears to depend on the force applied by the tip on the surface. Whereas the high force velocity enhancement is likely to stem from corrosive wear, the speed behavior at low force (<10 nN) differs drastically and can be interpreted as a consequence of the pressure solution of the crystal induced by the tip force. The step velocity evolution with the force obeys the known kinetic law of pressure solution. Hence these experiments enable us to evidence a first atomic mechanism at the origin of pressure solution.     

Joint acquisition-processing approach to optimize observation scales in noisy imaging

In imaging, the choice of an observation scale is conventionally settled by the operator in charge of the image acquisition, who is left alone with tuning the framing and zooming parameters of the imaging system. In a somewhat decoupled manner, the operator in charge of processing the data has access to the images after their acquisition, and seeks to extract information from the observed scene. This Letter proposes a manifestation of the interest of an alternative joint acquisition-processing approach. We demonstrate with quantitative informational measures how the choice of an observation scale can be directly related to the performance of the final information processing task. Illustrations are given with various tools from statistical information theory with possible applications of practical interest to any noisy imaging domains.     

Microfluidic Assisted Flash Precipitation of Photocrosslinkable Fluorescent Organic Nanoparticles for Fine Size Tuning and Enhanced Photoinduced Processes

Highly concentrated dispersions of fluorescent organic nanoparticles (FONs), broadly used for optical tracking, bioimaging and drug delivery monitoring, are obtained using a newly designed micromixer chamber involving high impacting flows. Fine size tuning and narrow size distributions are easily obtained by varying independently the flow rates of the injected fluids and the concentration of the dye stock solution. The flash nanoprecipitation process employed herein is successfully applied to the fabrication of bicomposite FONs designed to allow energy transfer. Considerable enhancement of the emission signal of the energy acceptors is promoted and its origin is found to result from polarity rather than steric effects. Finally, we exploit the high spatial confinement encountered in FONs and their ability to encapsulate hydrophobic photosensitizers to induce photocrosslinking. An increase in the photocrosslinked FON stiffness is evidenced by measuring the elastic modulus at the nanoscale using atomic force microscopy. These results pave the way toward the straightforward fabrication of multifunctional and mechanically photoswitchable FONs, opening novel opportunities in sensing, multimodal imaging, and theranostics.     

Sub-micromolar affinity of Escherichia coli NikR for Ni(II)

The dissociation constant of Ni(II) for Escherichia coli NikR was determined using three independent techniques, including binding kinetics, and shown to be in the sub-micromolar range.     

Discovery of a new series of jatrophane and lathyrane diterpenes as potent and specific P-glycoprotein modulators

A new series of diterpenes, the jatrophanes euphoscopin M (1), euphoscopin N (2) and euphornin L (3), and the lathyrane euphohelioscopin C (7) were isolated from plants of Euphorbia helioscopia L., together with four other known analogues, euphoscopin C (4), euphornin (5), epieuphoscopin B (6) and euphohelioscopin A (8). The new compound stereostructures were elucidated by NMR analysis and computational data. The resulting isolated diterpenes were found to be potent inhibitors of P-glycoprotein (ABCB1), while showing an absence of significant activity against BCRP (ABCG2), despite the high substrate overlapping of these transporters, thus including them in the third-generation class of specific multidrug transporter modulators.     

Multiple scattering from assemblies of dislocation walls in three dimensions. Application to propagation in polycrystals

The attenuation of ultrasound in polycrystalline materials is modeled with grain boundaries considered as arrays of dislocation segments, a model valid for low angle mismatches. The polycrystal is thus studied as a continuous medium containing many dislocation "walls" of finite size randomly placed and oriented. Wave attenuation is blamed on the scattering by such objects, an effect that is studied using a multiple scattering formalism. This scattering also renormalizes the speed of sound, an effect that is also calculated. At low frequencies, meaning wavelengths that are long compared to grain boundary size, then attenuation is found to scale with frequency following a law that is a linear combination of quadratic and quartic terms, in agreement with the results of recent experiments performed in copper [Zhang et al., J. Acoust. Soc. Am. 116(1), 109-116 (2004)]. The prefactor of the quartic term can be obtained with reasonable values for the material under study, without adjustable parameters. The prefactor of the quadratic term can be fit assuming that the drag on the dynamics of the dislocations making up the wall is one to two orders of magnitude smaller than the value usually accepted for isolated dislocations. The quartic contribution is compared with the effect of the changes in the elastic constants from grain to grain that is usually considered as the source of attenuation in polycrystals. A complete model should include this scattering as well.     

High sensitivity of diamond resonant microcantilevers for direct detection in liquids as probed by molecular electrostatic surface interactions

Resonant microcantilevers have demonstrated that they can play an important role in the detection of chemical and biological agents. Molecular interactions with target species on the mechanical microtransducers surface generally induce a change of the beam's bending stiffness, resulting in a shift of the resonance frequency. In most biochemical sensor applications, cantilevers must operate in liquid, even though damping deteriorates the vibrational performances of the transducers. Here we focus on diamond-based microcantilevers since their transducing properties surpass those of other materials. In fact, among a wide range of remarkable features, diamond possesses exceptional mechanical properties enabling the fabrication of cantilever beams with higher resonant frequencies and Q-factors than when made from other conventional materials. Therefore, they appear as one of the top-ranked materials for designing cantilevers operating in liquid media. In this study, we evaluate the resonator sensitivity performances of our diamond microcantilevers using grafted carboxylated alkyl chains as a tool to investigate the subtle changes of surface stiffness as induced by electrostatic interactions. Here, caproic acid was immobilized on the hydrogen-terminated surface of resonant polycrystalline diamond cantilevers using a novel one-step grafting technique that could be also adapted to several other functionalizations. By varying the pH of the solution one could tune the -COO(-)/-COOH ratio of carboxylic acid moieties immobilized on the surface, thus enabling fine variations of the surface stress. We were able to probe the cantilevers resonance frequency evolution and correlate it with the ratio of -COO(-)/-COOH terminations on the functionalized diamond surface and consequently the evolution of the electrostatic potential over the cantilever surface. The approach successfully enabled one to probe variations in cantilevers bending stiffness from several tens to hundreds of millinewtons/meter, thus opening the way for diamond microcantilevers to direct sensing applications in liquids. The evolution of the diamond surface chemistry was also investigated using X-ray photoelectron spectroscopy.     

Pressurizing conditions in helium-pressure-transmitting medium

We present quantitative measurements of the macroscopic non-hydrostatic stress and of the microscopic stress in samples compressed in a diamond anvil cell, using helium as a pressure-transmitting medium. These are based on the analysis of X-ray diffraction line shifts and widths. The macroscopic non-hydrostatic stress reaches 0.3–0.5 GPa at 150 GPa when the sample remains embedded in the pressure medium. The effect of this non-hydrostatic stress on the measured equations of state is estimated in the cases of gold, silver, molybdenum and copper. It is found to be negligible, except in the case of gold. We show that the analysis of the X-ray diffraction line shifts is a more sensitive way of detecting non-hydrostatic compression than the monitoring of the ruby luminescence signal. It can be used to detect when the sample is directly compressed between the diamond anvils. The sample geometry, in particular its thickness, has to be carefully chosen to prevent that situation.     

Synthesis of polycyclic aromatic hydrocarbon-based nanovehicles equipped with triptycene wheels

Two new nanovehicles that have extended aromatic platforms as the cargo zones have been obtained. Two strategies were considered for the formation of the perylene core from two naphthalene precursors. The first was based on a Scholl-type reaction involving an oxidant, and the second used a brominated derivative to perform a homocoupling reaction. The first strategy failed under diverse coupling conditions in the presence of several strong oxidants. Nevertheless, the use of CoF(3) in trifluoroacetic acid triggered a dimerization reaction between two ester groups of one molecule and the naphthalene unit of another, thereby surprisingly yielding a ten-membered carbon macrocycle. The second strategy encountered a lack of reactivity of the substrate under several homocoupling conditions. The dimerization was not easily performed but Ullmann-type conditions ultimately gave the expected product. The low yield and low solubility of the product encouraged us to modify our initial design. The synthesis of a new chassis that incorporated additional tert-butyl groups improved the solubility of the molecules and also prevented overcyclization of the aromatic platform by blocking these positions. Some p-phenylene spacers were also intercalated between the iodine and perylene centers to increase the reactivity of the halide towards coupling reactions. Two new chassis were obtained by Scholl-type oxidative coupling using FeCl(3) as the oxidant. The introduction of four triptycene wheels allowed the formation of the two corresponding nanovehicles.