Direct evidence for highly organized networks of circular surface micelles of surfactant at the air-water interface

We report the first direct evidence for the formation of circular surface micelles (hemimicelles) on the surface of water. These highly monodisperse 30 nm hemimicelles, made from a semifluorinated alkane deposited as a Langmuir monolayer, form organized hexagonal arrays as determined by small-angle X-ray diffraction conducted directly on the water surface at grazing incidence.     

Isoperimetric monotonicity and isoperimetric inequalities of Payne-Rayner type for the first eigenfunction of the Helmholtz problem

Summary We use the auxiliary boundary value problemV+V+1=0 to get isoperimetric integral inequalities for the first eigenfunction of the Helmholtz problem.

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Résumé A l'aide du problème aux limitesV+V+1=0, on établit des inégalités isopérimétriques intégrales pour la première fonction propre du problème de Helmholtz.

     

Unveiling Carbon Dioxide and Ethanol Diffusion in Carbonated Water-Ethanol Mixtures by Molecular Dynamics Simulations

The diffusion of carbon dioxide (CO2) and ethanol (EtOH) is a fundamental transport process behind the formation and growth of CO2 bubbles in sparkling beverages and the release of organoleptic compounds at the liquid free surface. In the present study, CO2 and EtOH diffusion coefficients are computed from molecular dynamics (MD) simulations and compared with experimental values derived from the Stokes-Einstein (SE) relation on the basis of viscometry experiments and hydrodynamic radii deduced from former nuclear magnetic resonance (NMR) measurements. These diffusion coefficients steadily increase with temperature and decrease as the concentration of ethanol rises. The agreement between theory and experiment is suitable for CO2. Theoretical EtOH diffusion coefficients tend to overestimate slightly experimental values, although the agreement can be improved by changing the hydrodynamic radius used to evaluate experimental diffusion coefficients. This apparent disagreement should not rely on limitations of the MD simulations nor on the approximations made to evaluate theoretical diffusion coefficients. Improvement of the molecular models, as well as additional NMR measurements on sparkling beverages at several temperatures and ethanol concentrations, would help solve this issue.     

Reinvestigating the Preferential Enrichment of DL-Arginine Fumarate: New Thoughts on the Mechanism of This Far from Equilibrium Crystallization Phenomenon

Preferential enrichment (PE) is a crystallization process, starting from either a racemic of slightly enantio-enriched solution (ca. +5%) that results in a high enantiomeric excess in the liquid phase (>+90%ee) and a slight opposite excess in the deposited crystals (−2 to −5%ee). The mechanism(s) of this symmetry-breaking phenomenon is (are) still a matter of debate since it eludes rationalization by phase diagram formalism. In this publication, we thoroughly reinvestigate the PE phenomenon of arginine fumarate by using a new approach: the process is monitored by introducing isotopically labeled arginine enantiomers into the crystallization medium to better understand the mass exchanges during crystallization. These experiments are supported by chiral HPLC-MS/MS. This study permits re-evaluating the criteria that were thought mandatory to perform PE. In particular, we show that PE occurs by a continuous exchange between the solution and the crystals and does not require the occurrence of a solvent-mediated solid–solid phase transition.     

Pharmacomodulation of a ligand targeting the HBV capsid hydrophobic pocket

Hepatitis B virus (HBV) is a small enveloped retrotranscribing DNA virus and an important human pathogen. Its capsid-forming core protein (Cp) features a hydrophobic pocket proposed to be central notably in capsid envelopment. Indeed, mutations in and around this pocket can profoundly modulate, and even abolish, secretion of enveloped virions. We have recently shown that Triton X-100, a detergent used during Cp purification, binds to the hydrophobic pocket with micromolar affinity. We here performed pharmacomodulation of pocket binders through systematic modifications of the three distinct chemical moieties composing the Triton X-100 molecule. Using NMR and ITC, we found that the flat aromatic moiety is essential for binding, while the number of atoms of the aliphatic chain modulates binding affinity. The hydrophilic tail, in contrast, is highly tolerant to changes in both length and type. Our data provide essential information for designing a new class of HBV antivirals targeting capsid–envelope interactions.

Small-molecule binding to the Hepatitis B virus core protein hydrophobic pocket, a possible strategy for targeting viral particle assembly.     

A fast and low-cost dynamic calorimetric method for phase diagram estimation of binary systems

Journal of Thermal Analysis and Calorimetry - A dynamic calorimetric method based on infrared thermography has been used for the phase diagram estimation of binary systems of fatty organic...     

Detection of Frozen–Thawed Duck Fatty Liver by MALDI-TOF Mass Spectrometry: A Chemometrics Study

The marketing of poultry livers is only authorized as fresh, frozen, or deep-frozen. The higher consumer demand for these products for a short period of time may lead to the marketing of frozen–thawed poultry livers: this constitutes fraud. The aim of this study was to design a method for distinguishing frozen–thawed livers from fresh livers. For this, the spectral fingerprint of liver proteins was acquired using Matrix-Assisted Laser Dissociation Ionization-Time-Of-Flight mass spectrometry. The spectra were analyzed using the chemometrics approach. First, principal component analysis studied the expected variability of commercial conditions before and after freezing–thawing. Then, the discriminant power of spectral fingerprint of liver proteins was assessed using supervised model generation. The combined approach of mass spectrometry and chemometrics successfully described the evolution of protein profile during storage time, before and after freezing-thawing, and successfully discriminated the fresh and frozen–thawed livers. These results are promising in terms of fraud detection, providing an opportunity for implementation of a reference method for agencies to fight fraud.     

Bonding in Barium Boryloxides,Siloxides, Phenoxides and Silazides: A Comparison with the Lighter Alkaline Earths

Barium complexes ligated by bulky boryloxides [OBR₂]⁻ (where R=CH(SiMe₃)₂, 2,4,6-ⁱPr₃-C₆H₂ or 2,4,6-(CF₃)₃-C₆H₂), siloxide [OSi(SiMe₃)₃]⁻, and/or phenoxide [O-2,6-Ph₂-C₆H₃]⁻, have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ₂-X₁)(X₂)]₂ depends largely on the given pair of ligands X₁ and X₂. Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe₃)₂}₂)]⁻<[N(SiMe₃)₂]⁻<[OSi(SiMe₃)₃]⁻<[O(2,6-Ph₂-C₆H₃)]⁻<[OB(2,4,6-ⁱPr₃-C₆H₂)₂]⁻. This trend is the overall expression of 3 properties: steric constraints, electronic density and σ- and π-donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H−C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ₂-N(SiMe₃)₂}(OB{CH(SiMe₃)₂}₂)]₂ (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand-Ae bonding in all compounds. The ionic character of the Ae-ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ₂-X₁)(X₂)]₂ heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands.     

Two Years of Pesticides Monitoring in a Belgian Watershed

A monitoring study was carried out in 1998-1999 on a medium-sized (c. 4580 km²) watershed of the Dyle (or Dijle) river in central Belgium, composed of both rural and urbanized areas. This watershed may be considered as representative of a large part of the country. Samples were taken each month from seven sites along the course of the river, plus one from its major affluent the Demer. The eight molecules monitored were the main herbicides used on the major crops in the area, plus some used in nonagricultural sectors. The concentrations found were mostly in the 0-3 μg/L range, with some peaks between 3 and 14 μg/L. The averages over all spring and summer samples analyzed ranged from 0.14 (bentazone) to 1.54 μg/L (diuron). Time and space specific patterns could be observed.