Energy-filtered electron microscopy for imaging core–shell nanostructures

CuAg core–shell nanoparticles are synthesized by ultra-high vacuum thermal evaporation. We show on this system how the Energy-Filtered Transmission Electron Microscopy (EFTEM) technique allows one to improve the characterization by precisely pointing out the formation of core–shell arrangements in bimetallic nanoparticle assemblies. A criterion to measure the shell thickness from EFTEM images on unique core–shell nanoparticles is defined, that can be used for core–shell nanoparticles of any sizes, with shell thicknesses over 1 nm. It is based on the intensity variation along a line drawn across a core–shell nanoparticle on a EFTEM image. This criterion has been validated by a close comparison of the shell thickness measurements performed in this work and the ones obtained by acoustic micro-Raman spectroscopy. Using this criterion, we report a strong correlation between the size of the Cu cores and the formation of the core–shell arrangements in the nanoparticle assembly studied in this work. The influence of the Cu core shape is also evidenced. The characterisation of such systems using High Resolution TEM (HRTEM) is also discussed.     

Chemoenzymatic synthesis of α-halogeno-3-octanol and 4- or 5-nonanols. Application to the preparation of chiral epoxides

A study of the microbiological reduction of different α-halogenoketones (4-chloro-3-octanone, 4-chloro-5-nonanone, 5-bromo-4-nonanone and 5-chloro-4-nonanone) with several strains of microorganism showed great difficulty in reducing ketone functions located in the middle of carbon chains. However, by choosing the appropriate microorganism, several enantiomerically pure diastereoisomers of the corresponding halohydrins have been obtained and were transformed into chiral epoxides.     

The rheological properties of the arterial wall

Key words The rheological properties of rat arteries were studied in vitro. Using intact arterial segments undergoing large deformations in longitudinal and circumferential direction, both the stress-strain relationship and the corresponding histological changes with deformation are presented. Correlations between the mechanical properties and the histological structure are discussed.     

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

Recent studies have demonstrated the biological importance of the interaction of nitric oxide with proteins such as cytochrome-c or hemoglobin. In particular, the possibility that the nitrosonium cation, NO(+), could reversibly bind to sulfide atom type was proposed. At pH values of biological relevance, nitrosation was proposed to occur through the action of NO(+) carriers such as nitrosothiols or nitrosamines. In this context, the gas phase chemistry of protonated nitrosothiols is studied in the present work by a combination of mass spectrometry and computational methods.     

A very promising piezoelectric property of Ta2O5 thin films. II: Birefringence and piezoelectricity

Birefringent and piezoelectric properties of Ta₂O₅ ceramic thin films of monoclinic and trigonal structures were analyzed. The birefringence, observed by reflected polarized light microscopy, yields information on thin film microstructures, crystal shapes and sizes and on crystallographic orientations of grains of trigonal structure. Such an information was considered for investigating piezoelectric properties by laser Doppler vibrometry and by piezoresponse force microscopy. The vibration velocity was measured by applying an oscillating electric field between electrodes on both sides of a Ta₂O₅ film deposited on a Si substrate which was pasted on an isolating mica sheet. In this case, it is shown that the vibration velocity results were not only from a converse piezoelectric effect, proportional to the voltage, but also from the Coulomb force, proportional to the square of the voltage. A huge piezoelectric strain effect, up to 7.6%, is found in the case of Ta₂O₅ of trigonal structure. From an estimation of the electrical field through the Ta₂O₅ thin film, this strain likely corresponds to a very high longitudinal coefficient d₃₃ of several thousand picometers. Results obtained by piezoresponse force microscopy show that trigonal grains exhibit a polarization at zero field, which is probably due to stress caused expansion in the transition monoclinic-trigonal, presented in a previous article (part I).     

Embedding of Biological Regulatory Networks and Property Preservation

In the course of understanding biological regulatory networks (BRN), scientists usually start by studying small BRNs that they believe to be of particular importance to represent a biological function, and then, embed them in a larger network. Such a reduction can lead to neglect relevant regulations and to study a network whose properties can be very different from the properties of this network viewed as a part of the whole. In this paper we study, from a logical point of view, on which conditions concerning both networks, properties can be inherited by BRNs from sub-BRNs. We give some conditions on the nature of the network embeddings ensuring that dynamic properties on the embedded sub-BRNs are preserved at the level of the whole BRN.     

Hierarchical structure in polymer‐based drug delivery systems as probed by calorimetric measurements

Thermoporosimetry (TPM), a differential scanning calorimetry technique that relies on the shift of transition temperatures caused by the confinement of liquids, was applied to elucidate the complex morphology of drug‐loaded polymeric microcapsules prepared by the emulsion solvent evaporation method. For the very first time, TPM has been applied simultaneously with two liquids as structural probes. It was found that Miglyol, which dissolves the selected drug (Ibuprofen), is confined inside vesicles having a mean radius of 26.3 nm, whereas water, which is the continuous phase, is trapped inside a swollen polymeric network of Eudragit with an average mesh radius of 1.7 nm. A proposed hierarchical structure is given, which predicts that Eudragit microcapsules are formed from a collection of inert oil vesicles partitioned by polymeric Eudragit membranes swollen by water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1939–1945, 2010     

Synthesis and complete assignment of the 1H and 13C NMR signals of new acetamido and aminoflavonoid derivatives

The complete ¹H and ¹³C NMR assignment of 9 acetamidochalcones, 18 acetamidoflavones, 18 aminoflavones, 9 acetamidoflavonols and 9 aminoflavonols has been performed using one‐ and two‐dimensional NMR techniques including COSY, HMQC and HMBC experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Glycine Dimers: Structure,Stability, and Medium Effects

We report a study on different ionization states and conformations of the bimolecular (Gly)₂ system by means of quantum mechanical calculations. Optimized geometries for energy minima of the glycine dimer, as well as relative energies and free energies were computed as a function of the medium: gas phase, nonpolar polarizable solvent, and aqueous solution. The polarizable continuum model was employed to account for solvation effects. Energy calculations were done using the MP2/aug‐cc‐pVTZ and B3LYP/6‐311+G(2df,2p) methods on B3LYP/6‐31+G(d,p) optimized structures (some single‐point energy calculations were also done using the B3PW91 and PBE1KCIS methods). Ionized forms of the glycine dimer (either zwitterion–zwitterion or neutral–zwitterion) are predicted to exist in all media, in contrast to amino acid monomers. In aqueous solution, dimerization is an exergonic process (?4 kcal mol^?1). Thus, according to our results, zwitterion–zwitterion Gly dimers might be abundant in supersaturated glycine aqueous solutions, a fact that has been connected with the structure of α‐glycine crystals but that remains controversial in the literature. Another noticeable result is that zwitterion–zwitterion interactions are substantially underestimated when computed using methods based on density functional theory. For comparison, some calculations for the dimer of the simplest chiral amino acid alanine were done as well and differences to the glycine dimer are discussed.