Functional silica nanoparticles synthesized by water-in-oil microemulsion processes

Water-in-oil (W/O) microemulsion is a well-suitable confined reacting medium for the synthesis of structured functional nanoparticles of controlled size and shape. During the last decade, it allowed the synthesis of multi-functional silica nanoparticles with morphologies as various as core–shell, homogenous dispersion or both together. The morphology and properties of the different intermediates and final materials obtained through this route are discussed in the light of UV–Vis–NIR spectroscopy, dynamic light scattering (DLS) and X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and magnetometer SQUID analysis.     

Structural analysis of an unusual bioactive N-acylated lipo-oligosaccharide LOS-IV in Mycobacterium marinum

Although lipo-oligosaccharides (LOSs) are recognized as major parietal components in many mycobacterial species, their involvement in the host-pathogen interactions have been scarcely documented. In particular, the biological implications arising from the high degree of structural species-specificity of these glycolipids remain largely unknown. Growing recognition of the Mycobacterium marinum-Danio rerio as a specific host-pathogen model devoted to the study of the physiopathology of mycobacterial infections prompted us to elucidate the structure-to-function relationships of the elusive end-product, LOS-IV, of the LOS biosynthetic pathway in M. marinum. Combination of physicochemical and molecular modeling methods established that LOS-IV resulted from the differential transfer on the caryophyllose-containing LOS-III of a family of very unusual N-acylated monosaccharides, naturally present as different diastereoisomers. In agreement with the partial loss of pathogenecity previously reported in a LOS-IV-deficient M. marinum mutant, we demonstrated that this terminal monosaccharide conferred to LOS-IV important biological functions, including macrophage activating properties.     

Accumulative charge separation inspired by photosynthesis

Molecular systems that follow the functional principles of photosynthesis have attracted increasing attention as a method for the direct production of solar fuels. This could give a major carbon-neutral energy contribution to our future society. An outstanding challenge in this research is to couple the light-induced charge separation (which generates a single electron-hole pair) to the multielectron processes of water oxidation and fuel generation. New design considerations are needed to allow for several cycles of photon absorption and charge separation of a single artificial photosystem. Here we demonstrate a molecular system with a regenerative photosensitizer that shows two successive events of light-induced charge separation, leading to high-yield accumulation of redox equivalents on single components without sacrificial agents.     

Poly(ruthenium carbonyl spirobifluorenylporphyrin): a new polymer used as a catalytic device for carbene transfer

Oxidative electropolymerization of tetraspirobifluorenyl porphyrin ruthenium(II) carbonyl complexes can be used to coat Pt electrodes with polymeric films; after being removed from the electrode, these polymeric materials are able to catalyze the heterogeneous cyclopropanations and 2,3 sigmatropic rearrangements with ethyl diazoacetate.     

A spin transition molecular material with a wide bistability domain

[Fe(hyptrz)3](4-chloro-3-nitrophenylsulfonate)22 H2O (1; hyptrz=4-(3-hydroxypropyl)-1,2,4-triazole) has been synthesized and its physical properties have been investigated by several physical techniques including magnetic susceptibility measurements, calorimetry, and M?ssbauer, optical, and EXAFS spectroscopy. Compound 1 exhibits a spin transition below room temperature, together with a very wide thermal hysteresis of about 50 K. This represents the widest hysteresis loop ever observed for an FeII-1,2,4-triazole spin transition material. The cooperativity is discussed on the basis of temperature-dependent EXAFS studies and of the structural features of a CuII analogue. The EXAFS structural model of (1) in both spin states is compared to that obtained for a related material whose spin transition occurs above room temperature. EXAFS spectroscopy suggests that 1,2,4-triazole chain compounds retain a linear character whatever the spin state of the iron(II).     

Solid-state synthesis of boron subnitride, B6N: myth or reality?

Solid-state synthesis of boron subnitride, B₆N, as a result of chemical interaction between boron and boron nitride at 7.5 GPa and 1700 °C has been previously reported by Hubert et al. However, a critical analysis of the results has shown that the evidence for the formation of boron subnitride with B₆O-like structure is inconclusive. We have studied in situ the interaction between boron and BN at the same p–T conditions using X-ray diffraction with synchrotron radiation. At 7.4 GPa and 1700 °C the formation of a new phase has not been observed. At the same time, HP–HT treatment has resulted in strong and unpredictable preferred orientation of boron crystallites. This leads to the rise of some weak boron reflections that might be erroneously attributed to the appearance of a new phase. To cite this article: V.L. Solozhenko et al., C. R. Chimie 9 (2006).     

Computational methods for discrete hidden semi-Markov chains

We propose a computational approach for implementing discrete hidden semi-Markov chains. A discrete hidden semi-Markov chain is composed of a non-observable or hidden process which is a finite semi-Markov chain and a discrete observable process. Hidden semi-Markov chains possess both the flexibility of hidden Markov chains for approximating complex probability distributions and the flexibility of semi-Markov chains for representing temporal structures. Efficient algorithms for computing characteristic distributions organized according to the intensity, interval and counting points of view are described. The proposed computational approach in conjunction with statistical inference algorithms previously proposed makes discrete hidden semi-Markov chains a powerful model for the analysis of samples of non-stationary discrete sequences. Copyright © 1999 John Wiley & Sons, Ltd.