Asymmetric catalytic hydrogenation. Design of new Ru catalysts and chiral ligands: from laboratory to industrial applications

This Account covers the design of Ru catalysts and ligands. Two classes of chiral phosphine ligands are prepared: the electron-rich trans-2,4-substituted phosphetanes, readily available from optically pure 1,3-diol cyclic sulfates, and atropoisomeric ligands (SYNPHOS, MeO-NAPhePHOS, bearing heterotopic biaryl moieties, and a chiral water-soluble diguanidinium binaphthyl diphosphine, Digm-BINAP). Applications of these ligands to rhodium- and ruthenium-mediated hydrogenation of ketones and olefins have been reported with high enantioselectivities. The recognition abilities of Ru-SYNPHOS for a wide range of ketones is superior to those observed with BINAP, MeO-NAPhePHOS, and MeO-BIPHEP. Several biologically active compounds have been prepared through dynamic kinetic resolution. This work gives access to a number of highly active catalysts of the type [Ru(biphosphane)(H)(eta(6)-cot)]BF(4). These catalysts have demonstrated their utility in the enantioselective hydrogenation of the tetrasubstituted cyclopentenone "dehydrodione", which leads to the commercially important perfume component Paradisone (Firmenich).     

Various issues relating to computational fluid dynamics simulations of carotid bifurcation flow based on models reconstructed from three-dimensional ultrasound images

Computational fluid dynamics (CFD) flow simulation techniques have the potential to enhance understanding of how haemodynamic factors are involved in atherosclerosis. Recently, three-dimensional ultrasound has emerged as an alternative to other three-dimensional imaging techniques, such as magnetic resonance angiography (MRA). The method can be used to generate accurate vascular geometry suitable for CFD simulations and can be coupled with Doppler ultrasound to provide physiologically realistic flow boundary conditions. However, there are various ways to utilize the flow data acquired, possibly leading to different results regarding both flow and wall shear stress patterns. A disadvantage of three-dimensional ultrasound for imaging the carotid bifurcation has been established as being the scanning limitation of the jawbone position. This may make artificial extensions of the internal and/or external carotid arteries necessary, which in turn may influence the predicted flow patterns. Flow simulations were carried out for three outflow calculation schemes as well as four geometries with different extensions to the carotid daughter vessels. It was found that variation of flow patterns was more strongly influenced by the outflow conditions than by the extensions of the daughter vessels. Consequently, it is recommended that for future CFD simulations of carotid flow using three-dimensional ultrasound data, the outflow boundary conditions should rely on the most accurate measurement available, and flow data recorded in the common and internal carotid are considered more reliable than data from the external carotid. Even though the extended lengths of the daughter vessels have insignificant effects on the predicted haemodynamic parameters, it would be a safer option to extend the internal carotid by approximately three times the diameter of the common carotid artery.     

High resolution processing techniques for ultrasound doppler velocimetry in the presence of colored noise. Part II: Multiplephase pipe-flow velocity measurement

For pt.I see ibid., vol.50, no.3, p.267-78 (2003). This paper presents an application of continuous wave ultrasound Doppler velocity measurements to two-phase flow in pipes. In many petroleum wells, the multiphase flow is separated into two phases: the first is a liquid phase and the second is a gas phase with small scatterers. The problem of multiphase velocity profile measurements has not been satisfactorily solved by classical approaches due to the multiphase nature of the fluid and the presence of colored noise, which introduces a significant bias in classical frequency estimators. We propose the use of resolution frequency techniques to overcome the classical limitations. Direct estimation of Doppler frequency then obtained using either time frequency maximum frequency or arguments of poles of the parametric model that identifies the Doppler part of the signal is discussed. The tests made with synthetic Doppler signals and two-phase flow have demonstrated the excellent performance of the high resolution techniques based on reassignment and parametric techniques.     

Polarization independence of a one-dimensional grating in conical mounting

We demonstrate theoretically a polarization-independent guided-mode resonant filter with only a one dimensional grating. A rigorous method, the modal method by Fourier expansion, is used to compute the diffracted efficiencies of the grating. Wave-vector analysis fails to correctly design a polarization-independent structure. We show that a rigorous analysis of the resonances must be employed to obtain such a device; using a pole approach, we study the effects of grating parameters on the resonances of both polarizations.     

Modeling Human Judgment of Digital Imagery for Multimedia Retrieval

The application of machine learning techniques to image and video search has been shown to boost the performance of multimedia retrieval systems, and promises to lead to more generalized semantic search approaches. In particular, the availability of large training collections allows model-driven search using a substantial number of semantic concepts. The training collections are obtained in a manual annotation process where human raters review images and assign predefined semantic concept labels. Besides being prone to human error, manual image annotation is biased by the view of the individual annotator because visual information almost always leaves room for ambiguity. Ideally, several independent judgments are obtained per image, and the inter-rater agreement is assessed. While disagreement between ratings bears valuable information on the annotation quality, it complicates the task of clearly classifying rated images based on multiple judgments. In the absence of a gold standard, evaluating multiple judgments and resolving disagreement between raters is not trivial. In this paper, we present an approach using latent structure analysis to solve this problem. We apply latent class modeling to the annotation data collected during the TRECVID 2005 Annotation Forum, and demonstrate how to use this statistic to clearly classify each image on the basis of varying numbers of ratings. We use latent class modeling to quantify the annotation quality and discuss the results in comparison with the well-known Kappa inter-rater agreement measure.     

High pass filter with above IC integrated SrTiO3 high K MIM capacitors

This paper describes realization and characterization of SrTiO₃ (STO) high K MIM capacitors above BiCMOS integrated circuit (IC). These capacitances are connected to IC and are used as coupling capacitors in order to realize a high pass filter. Surface capacitance achieved is 10 nF/mm² with capacitance value of 1.2 nF. The process for STO MIM fabrication does not exceed 400 °C, which is compatible with interconnections. Typical K and dielectric losses values obtained are, respectively 110% and 2%. Yield obtained reaches 83% for capacitors. A functional high pass filter using these STO capacitors was realized in this study. It exhibits a cut-off frequency at 6.5 kHz and a constant gain at higher frequencies of −1.3 dB.     

The MISTIGRI thermal infrared project: scientific objectives and mission specifications

This article presents the MISTIGRI project of a microsatellite developed by the French space agency Centre National d'Etudes Spatiales (CNES) in cooperation with Spain (Image Processing Laboratory of the University of Valencia and Centro para el Desarrollo Tecnológico Industrial (CDTI)). MISTIGRI is a mission that has the originality of combining a high spatial resolution (～50 m) with a daily revisit in the thermal infrared (TIR). MISTIGRI is an experimental mission devoted to demonstrate the potential of such TIR data for future operational missions. The scientific goals and expected applications of the mission are described: they encompass the monitoring of (i) agricultural areas and related hydrological processes, (ii) urban areas, and (iii) coastal areas and continental waters. Then, the specifications on spatial resolution, revisit frequency, overpass time, and spectral configuration are justified. The strategy of the mission is based on the combination with a network of long-term experimental sites. It will also make possible observing some areas facing rapid climatic change. The choice of the orbit is presented. Finally, we give rapid overviews of both the instrumental concept and the proposed mission architecture.     

Nanomaterials based on phosphorus dendrimers

Dendrimers constitute an increasingly important field of research in chemistry for more than 15 years. After pioneering works concerning synthesis, the interest in dendrimers is now mainly driven by their properties and applications. This Account will emphasize the properties of a special class of dendrimers, that is, phosphorus-containing dendritic macromolecules, as tools for the elaboration of nanomaterials. Indeed, these dendrimers can be considered themselves as materials, or they can be used as an intrinsic constituent of a material or as a modifier of the surface of a material. In this latter case, a fundamental work about surfaces covalently modified by dendrimers recently opened the way to the elaboration of DNA chips.     

2-Methylthiazolidine and 4-ethylguaiacol,male sex pheromone components of the cockroachNauphoeta cinerea (dictyoptera,blaberidae): A reinvestigation

InNauphoeta cinerea, male calling behavior is associated with sex pheromone release by the sternal glands. The male pheromone that attracts females from a distance is a mixture of 2-methylthiazolidine and 4-ethylguaiacol. It is active at very low concentrations, 0.05 and 0.01 ng, respectively. Two other compounds, 3-hydroxy-2-butanone and 2-methyl-2thiazoline, act at close range, keeping the female in the vicinity of the male. The function of the volatile pheromone and those of previously described contact pheromones are discussed in regard to their possible involvement in the establishment of male dominant-subordinate relationships.     

Fermentation by Amylolytic Lactic Acid Bacteria and Consequences for Starch Digestibility of Plantain, Breadfruit, and Sweet Potato Flours

The potential of tropical starchy plants such as plantain (Musa paradisiaca), breadfruit (Artocarpus communis), and sweet potato (Ipomoea batatas) for the development of new fermented foods was investigated by exploiting the capacity of some lactic acid bacteria to hydrolyze starch. The amylolytic lactic acid bacteria (ALAB) Lactobacillus plantarum A6 and Lactobacillus fermentum Ogi E1 were able to change the consistency of thick sticky gelatinized slurries of these starchy fruits and tubers into semiliquid to liquid products. Consequently, a decrease in apparent viscosity and an increase in Bostwick flow were observed. These changes and the production of maltooligosaccharides confirmed starch hydrolysis. Sucrose in sweet potato was not fermented by strain A6 and poorly fermented by strain Ogi E1, suggesting possible inhibition of sucrose fermentation. In all 3 starchy plants, rapidly digestible starch (RDS) was higher than slowly digestible starch (SDS) and resistant starch (RS) represented between 17% and 30% dry matter (DM). The digestibility of plantain was not affected by fermentation, whereas the RDS content of breadfruit and sweet potato decreased and the RS content increased after fermentation. Practical Application: The characteristics resulting from different combinations of gluten free starchy plants (plantain, breadfruit, sweet potato) and amylolytic lactic acid bacteria (ALAB) offer opportunities to develop new functional fermented beverages, mainly for breadfruit and sweet potato, after further investigation of their formulation, sensory attributes, nutritional, and prebiotic characteristics.