(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Additions of enantiopure alpha-sulfinyl carbanions to (S)-N-sulfinimines: asymmetric synthesis of beta-amino sulfoxides and beta-alphamino alcohols

The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.     

Segmentation under geometrical conditions using geodesic active contours and interpolation using level set methods

Let I: be a given bounded image function, where is an open and bounded domain which belongs to ⁿ. Let us consider n=2 for the purpose of illustration. Also, let S={x_i}_i be a finite set of given points. We would like to find a contour , such that is an object boundary interpolating the points from S. We combine the ideas of the geodesic active contour (cf. Caselles et al. [7,8]) and of interpolation of points (cf. Zhao et al. [40]) in a level set approach developed by Osher and Sethian [33]. We present modelling of the proposed method, both theoretical results (viscosity solution) and numerical results are given. AMS subject classification 49L25, 74G65, 68U10     

Detection of multicomponent signals: effect of difference in level between components

The detection of multicomponent signals for which the components are not equidetectable is precisely investigated as a function of the level difference ΔL(i∕j) between components. The detection thresholds are determined for a seven-tone complex signal with random starting phases masked by white noise. Level differences between the components are examined. A model for non-equidetectable conditions based on the statistical summation model is described. The improvement in detection is calculated from the level difference between components that is related to the thresholds for single components. The model predictions are in accordance with the experimental results.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

Approximation of surfaces with fault(s) and/or rapidly varying data, using a segmentation process, D m -splines and the finite element method

In many problems of geophysical interest, one has to deal with data that exhibit complex fault structures. This occurs, for instance, when describing the topography of seafloor surfaces, mountain ranges, volcanoes, islands, or the shape of geological entities, as well as when dealing with reservoir characterization and modelling. In all these circumstances, due to the presence of large and rapid variations in the data, attempting a fitting using conventional approximation methods necessarily leads to instability phenomena or undesirable oscillations which can locally and even globally hinder the approximation. As will be shown in this paper, the right approach to get a good approximant consists, in effect, in applying first a segmentation process to precisely define the locations of large variations and faults, and exploiting then a discrete approximation technique. To perform the segmentation step, we propose a quasi-automatic algorithm that uses a level set method to obtain from the given (gridded or scattered) Lagrange data several patches delimited by large gradients (or faults). Then, with the knowledge of the location of the discontinuities of the surface, we generate a triangular mesh (which takes into account the identified set of discontinuities) on which a D ^m -spline approximant is constructed. To show the efficiency of this technique, we will present the results obtained by its application to synthetic datasets as well as real gridded datasets in Oceanography and Geosciences.     

“Smart” nanomaterials for cancer therapy

Recent development in nanotechnology has provided new tools for cancer therapy and diagnostics. Because of their small size, nanoscale devices readily interact with biomolecules both on the cell surface and inside the cell. Nanomaterials, such as fullerenes and their derivatives, are effective in terms of interactions with the immune system and have great potential as anticancer drugs. Comparatively, other nanomaterials are able to load active drugs to cancer cells by selectively using the unique tumor environment, such as their enhanced permeability, retention effect and the specific acidic microenvironment. Multifunctional and multiplexed nanoparticles, as the next generation of nanoparticles, are now being extensively investigated and are promising tools to achieve personalized and tailored cancer treatments.     

Vibration sensitive behaviour of a connecting angle. Case of coupled beams and plates

In this paper semi-infinite one- and two-dimensional (1-D and 2-D) coupled structures are considered in order to find conditions under which coupling effects can induce hypersensitive vibrating behaviour. The approach is based on classical wave decomposition, and the first point is to show that high sensitivity can exist in such simple systems. Then, for the case of beams, it is shown that two critical coupling angles can be defined, and that their values depend only on wave number ratio. A similar study is then performed on semi-infinite coupled plates, and the existence of a critical coupling angle is shown. Its value can be determined using three structural parameters. The results are finally compared to finite coupled structures.