Nanoscale mapping of plasmon resonances of functional multibranched gold nanoparticles

The optical response of multibranched gold nanoparticles is studied by means of electron energy-loss spectroscopy (EELS) in aberration corrected STEM mode. In every case the plasmon response is constant and variations in the maxima positions were found to be dependent on the branches aspect ratio. The good spatial resolution combined with the high energy resolution (0.18 eV) of the monochromated electron beam allows mapping the different plasmonic modes along the entire nanoparticles ranging from 0.7 eV up to 2.25 eV.     

Convex Quantum Logic

In this work we study the convex set of quantum states from a quantum logical point of view. We consider an algebraic structure based on the convex subsets of this set. The relationship of this algebraic structure with the lattice of propositions of quantum logic is shown. This new structure is suitable for the study of compound systems and shows new differences between quantum and classical mechanics. These differences are linked to the nontrivial correlations which appear when quantum systems interact. They are reflected in the new propositional structure, and do not have a classical analogue. This approach is also suitable for an algebraic characterization of entanglement and it provides a new entanglement criteria.     

Fluctuation Bounds for Chaos Plus Noise in Dynamical Systems

We are interested in time series of the form y _n =x _n +ξ _n where {x _n } is generated by a chaotic dynamical system and where ξ _n models observational noise. Using concentration inequalities, we derive fluctuation bounds for the auto-covariance function, the empirical measure, the kernel density estimator and the correlation dimension evaluated along y ₀,…,y _n , for all n. The chaotic systems we consider include for instance the Hénon attractor for Benedicks-Carleson parameters.     

Combining classification and regression approaches for the quantification of highly overlapping capillary electrophoresis peaks by using evolutionary sigmoidal and product unit neural networks

This is a study of the potential of neural networks built by using different transfer functions (sigmoidal, product and sigmoidal–product units) designed by an evolutionary algorithm to quantify highly overlapping electrophoretic peaks. To test this approach, two aminoglycoside antibiotics, amikacin and paramomycin, were quantified from samples containing either only one component or mixtures of them though capillary zone electrophoresis (CZE) with laser‐induced fluorescence (LIF) detection. The three models assayed used as input data the four‐parameter Weibull curve associated with the profile of the electrophoretic peak and in some cases the class label for each sample estimated by cluster analysis. The combination of classification and regression approaches allowed the establishment of straightforward network topologies enabling the analytes to be quantified with great accuracy and precision. The best models for mixture samples were provided by product unit neural networks (PUNNs), 4:4:1 (14 weights) for both analytes, after discrimination by cluster analysis, allowing the analytes to be quantified with great accuracy: 8.2% for amikacin and 5.6% for paromomycin within the standard error of prediction for the generalization test, SEP_G. For comparison, partial least square regression was also used for the resolution of these mixtures; it provided a minor accuracy: SEP_G 11.8 and 15.7% for amikacin and paramomycin, respectively. The reduced dimensions of the neural networks models selected enabled the derivation of simple quantification equations to transform the input variables into the output variable. These equations can be more easily interpreted from a chemical point of view than those provided by other ANN models. Copyright © 2007 John Wiley & Sons, Ltd.     

Encapsulation of Tetraazaannulenato Compounds in Matrix by Sol-Gel Process

The hybrid organic-inorganic catalyst constituted by {5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraaza[14]annulenato} nickel (II), NiTMTAA, encapsulated in an alumina matrix has been prepared. NiTMTAA was synthesized by the reaction of nickel acetate with o-phenylenediamine in the presence of 2,4-pentanedione under argon atmosphere. The alumina hybrid material was obtained by a non hydrolytic sol-gel route, through the condensation of aluminum chloride with diisopropylether in the presence of NiTMTAA. The material has been prepared through precipitation from a gel. Characterization of the alumina hybrid material has been performed by ultra violet-visible spectroscopy, electron spectroscopic imaging, surface area, atomic absorption, infrared spectroscopy, and thermogravimetric analysis. The ultra violet-visible absorption spectrum of the hybrid material has bands characteristic of the NiTMTAA compound showing that the structure of NiTMTAA has been preserved in the hybrid material. The new material has a surface area of 300 m²/g. The electron image was that of a non-crystalline microstructure. Comparison between the leaching of NiTMTAA from NiTMTAA adsorbed on commercial neutral alumina confirm that in the non-hydrolytic materials the NiTMTAA is entrapped and not only adsorbed on the alumina surface. The use of conventional hydrolytic sol-gel process leads to the complete leaching of NiTMTAA from matrix, underlining the importance of the non-hydrolytic alumina gel process in the matrix preparation. The new catalysts prepared were tested for their ability to catalyze the epoxidation of (Z)-cyclooctene using iodosylbenzene as oxygen donor, giving moderate yields in the epoxidation (40%), while the homogeneous NiTMTAA is inactive due to NiTMTAA bleaching. These results emphasize the effect of the non-hydrolytic alumina matrix to prevent chemical degradation of NiTMTAA.     

Comparative study of 2‐amino and 3‐aminobenzoic acid copolymerization with aniline synthesis and copolymer properties

Polyanilines soluble in an aqueous basic medium were synthesised by copolymerization of aniline (ANI) with both 2 and 3‐aminobenzoic acids (ABA). Different composition copolymers were prepared by varying the ANI/ABA feed ratio. Poly(aniline‐co‐2‐aminobenzoic acid) (PANI2ABA) and poly(aniline‐co‐3‐aminobenzoic acid) (PANI3ABA) displayed differences in their properties, such as specific charge and fluorescence behavior because the reactivity of 2‐aminobenzoic (2ABA) and 3‐aminobenzoic (3ABA) acids are very different. The new materials were characterized by X‐ray photoelectron, Fourier transform infrared, and Raman spectroscopies. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5587–5599, 2004     

Onμ-recurrent nonsingular endomorphisms

We show that the Maharam skew product ofμ-recurrent nonsingular endomorphisms is conservative and give some applications. Among them is the construction of a conservative ergodic invertible natural extension forμ-recurrent ergodic nonsingular endomorphisms. Supported in part by a Williams College Faculty Research Grant.     

Overview of optical techniques that measure displacements: Murray lecture

Optical techniques that measure displacements play a very important role in current experimental mechanics, material sciences and metrology. This paper presents a survey of developments in these techniques from a personal experience point of view. Three main aspects are considered. Mathematical and numerical models used in the interpretation of fringe information and the corresponding data processing techniques. Optical and electro-optical developments that have taken place to improve the sensitivity, and the efficiency of these methods to make them competitive with purely numerical methods. Applications that have arisen from the synergy between advanced computational capabilities and optics are also presented.