Towards Polyoxometalate‐Cluster‐Based Nano‐Electronics

We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO₂, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom‐built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non‐volatile molecular memories (NVMM) or flash‐RAM.     

Evaluation of viscoelastic constants of metallic materials by laser-ultrasonics at elevating temperature

The main objective of this study is the determination of elastic moduli and viscosity coefficients of metals at elevating temperature up to melting point. More specifically, it involves the analysis of the propagation of acoustic waves generated and detected simultaneously by laser-ultrasonic for the measurement of longitudinal and shear velocities. This preliminary work primarily concerns Tin (Sn) metal known for its low melting point and attenuation coefficient.     

Electrically induced flows in the vicinity of a dielectric stripe on a conducting plane

We report a theoretical and experimental study of the hydrodynamic flow induced by an a.c. electric field in the vicinity of a dielectric stripe deposited on a conducting plate. In the theoretical part, we model the stripe as a small change of the surface capacitance of the plate, and a perturbative approach is used to perform the calculations. This approach predicts an outwards rectified electro-osmotic slip along the surface that generates two steady counter-rotating rolls, the size of which decreases with the frequency. In the experimental section, we use tracers to determine the structure of the flow and investigate its dependence on the frequency and the amplitude of the applied voltage. The structure and amplitude of the observed flow compares satisfactorily with the theoretical analysis. This could guide the design of surface-controlled flows and help to understand the collective behavior of colloids near electrodes. Received 20 June 2002 RID="a" ID="a"e-mail: nadal@crpp.u-bordeaux.fr     

Synthesis of vulpinic acids from dimethyl tartrate

A series of vulpinic acids differing by the aryl or heteroaryl groups placed in the ester α-position were prepared by Suzuki-Miyaura cross-coupling involving a common iodide and the corresponding aryl boronates. The preparation of the iodide precursor from (+)-dimethyl l-tartrate required four steps: the esterification of one hydroxyl group, a Dieckmann cyclization allowing the construction of the tetronic acid moiety, a dehydration leading to the installation of the exocyclic double bond and lastly, an N-iodosuccinimide-mediated iodation of the alkene obtained.     

Towards the Accurate Calculation of 183W NMR Chemical Shifts in Polyoxometalates: The Relevance of the Structure

DFT calculations were carried out to study ¹⁸³W NMR chemical shifts in the family of the Keggin anions with formula α‐[XW₁₂O₄₀]^q? (X=B, Al, Si, P, Ga, Ge, As, Zn), in the β‐ and γ‐[SiW₁₂O₄₀]^4? geometric isomers, in the derivative Dawson anion [P₂W₁₈O₆₂]^6?, and in the most symmetrical Lindqvist [W₆O₁₉]^2? anion and its derivative [W₁₀O₃₂]^4?. In this article, we show that the geometry employed in the calculation of NMR chemical shifts in polyoxotungstates is extremely important if we want to be quantitative. Using very large basis sets of QZ4P quality and taking into account the conductor‐like screening model (COSMO) to account for solvent effects (aqueous and organic solutions), good geometries were found for the polyoxoanions. From these optimal geometries the ¹⁸³W NMR chemical shifts were computed with the more standard basis sets of TZP quality and including spin–orbit corrections inside the zero‐order regular approximation (ZORA) to describe the relativistic effects of the internal electrons. With this strategy the mean absolute error between experimental and theoretical values was found to be less than 10 ppm, which is similar to the experimental error. We also discuss how the geometry of the polyoxoanion influences on the shielding.     

Electron cotunneling transport in gold nanocrystal arrays

We describe current-voltage (I-V) characteristics of alkyl-ligated gold nanocrystals ~5 nm arrays in a long screening length limit. Arrays with different alkyl ligand lengths have been prepared to tune the electronic tunnel coupling between the nanocrystals. For long ligands, electronic diffusion occurs through sequential tunneling and follows activated laws, as a function of temperature σ∝e(-T(0)/T) and as a function of electric field I∝e(-E(0)/E). For better conducting arrays, i.e., with small ligands, the transport properties cross over to the cotunneling regime and follow Efros-Shklovskii laws as a function of temperature σ∝e(-(T(ES)/T)(1/2) and as a function of electric field I∝e(-(E)(ES)/E)(1/2). The data show that electronic transport in nanocrystal arrays can be tuned from the sequential tunneling to the cotunneling regime by increasing the tunnel barrier transparency.     

Graphical Representations of Speed: Obstacles Preservice K‐8 Teachers Experience

This study examines the difficulties college students experience when creating and interpreting graphs in which speed is one of the variables. Nineteen students, all preservice elementary or middle school teachers, completed an upper‐level course exploring algebraic concepts. Although all of these preservice teachers had previously completed several mathematics courses, including calculus, they demonstrated widespread misconceptions about the variable speed. This study identifies four cognitive obstacles held by the students, provides excerpts of their graphical constructions and verbal interpretations, and discusses potential causes for the confusion. In particular, misconceptions arose when students interpreted the behavior and nature of speed within a graphical context, as well as in situations where they were required to construct a graph involving speed as a variable. The study concludes by offering implications for the teaching and learning of speed and its interpretation within a graphical setting.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.