Probing the self-assembly of inorganic cluster architectures in solution with cryospray mass spectrometry: growth of polyoxomolybdate clusters and polymers mediated by silver(I) ions

Cryospray mass spectrometry (CSI-MS) has been used to probe the mechanism of self-assembly of polyoxometalate clusters in solution. By using CSI-MS and electronic absorbance spectroscopy it was possible to monitor in real-time the self-assembly of polymeric chains based on [Ag 2Mo 8O 26] (2-) n building blocks. The role of the Ag (I) ion in the solution state rearrangement of molybdenum Lindqvist ({Mo 6}) into the silver-linked beta-octamolybdate ({Mo 8}) structure (( n-C 4H 9) 4N) 2 n [Ag 2Mo 8O 26] n ( 1) is revealed in unprecedented detail. A monoanionic series, in particular [AgMo m O 3 m+1 ] (-) where m = 2 to 4, and series involving mixed oxidation state polyoxomolybdate species, which illustrate the in-solution formation of the (Ag{Mo 8}Ag) building blocks, have been observed. CSI-MS detection of species with increasing metal nuclearity concomitant with increasing organic cation contribution supports the hypothesis that the organic cations used in the synthesis play an important structure-directing role in polyoxometalate (POM) growth in solution. A real-time decrease in [{Mo 6}] and associated increase in [{Mo 8}] have been observed using CSI-MS and electronic absorbance spectroscopy, and the rate of {Mo 6} interconversion to {Mo 8} was found to decrease on increasing the size of the countercation. This result can be attributed to the steric bulk of larger organic groups hindering {Mo 6} to {Mo 8} rearrangement and hindering the contact between silver cations and molybdenum anions.     

Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices

Polyoxometalates represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form structures that can bridge several length scales. The new building block principles that have been discovered are beginning to allow the design of complex clusters with desired properties and structures and several structural types and novel physical properties are examined. In this critical review the synthetic and design approaches to the many polyoxometalate cluster types are presented encompassing all the sub-types of polyoxometalates including, isopolyoxometalates, heteropolyoxometalates, and reduced molybdenum blue systems. As well as the fundamental structure and bonding aspects, the final section is devoted to discussing these clusters in the context of contemporary and emerging interdisciplinary interests from areas as diverse as anti-viral agents, biological ion transport models, and materials science.     

Wetting and electrical properties of the human hair surface: delipidation observed at the nanoscale

The electrostatic properties and the wetting behaviour of the human hair surface at the nanometric scale have been investigated by using atomic force microscopy (AFM). Surface potential imaging was used to determine the electrostatic properties while non-contact mode AFM was used to investigate the wetting properties of a test liquid, squalane. We have studied natural hair and hair in which different covalently (18-methyleicosanoic acid) and non-covalently bound fatty acids present at the cuticle surface were selectively extracted. This study shows how the removal of these acids causes various profound changes in hair wettability at the cuticle scale.     

pH-dependence of the aqueous electrochemistry of the two-electron reduced alpha-[Mo18O54(SO3)] sulfite Dawson-like polyoxometalate anion derived from its triethanolammonium salt

The electrochemistry of the Dawson-like sulfite polyoxometalate anion alpha-[Mo18O54(SO3)2]6-, derived from the TEAH6{alpha-[Mo18O54(SO3)2]} salt (TEAH+ is the triethanolammonium cation; pKa=7.8), has been investigated in aqueous media using cyclic and rotated disk voltammetry at glassy carbon electrodes and bulk electrolysis, with a focus on the pH-dependence for oxidation to alpha-[Mo18O54(SO3)2]4-. In buffered media at pH>or=4, the cyclic voltammetric response for alpha-[Mo18O54(SO3)2]6- reveals two partially resolved one-electron oxidation processes corresponding to the sequential generation of alpha-[Mo18O54(SO3)2]5- and alpha-[Mo18O54(SO3)2]4-. At lower pH, using electrolytes containing sulfuric acid, the two waves coalesce but the individual apparent E0' reversible formal potential values for the two processes can be extracted down to pH 2 by assuming that reversible protonation accompanies fast electron transfer. The results for 2相似文献   

Treatment of SMC Composite Waste for Recycling as Reinforcing Fillers in Thermoplastics

Needs for recycling thermoset composite materials are considerably increasing. Unfortunately, such materials are particularly difficult to recycle due to their crosslinked nature. In this paper, we focus on the case of Sheet Moulding Compounds (SMC), which consist of an unsaturated polyester filled with glass fibres and calcium carbonate. We consider the possibilities of mechanical treatments allowing to obtain ground fractions that could be used as fillers for the reinforcement of thermoplastics. Two processes are described and compared with an existing industrial one. Finally, optimised fractions of SMC waste are introduced into polypropylene, leading to promising results in term of mechanical properties.     

A theoretical approach to the thermochemistry of the polymerization of some derivatives of the monomers CH2X (X = CH2, NH,O)

In this work, we have calculated the thermodynamic parameters of the polymerization of some derivatives of the species CH₂X (X = CH₂, NH, O), using ab initio methods of quantum chemistry and the usual formalism of statistical thermodynamics. It is shown that the Gibbs functions ΔG(l, c) corresponding to CH₂NOCH₃, CNCHNCN, CF₂O and all the percyano derivatives are largely positive which indicates that the spontaneous (radical or ionic) chain polymerization of these monomers is thermodynamically prohibited.     

A general approach for computing unsteady 3D thin lifting and/or propulsive systems derived from a complete theory

This paper presents the basis of a numerical method for unsteady aerodynamic computation around thin lifting and/or propulsive systems with arbitrary variable geometries, involving the velocity field, the velocity potential, the pressure field and the wake characteristics (geometry and vortex strength). Most of the corresponding theory actually stems from the unsteady wake model established by Mudry, in which the wake is considered to be a median layer, characterized by a pair of functions on which Mudry founded the concept of continuous vortex particle. The governing relations of the continuous problem are then the flow tangency condition, the wake integro‐differential evolution equation, and a flow regularity condition at the trailing edge. This constitutes a rigorous and complete theoretical formulation of this problem, from which a discretization scheme and a numerical method of solution are derived. The view of the vortex wake is similar to the one in the classical vortex lattice approaches, but uses a discrete vortex particle concept, particularly well suited for the prediction of the unsteady wake deformation. This, together with the continuous theory, ensures the computing method compares favorably with the classical methods in terms of flexibility and computing costs. In order to demonstrate the capabilities of the present method, the calculation of flapping wings of variable geometry is also presented. Copyright © 1999 John Wiley & Sons, Ltd.