Does charge carrier dimensionality increase in mixed-valence salts of tetrathiafulvalene-terminated dendrimers?

[structure: see text] In four new dendrimers terminated by 12 electroactive tetrathiafulvalenyl substituents, the tridimensional character of the inter- and intradendrimeric charge and electron transfer, and hence of the electroconductivity, is evidenced by examination of the electronic spectra of their corresponding neutral state and cation radical, dication, and mixed-valence salts, including a closed-shell anion.     

Does the gradient-regulated connection improve the description of correlated metal bond properties?

Gradient-regulated connection (GRAC) is a generalized gradient approximation exchange density functional designed by combining the revPBE and PW91 exchange functionals to impose their behaviors in the slowly- and fast-varying density regions, respectively. Such a construction allows one single density functional to accurately estimate both covalent and weak interactions occurring in main-group-based molecular systems. For the first time, the assessment of the performance of the GRAC exchange functional is extended to the modeling of various metal bond energy and structure properties. This assessment shows that when GRAC is coupled with the Perdew, Burke, Ernzerhof (PBE) correlation, the resulting exchange-correlation density functional is an excellent alternative to global hybrids to model bond dissociation energy, atomic electronic excitation energy, and bond length structure properties of single-reference metal bonds. It also shows that coupling with the Tognetti, Cortona, Adamo (TCA) correlation constitutes a robust approach to tackle energy bond properties of organometallic complexes with multi-reference character.     

Does amino acid sequence determine the properties of Aβ dimer?

The effect of random reshuffling of amino acids on the properties of dimers formed by Aβ peptides is studied using replica exchange molecular dynamics and united atom implicit solvent model. We show that thermodynamics of dimer assembly and the dimer globule-like state are not affected by sequence permutation. Furthermore, sequence reshuffling does not change the distributions of non-local interactions and, to a large extent, amino acids in the dimer volume. To rationalize these results, we demonstrate that Gaussian statistics applies surprisingly well to the end-to-end distances of the peptides in the dimer implying that non-bonded interactions between distant along the chain amino acids are effectively screened. This observation suggests that peptides in the dimer behave as ideal chains in polymer melt, in which amino acids lose their "identity" and therefore the memory of sequence position. As a result large-scale properties of the dimer become universal or sequence independent. Comparison of our simulations with the prior theoretical studies and their implications for experiments are discussed.     

Microscopic simulations of molecular cluster decay: Does the carrier gas affect evaporation?

We develop a kinetic theory of cluster decay by considering the stochastic motion of molecules within an effective potential of mean force (PMF) due to the cluster. We perform molecular dynamics simulations on a 50-atom argon cluster to determine the mean radial force on a component atom and hence the confining potential of mean force. Comparisons between isolated clusters and clusters thermostatted through the presence of a 100-atom helium carrier gas show that the heat bath has only a slight effect upon the PMF. This confirms the validity of calculations of cluster properties using isolated cluster simulations. The PMF is used to calculate the atomic evaporation rate from these clusters, and results are compared with the predictions of the capillarity approximation together with detailed balance, both components of the classical theory of aerosol nucleation.     

Does magnetic treatment of water change its properties?

Some properties and functions of water treated under magnetic field were examined. No change in properties of pure water distilled from ultrapure water in vacuum was observed by magnetic treatment. However, when the same magnetic treatment was carried out after the distilled water was exposed to O2, water properties such as vibration modes and electrolytic potential were changed. The degree of magnetic treatment effect on water was quantitatively evaluated by contact angle.     

Does compressibility affect the results obtained by small angle neutron scattering?

Recently a few papers have been devoted to the scattering by polymer solutions and blends^(1,2) assuming that the systems under investigation are compressible, contrarily to what is usually done. This is motivated by the fact that if one uses the theory of incompressible mixtures in scattering experiments, one obtains values of the Flory⁽³⁾ χ parameter which are inconsistent with the values obtained by other techniques. In this paper we would like to show that, contrarily to what has been said, the effect of compressibility can be easily evaluated; it is very small and already corrected in the classical treatment of the data used in light or neutron scattering experiments.     

Comparative study of the performance of columns packed with several new fine silica particles. Would the external roughness of the particles affect column properties?

We measured and compared the characteristics and performance of columns packed with particles of five different C(18)-bonded silica, 3 and 5 microm Luna, 3 microm Atlantis, 3.5 microm Zorbax, and 2.7 microm Halo. The average particle size of each material was derived from the SEM pictures of 200 individual particles. These pictures contrast the irregular morphology of the external surface of the Zorbax and Halo particles and the smooth surface of the Luna and Atlantis particles. In a wide range of mobile phase velocities (from 0.010 to 3 mL/min) and at ambient temperature, we measured the first and second central moments of the peaks of naphthalene, insulin, and bovine serum albumin (BSA). These moments were corrected for the contributions of the extra-column volumes to calculate the reduced HETPs. The C-terms of naphthalene and insulin are largest for the Halo and Zorbax materials and the A-term smallest for the Halo-packed column. The Halo column performs the best for the low molecular weight compound naphthalene (minimum reduced HETP, 1.4) but is not as good as the Atlantis or Luna columns for the large molecular weight compound insulin. The Zorbax column is the least efficient column because of its large C-term. The lowest sample diffusivity through these particles, alone, does not account for the results. It is most likely that the roughness of the external surface of the Halo and Zorbax particles limit the performance of these columns at high flow rates generating an unusually high film mass transfer resistance.     

How does γ-irradiation affect the properties of a microfiltration membrane constituted of two polymers with different radiolytic behavior?

The objective of this work is to present the behavior of a fluorinated microporous membrane composed of poly(vinylidene fluoride) (PVDF) mechanically reinforced by a polyamide-66 (PA-66) fabric under γ-irradiation with dose ranging between 0 and 100 kGy, in inert atmosphere and at room temperature. Particular attention was paid to the evolution of mechanical properties, the surface morphology and pores size distribution of this membrane, in order to study the filtration capacity and selectivity with increasing radiation dose. Moreover, the repartition of the generated radicals onto the two components of the membrane was achieved by electron spin resonance (ESR) spectroscopy. Two different regimes are observed depending on the dose range, and a correlation between the mechanical behavior of the membrane and the evolution of the concentration of the radicals in the PA fabric is observed. Globally, the porosity of the surface membrane does not vary whatever the dose may be, but the mechanical properties of the membrane as well as the permeability are strongly affected, even for low radiation dose such as 10 kGy. These results are related to chain scissions on the PA fabric, which occurred preferentially, compared to cross-linking, in the investigated dose range.     

Does chemometrics enhance the performance of electroanalysis?

This review explores the question whether chemometrics methods enhance the performance of electroanalytical methods. Electroanalysis has long benefited from the well-established techniques such as potentiometric titrations, polarography and voltammetry, and the more novel ones such as electronic tongues and noses, which have enlarged the scope of applications. The electroanalytical methods have been improved with the application of chemometrics for simultaneous quantitative prediction of analytes or qualitative resolution of complex overlapping responses. Typical methods include partial least squares (PLS), artificial neural networks (ANNs), and multiple curve resolution methods (MCR-ALS, N-PLS and PARAFAC). This review aims to provide the practising analyst with a broad guide to electroanalytical applications supported by chemometrics. In this context, after a general consideration of the use of a number of electroanalytical techniques with the aid of chemometrics methods, several overviews follow with each one focusing on an important field of application such as food, pharmaceuticals, pesticides and the environment. The growth of chemometrics in conjunction with electronic tongue and nose sensors is highlighted, and this is followed by an overview of the use of chemometrics for the resolution of complicated profiles for qualitative identification of analytes, especially with the use of the MCR-ALS methodology. Finally, the performance of electroanalytical methods is compared with that of some spectrophotometric procedures on the basis of figures-of-merit. This showed that electroanalytical methods can perform as well as the spectrophotometric ones. PLS-1 appears to be the method of practical choice if the %relative prediction error of ∼±10% is acceptable.     

Synthesis of sulfonimide-based dendrimers and dendrons possessing mixed 1 → 2 and 1 → 4 branching motifs

The synthesis of dendrimers and a chlorosulfo-dendron possessing a unique combination of 1?→?2 and 1?→?4 branching types is described. The procedure consists of a two-step preparation of 3,5-dinitrobenzene-1-sulfonyl chloride, which was used for the persulfonylation of p-toluidine and 4-(benzylthio)aniline. The obtained tetranitro compounds were reduced to the corresponding tetraamines. The latter were decorated with eight 4-toluene sulfonyl groups each to furnish the corresponding dendrimers. Oxidation of the dendrimer possessing a 4-(benzylthio)phenylene core with N-chlorosuccinimide resulted in the formation of a dendron with a sulfonyl chloride functionality at the focal point.     

Does the valence state of an ion affect its diffusivity? Part I: Oxygen activity dependence of the diffusion of iron in alumina-doped MgO

To investigate whether a change in the valence state of tracer ions affects their diffusivity or not, the iron tracer diffusion in Al₂O₃-doped MgO, in which 0.5% of the cations were Al³⁺ ions, has been studied experimentally. Samples were prepared from high purity aluminum and magnesium nitrates using a chemical solution method and from powders of high purity Al₂O₃ and MgO. Because the concentration of the Al³⁺ dopant ions present in the samples was much larger than that of all other impurities, the concentration of the majority point defects, cation vacancies, was determined by the Al³⁺ concentration. Therefore, when changing the oxygen activity, the diffusivity of iron tracer ions can only be altered by changes in their valence state. Measurements of iron tracer diffusion coefficients were performed as a function of the oxygen activity at 1100 and 1200 °C. The experimental results indicate that the mean diffusivity of iron ions in Al₂O₃-doped MgO increases with increasing oxygen activity at both temperatures, suggesting that Fe³⁺ ions diffuse in Al₂O₃-doped MgO faster than Fe²⁺ ions.     

A new class of protein mimics: preparation and electrophoretic properties of polycationic β-alanine-based dendrimers

The synthesis and characterization of a series of polyammonium β-alanine containing dendrimers 4-6 were reported. Such polycationic species were shown to exhibit electrophoretic behavior similar to that of protein molecules such as lysozyme and aprotinin in acidic polyacrylamide gel electrophoresis. It was also found that their electromobility was directly related to their molecular size, and hence such biomimetic dendrimers are potential molecular weight markers for protein analysis.     

Does the chromatomembrane cell improve the quality of environmental analysis?

With the intention of combining partition chromatography and membrane techniques, we succeeded in developing the chromatomembrane cell which has proved to be reliable as an extraction and preconcentration manifold in flow injection analysis. With this technique, two immiscible phases can be induced to flow independently through a block of biporous (macro and micro) PTFE in order to promote analyte exchange. Consequently, the application of chromatomembrane cells in environmental analysis resolves all problems of sample pretreatment simply and effectively whenever a preconcentration step by gas/liquid or liquid/liquid solvent extraction is included. The link-up with analyzers (AAS, UV–Vis photometry, GC, IC, HPLC, voltammetry, ion selective electrodes, etc.) makes possible computer aided automization for environmental monitoring.     

Does confining the hard-sphere fluid between hard walls change its average properties?

We use grand canonical transition-matrix Monte Carlo and discontinuous molecular dynamics simulations to generate precise thermodynamic and kinetic data for the equilibrium hard-sphere fluid confined between smooth hard walls. These simulations show that the pronounced inhomogeneous structuring of the fluid normal to the confining walls, often the primary focus of density functional theory studies, has a negligible effect on many of its average properties over a surprisingly broad range of conditions. We present one consequence of this insensitivity to confinement: a simple analytical equation relating the average density of the confined fluid to that of the bulk fluid with equal activity. Nontrivial implications of confinement for average fluid properties do emerge in this system, but only when the fluid is both (i) dense and (ii) confined to a gap smaller than approximately three particle diameters. For this limited set of conditions, we find that "in-phase" oscillatory deviations in excess entropy and self-diffusivity (relative to the behavior of the bulk fluid at the same average density) occur as a function of gap size. These paired thermodynamic/kinetic deviations from bulk behavior appear to reflect the geometric packing frustration that arises when the confined space cannot naturally accommodate an integer number of particle layers.     

How does dielectric solvation affect the size of an ion?

The effect of solvation by a continuum dielectric on the size of an ion is examined using electronic structure calculations. Various measures correlated with size are considered, including the root-mean-square radius of the electronic charge density, the amount of solute charge penetrating outside the cavity, the electronic radial distribution function, the nucleus-electron potential energy, and the electron-electron potential energy. Calculations are made on several representative ionic solutes, and it is found that every measure indicates that the application of a dielectric makes the cations larger and the anions smaller. These counterintuitive trends are examined, and a plausible explanation is offered for the observed behavior.     

Assessment of solvent effects: do weak alignment media affect the structure of the solute?

Alignment media used for measuring residual dipolar couplings, such as solutions of filamentous phages, phospholipid mixtures, polyacrylamide gels and various lyotropic liquid crystalline systems were investigated with respect to solvent effects on molecular structure. Structural parameters of the small rigid model compound 13C-acetonitrile were calculated from dipolar couplings and variations from expectation values were used for assessment of solvent effects. Only minor solvent effects were observed for most of the media employed and the measured structural data are in good agreement with microwave data and theoretical predictions.     

Structure and optoelectronic properties of PbSe quantum dots /PVA. Does the polymer molecular weight matter?

Polyvinyl alcohol (PVA) with different molecular weights (8000, 14,000, and 132,000 g/mol) capped lead selenide (PbSe) quantum dots (QDs) are prepared. The nanocomposites are characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). XRD and TEM studies show that the particle size of PbSe QDs decrease with the increase in PVA molecular weight and/or PVA amount. This may be due to the increase in molecular weight inhibiting further growth of PbSe into the polymer matrix. Thermogravimetric analysis showed that the introduction of PbSe QDs into PVA decreases the crystallinity of the polymer. The optical absorption spectroscopy of prepared nanocomposites showed that the absorption peaks are strongly shifted to the lower wavelength (blue shift) from near infrared region to visible region by increasing the PVA molecular weight. The (I–V) characteristic curves of the PVA/PbSe nanocomposite films under illumination showed a photovoltaic cell‐like behavior. The results indicated that as the molecular weight of polymer increases, the conversion efficiency increases. Copyright © 2010 John Wiley & Sons, Ltd.     

How does cross-linking affect the stability of block copolymer vesicles in the presence of surfactant?

Block copolymer vesicles are conveniently prepared directly in water at relatively high solids by polymerization-induced self-assembly using an aqueous dispersion polymerization formulation based on 2-hydroxypropyl methacrylate. However, dynamic light scattering studies clearly demonstrate that addition of small molecule surfactants to such linear copolymer vesicles disrupts the vesicular membrane. This causes rapid vesicle dissolution in the case of ionic surfactants, with nonionic surfactants proving somewhat less destructive. To address this problem, glycidyl methacrylate can be copolymerized with 2-hydroxypropyl methacrylate and the resulting epoxy-functional block copolymer vesicles are readily cross-linked in aqueous solution using cheap commercially available polymeric diamines. Such epoxy-amine chemistry confers exceptional surfactant tolerance on the cross-linked vesicles and also leads to a distinctive change in their morphology, as judged by transmission electron microscopy. Moreover, pendent unreacted amine groups confer cationic character on these cross-linked vesicles and offer further opportunities for functionalization.