Double-wall carbon nanotubes: The outer shell may pattern the structure of the inner one

An existing model [L. Bellarosa, E. Bakalis, M. Melle-Franco, F. Zerbetto, Nano Lett. 6 (2006) 1950] predicts that the structures of the seven double-wall carbon nanotubes, DWCNTs, identified by high-resolution transmission electron microscopy [L. Guan, K. Suenaga, S. Iijima, Nano Lett. 8 (2008) 459] are the most stable. Since the samples were obtained from single-wall carbon nanotubes, SWCNTs, filled with ferrocene molecules that were annealed at 1273 K for 24 h, it is concluded that under proper conditions the host SWCNT patterns the formation of the inner one to form the most stable pair.     

Modelling the use of lanthanides(III) as probes at calcium(II) binding sites in biological systems: Preparation and characterization of neodymium(III) and calcium(II) malonamato(-1) complexes

A bioinorganic approach into the problem of the isomorphous substitution of calcium(II) by lanthanide(III) ions in biological systems is discussed. Reactions of malonamic acid (H₂malm) with Ca^II and Nd^III sources under similar conditions yielded the compounds [Ca(Hmalm)₂]_n (1), [Nd(Hmalm)₂(H₂O)₂]_n(NO₃)_n (2) and [Nd(Hmalm)₂(H₂O)₂]_nCl_n·2nH₂O (3·2nH₂O). Their X-ray crystal structure data show that the malonamate(-1) ligand presents two different ligation modes and coordinates through the two carboxylate and the amide-O atoms, thus bridging three Ca^II ions in 1 and two Nd^III ions in 2 and 3·2nH₂O. Complex 1 is a 3D coordination polymer based on neutral repeating units, whereas 2 and 3·2nH₂O are 1D coordination polymers based on the same cationic repeating unit. Hydrogen bonding interactions further stabilize the 3D framework structure of 1 and assemble the 1D chains of 2 and 3·2nH₂O into 3D networks. The three complexes were characterized spectroscopically (IR, far-IR, and Raman) and the thermal decomposition of 2 and 3·2nH₂O was monitored by TG/DTA and TG/DTG measurements. Variable-temperature magnetic susceptibility data for 2 are also reported. The bioinorganic chemistry relevance of our results is discussed.     

Continuous symmetry reduction and return maps for high-dimensional flows

We present two continuous symmetry reduction methods for reducing high-dimensional dissipative flows to local return maps. In the Hilbert polynomial basis approach, the equivariant dynamics is rewritten in terms of invariant coordinates. In the method of moving frames (or method of slices) the state space is sliced locally in such a way that each group orbit of symmetry-equivalent points is represented by a single point. In either approach, numerical computations can be performed in the original state space representation, and the solutions are then projected onto the symmetry-reduced state space. The two methods are illustrated by reduction of the complex Lorenz system, a five-dimensional dissipative flow with rotational symmetry. While the Hilbert polynomial basis approach appears unfeasible for high-dimensional flows, symmetry reduction by the method of moving frames offers hope.     

Transient gas flow simulation using an Adaptive Method of LinesSimulation d'écoulements dans un gazoduc par la méthode adaptative de lignes

Designing natural gas pipelines to safely and efficiently handle unsteady flows, requires knowledge of pressure drop, flowrate and temperature distribution throughout the system. The accurate prediction of these parameters is essential in order to achieve optimum cumulative deliverability, and safe and reliable operation. An Adaptive Method of Lines algorithm is formulated for the solution of Euler system of equations, which fully simulates slow and fast transients. Two test cases present the improvement of the numerical solution from grid adaptation. Good results are obtained both for slow and fast transients simulations proving that the suggested numerical procedure is appropriate for such predictions. To cite this article: E. Tentis et al., C. R. Mecanique 331 (2003).     

Monte Carlo simulations of a coarse grained model for an athermal all-polystyrene nanocomposite system

The structure of a polystyrene matrix filled with tightly cross-linked polystyrene nanoparticles, forming an athermal nanocomposite system, is investigated by means of a Monte Carlo sampling formalism. The polymer chains are represented as random walks and the system is described through a coarse grained Hamiltonian. This approach is related to self-consistent-field theory but does not invoke a saddle point approximation and is suitable for treating large three-dimensional systems. The local structure of the polymer matrix in the vicinity of the nanoparticles is found to be different in many ways from that of the corresponding bulk, both at the segment and the chain level. The local polymer density profile near to the particle displays a maximum and the bonds develop considerable orientation parallel to the nanoparticle surface. The depletion layer thickness is also analyzed. The chains orient with their longest dimension parallel to the surface of the particles. Their intrinsic shape, as characterized by spans and principal moments of inertia, is found to be a strong function of position relative to the interface. The dispersion of many nanoparticles in the polymeric matrix leads to extension of the chains when their size is similar to the radius of the dispersed particles.     

Interfacial thermodynamics of gallic acid adsorption on a chargeable hydrophobic surface

The thermodynamics of adsorption of gallic acid (GA, 3,4,5-trihydroxylbenzoic acid) on the hanging mercury drop electrode (HMDE) surface was studied by temperature-dependent stripping voltammetry (TD-SV), at physiological pH 7.4. The thermodynamic parameters, e.g., Gibbs free energy, ΔG(ADS), enthalpy, ΔΗ(ADS) and entropy, ΔS(ADS), of adsorption have been determined at physiological temperatures 2-40 °C. Chemisorption of the radical species ≡[GA(OH)(2)(O(-))]* is the energetically important reaction. The thermodynamic data show a complex mechanism of adsorption of GA on the electrode surface, which is strongly dependent on temperature. At low-temperatures T<12 °C, adsorption is controlled by enthalpy, while at T>22 °C, adsorption is entropy driven. In the temperature range 12 °C and 22 °C, a combined enthalpy-entropy stabilization occurs. A mechanism is proposed which analyses the implication of thermodynamics to the interfacial adsorption of polyphenols with cell membranes under physiological conditions.     

First-principles calculations of the electronic and geometrical structures of neutral [Sc,O,H] molecules and the monocations, ScOH(0,+) and HScO(0,+)

Using multireference configuration interaction and coupled-cluster methodologies, with quadruple-ζ basis sets, we explored the potential energy surfaces of the ground and excited states of the neutral and cationic triatomics [Sc,O,H](0,+). In its ground state, the neutral species is trapped into either a linear ScOH or a bent HScO conformation; these two minima are approximately equal in energy and separated by a barrier of 40 kcal/mol. The linear ScOH structure is preferred by the excited states of the neutral species and by all of the electronic states of the charged molecular systems that we studied in this work. Both ScOH and ScOH(+) present ionic characters, Sc(+)OH(-) and Sc(2+)OH(-), similar to those found for the isovalent ScF(0,+) species. The HScO(0,+) structures are obtained by covalent or dative interaction of hydrogen and ScO(0,+). For most of the minima located in this work, we calculated geometries, vibrational frequencies, binding energies, excitation energies, and dipole moments. Our numerical results agree well with existing experimental data.     

Atomistic simulation of lipid and DiI dynamics in membrane bilayers under tension

Membrane tension modulates cellular processes by initiating changes in the dynamics of its molecular constituents. To quantify the precise relationship between tension, structural properties of the membrane, and the dynamics of lipids and a lipophilic reporter dye, we performed atomistic molecular dynamics (MD) simulations of DiI-labeled dipalmitoylphosphatidylcholine (DPPC) lipid bilayers under physiological lateral tensions ranging from -2.6 mN m(-1) to 15.9 mN m(-1). Simulations showed that the bilayer thickness decreased linearly with tension consistent with volume-incompressibility, and this thinning was facilitated by a significant increase in acyl chain interdigitation at the bilayer midplane and spreading of the acyl chains. Tension caused a significant drop in the bilayer's peak electrostatic potential, which correlated with the strong reordering of water and lipid dipoles. For the low tension regime, the DPPC lateral diffusion coefficient increased with increasing tension in accordance with free-area theory. For larger tensions, free area theory broke down due to tension-induced changes in molecular shape and friction. Simulated DiI rotational and lateral diffusion coefficients were lower than those of DPPC but increased with tension in a manner similar to DPPC. Direct correlation of membrane order and viscosity near the DiI chromophore, which was just under the DPPC headgroup, indicated that measured DiI fluorescence lifetime, which is reported to decrease with decreasing lipid order, is likely to be a good reporter of tension-induced decreases in lipid headgroup viscosity. Together, these results offer new molecular-level insights into membrane tension-related mechanotransduction and into the utility of DiI in characterizing tension-induced changes in lipid packing.     

TiO2-ZrO2 affinity chromatography polymeric microchip for phosphopeptide enrichment and separation

We fabricated a TiO(2)-ZrO(2) affinity chromatography micro-column on 2 mm PMMA plates, and demonstrated the enrichment and separation of (a) a standard mono- and tetra-phosphopeptide, and (b) phosphopeptides contained in a tryptic digest of β-Casein. The chromatography column consisted of 32 parallel microchannels with common input and output ports and was fabricated by lithography directly on the polymeric substrate followed by plasma etching (i.e. standard MEMS processing) and sealed with lamination. The liquid deposited TiO(2)-ZrO(2) stationary phase was characterized by X-ray diffraction and was found to be mostly TiO(2) and ZrO(2) in crystalline phases. Off-chip UV detection and MALDI MS identification of the separated effluents were used. The chip had a capacity of >1.4 μg (0.7 nmol) of a prototype mono-phosphopeptide and a recovery of 94 ± 3%, and can be used with small samples (less than 0.1 μL depending on the syringe pump used). The chip design allows an expansion of its capacity by means of increasing the number of parallel microchannels at a constant sample volume. Our approach provided an alternative to off-line extraction tips (with typical capacities of 1-2 μg and sample volumes of 1-10 μL), and to on-chip efforts based on packed bed and frit formats.     

Measuring Customer Satisfaction Using a Collective Preference Disaggregation Model

A new model to assess customer satisfaction is developed through this paper. The proposed model is based on the principles of multicriteria analysis, using ordinal regression techniques. The procedure uses survey's data on customer satisfaction criteria and disaggregates simultaneously all the global satisfaction judgments via a linear programming disaggregation formulation. The model provides collective global and partial satisfaction functions as well as average satisfaction indices. These results sufficiently describe customer behavior and they can be used in the strategic planning of an organization. The implementation of the model in three real world applications is used for illustration and for testing the model's reliability. Finally, several extensions and future research in the area of customer satisfaction analysis are discussed.