Supramolecular assembly of strongly chemisorbed size- and shape-defined chiral clusters: S- and R-alanine on Cu(110)

The bonding and self-assembly of a chirally organized monolayer of alanine on the Cu(110) surface has been investigated using reflection-absorption infrared spectroscopy, low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM). This multitechnique approach has enabled an in-depth understanding of the hierarchy of chirality transfer: from a single adsorbed molecule, to size-defined chiral clusters, and then to an overall chiral assembly. The data have indicated that the alanine is in its anionic form, bound to the copper surface through the oxygens of the ionized carboxylate group and the nitrogen of the neutral amino group. Importantly, the methyl group is held away from the surface, resulting in direct chirality transfer into the footprint of the adsorbed alanine molecules, with the local adsorption motif for S-alanine being the mirror image of that created for R-alanine. STM has shown that S-alanine molecules self-organize to form size-defined chiral clusters of six or eight molecules at the surface, interspersed with chiral channels of bare metal. Together, these clusters and channels further self-assemble into a chiral array with one unique chiral domain sustained across the entire surface. A similar chiral assembly, but with the mirror organization, has been observed for R-alanine. Structural models for the individual clusters are proposed, and in conjunction with LEED data, overall models for these chiral phases of both S- and R-alanine have been constructed. Overall, this adsorption system has been found to be both strongly chemisorbed and capable of extensive intermolecular H-bonding, causing stresses that lead not only to the chiral self-organization of molecules but also to a specific self-organization of the empty chiral channels and spaces that intersperse the structure which, in turn, chirally assemble across macroscopic length scales to give a surface with global organizational chirality.     

Lagrangian velocity statistics in turbulent flows: effects of dissipation

We use the multifractal formalism to describe the effects of dissipation on Lagrangian velocity statistics in turbulent flows. We analyze high Reynolds number experiments and direct numerical simulation data. We show that this approach reproduces the shape evolution of velocity increment probability density functions from Gaussian to stretched exponentials as the time lag decreases from integral to dissipative time scales. A quantitative understanding of the departure from scaling exhibited by the magnitude cumulants, early in the inertial range, is obtained with a free parameter function D(h) which plays the role of the singularity spectrum in the asymptotic limit of infinite Reynolds number. We observe that numerical and experimental data are accurately described by a unique quadratic D(h) spectrum which is found to extend from h(min) approximately 0.18 to h(max) approximately 1.     

Oscillating viscosity in a lyotropic lamellar phase under shear flow

We report some time-dependent behavior of lyotropic lamellar phase under shear flow. At fixed stress, near a layering instability, the system presents an oscillating shear rate. We build up a new stress versus shear rate diagram that includes temporal behavior. This diagram is made of two distinct branches of stationary states which correspond, respectively, to disordered and ordered multilamellar vesicle phases. When increasing the shear stress, prior to the transition to the ordered structural state, sustained oscillations of the viscosity are recorded. They correspond to periodic structural change of the entire sample between a disordered and a ordered state of multilamellar vesicles.     

Suppression of the sawtooth instability in a storage ring by free-electron laser: an example of nonlinear stabilization by noise

The stabilization of nonlinear excitations by noise is a topic of fundamental importance in many physical problems. We discuss a genuine example within the context of storage ring-free electron laser physics, by presenting a model which allows the characterization of the system evolution and the determination of the conditions leading to the suppression of instabilities of sawtooth type. The conclusions of the model are confirmed by a comparison with experimental results on the Super Aco Storage Ring-Free Electron Laser.     

Acoustical imaging through a multiple scattering medium using a time-reversal mirror

Acoustical imaging is based on the ability to focus an acoustic beam inside the zone of interest. This remains an issue through a high-order multiple scattering medium because the electronic delay lines that enable one to focus through a multiple scattering medium are a priori unknown. Using time-reversal principles, we show that images can be obtained through a very disordered medium. Surprisingly, the images are better than those obtained in a homogeneous medium with a classical imaging device.     

Structure-energy relationship in barbituric acid: a calorimetric, computational, and crystallographic study

This paper reports the value of the standard (p(o) = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K for barbituric acid. The enthalpies of combustion and sublimation were measured by static bomb combustion calorimetry and transference (transpiration) method in a saturated N2 stream and a gas-phase enthalpy of formation value of -(534.3 +/- 1.7) kJ x mol(-1) was determined at T = 298.15 K. G3-calculated enthalpies of formation are in very good agreement with the experimental value. The behavior of the sample as a function of the temperature was studied by differential scanning calorimetry, and a new polymorph of barbituric acid at high temperature was found. In the solid state, two anhydrous forms are known displaying two out of the six hydrogen-bonding patterns observed in the alkyl/alkenyl derivatives retrieved from the Cambridge Crystallographic Database. The stability of these motifs has been analyzed by theoretical calculations. X-ray powder diffraction technique was used to establish to which polymorphic form corresponds to the commercial sample used in this study and to characterize the new form at high temperature.     

Representations of set-valued risk measures defined on the l-tensor product of Banach lattices

We obtain a representation for set-valued risk measures which are defined on the completed \(l\) -tensor product \(E\widetilde{\otimes }_l G\) of Banach lattices \(E\) and \(G\) . This representation extends known representations for set-valued risk measures defined on Bochner spaces \(L^p(\mathbb {P}, \mathbb {R}^d)\) of \(p\) -integrable functions with values in \(\mathbb {R}^d\) .     

Excess heat capacities of ternary systems containing chlorobenzene or chloronaphthalene

Densities and heat capacities of ternary systems were determined at 25°C. The ternary systems consisted of: a polar molecule (component 1) + a mixture of alkanes (components 2 and 3) of different sizes and shapes. Five such systems were studied: chlorobenzene + cyclohexane + n-heptane; chlrobenzene + cyclohexane + n-hexadecane; chlorobenze + cyclohexane + isooctane; chlorobenzene + isooctane + n-heptane; 1-chloronaphthalene + isooctane + n-heptane. The excess molar volumes and heat capacities were obtained along dilution lines by component 1 (chlorobenzene or 1-chloronaphthalene) of mixtures of components 2 and 3 (at fixed component 2 mole fraction X₂). Unexpectedly the excess heat capacities C _p1(23) ^E of the pseudo-binaries {1+(2+3)} do not always fall between the two (limiting) curves of C _p12 ^E and C _p13 ^E corresponding to the two binaries {1+2} and {1+3}. Instead, especially for {chlorobenzene + cyclohexane + an n-alkane} the C _p1(23) ^E curves are displaced toward less negative values, even beyond the limiting values corresponding to the binaries. This correlates semi-quantitatively with the negative C _p23 ^E of the binary {2+3}.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30-June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Application of a chemical equilibrium model to thermodynamic functions of transfer of alcohols from water to aqueous surfactants

In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models.