Self-assembled alkanethiol structures on gold: A further insight into the origins of structural rearrangement phenomena

Self-assembled structures of alkanethiols that have been deposited on gold from ethanolic solutions are susceptible to both chemical and physical changes: ethanol provides a medium for the formation of S-alkyl hydrogen thiocarbonates and related compounds via reaction with dissolved, atmospheric, CO₂. Deposition from ethanolic solutions results in multilayered structures incorporating these compounds, which at room temperature are susceptible to time-dependent structural rearrangement and molecular migration.     

Distributions with Heavy Tails in Orlicz Spaces

This paper relies on the application of Kantorovich functionals on quasi-interior points of the positive cone for certain classes of Orlicz spaces. Particularly we provide the asymptotic calculation of the ruin probability in the renewal risk model under heavy-tailed claims in the Orlicz spaces. This application assures the extension of classical asymptotic theory of regular variation.     

A Monoidal Category for Perturbed Defects in Conformal Field Theory

Starting from an abelian rigid braided monoidal category C{\mathcal{C}} we define an abelian rigid monoidal category C_F{\mathcal{C}_F} which captures some aspects of perturbed conformal defects in two-dimensional conformal field theory. Namely, for V a rational vertex operator algebra we consider the charge-conjugation CFT constructed from V (the Cardy case). Then C = Rep(V){\mathcal{C} = {\rm Rep}(V)} and an object in C_F{\mathcal{C}_F} corresponds to a conformal defect condition together with a direction of perturbation. We assign to each object in C_F{\mathcal{C}_F} an operator on the space of states of the CFT, the perturbed defect operator, and show that the assignment factors through the Grothendieck ring of C_F{\mathcal{C}_F}. This allows one to find functional relations between perturbed defect operators. Such relations are interesting because they contain information about the integrable structure of the CFT.     

A simple and effective method for phosphoryl transfer using TiCl(4) catalysis

[reaction: see text] A number of Lewis acids have been evaluated as catalysts for the phosphoryl transfer, the most efficient being TiCl(4). Application of this methodology to the phosphorylation of a number of representative target alcohols is presented     

Nonlocal dynamics of spontaneous imbibition fronts

We have studied spontaneous imbibition fronts generated by capillary rise between two roughened glass plates, the separation d of which varied between 10 and 50 microm. Perfect agreement with Washburn's law was obtained. We have determined the roughness exponent chi of the fronts, and found chi=0.81+/-0.01 for small length scales. Above a certain crossover length xi, it reached chi=0.58+/-0.04, as predicted by the quenched noise Kardar-Parisi-Zhang equation. The crossover length is found to scale with the plate separation as sqrt[d], as predicted by recent models which properly include nonlocal dynamics effects on the front. We believe this to be the first clear identification of crossover from nonlocal to local dynamics.     

Sample restriction using radiofrequency field selective pulses in high-resolution solid-state NMR

In this article a method is suggested for restricting a sample (spatial localization) by preparing the magnetization with a phase-modulated radiofrequency pulse which inverts magnetization only over a very narrow range of radiofrequency field strengths. This is the most efficient method, in terms of sensitivity, of restricting the sample to improve rf homogeneity. The method is demonstrated by using it to improve the resolution obtained in a homonuclear dipolar decoupling experiment.     

Two-dimensional high-resolution NMR spectra in matched B(0) and B(1) field gradients

In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems.     

Irreversibility and polymer adsorption

Physisorption or chemisorption from dilute polymer solutions often entails irreversible polymer-surface bonding. We present a theory of the resultant nonequilibrium layers. While the density profile and loop distribution are the same as for equilibrium layers, the final layer comprises a tightly bound inner part plus an outer part whose chains make only fN surface contacts where N is chain length. The contact fractions f follow a broad distribution, P(f) approximately f(-4/5), in rather close agreement with strong physisorption experiments [H. M. Schneider, Langmuir 12, 994 (1996)]].     

Interactive resonant scattering by a cluster of air bubbles in water

An exact, analytical solution is developed for the problem of acoustic-wave scattering from a cluster of ideal, gaseous, spherical bubbles in an unbounded, homogeneous, host fluid. This solution takes into account all modes of oscillation of the bubbles as well as all interactions between them; it is applicable to a wide range of bubble sizes and excitation frequencies. In the low frequency regime, the theory of this paper is shown to reduce to the "monopole" approximation, the effect of higher-order modes being non-negligible only for very small bubble-to-bubble separations. A numerical study of interactive backscattering from small clusters, comprising up to three ideal bubbles, is presented. Interactions between the bubbles are shown to produce downward shifts in the resonance frequency of the cluster, when the scattering configuration is symmetric. Furthermore, asymmetries of the scattering configuration are shown to generate sharp resonances at frequencies above the resonance of the symmetric mode. The results of this paper agree with previous theoretical and experimental work.     

The ultrasensitivity of living polymers

Synthetic and biological living polymers are self-assembling chains whose chain length distributions (CLDs) are dynamic. We show these dynamics are ultrasensitive: Even a small perturbation (e.g., temperature jump) nonlinearly distorts the CLD, eliminating or massively augmenting short chains. The origin is fast relaxation of mass variables (mean chain length, monomer concentration) which perturbs CLD shape variables before these can relax via slow chain growth rate fluctuations. Viscosity relaxation predictions agree with experiments on the best-studied synthetic system, alpha-methylstyrene.