Taylor dispersion monitored by electrospray mass spectrometry: a novel approach for studying diffusion in solution

This work describes a novel approach for monitoring analyte diffusion in solution that is based on electrospray ionization mass spectrometry (ESI-MS). A mass spectrometer at the end of a laminar flow tube is used to measure the Taylor dispersion of an initially sharp boundary between two solutions of different analyte concentration. This boundary is dispersed by the laminar flow profile in the tube. However, this effect is diminished by analyte diffusion that continuously changes the radial position, and hence the flow velocity of individual analyte molecules. The steepness of the resulting dispersion profile therefore increases with increasing diffusion coefficient of the analyte. A theoretical framework is developed to adapt the equations governing the dispersion process to the case of mass spectrometric detection. This novel technique is applied to determine the diffusion coefficients of choline and cytochrome c. The measured diffusion coefficients, (11.9 +/- 1.0) x 10(-10) m(2) s(-1) and (1.35 +/- 0.08) x 10(-10) m(2) s(-1), respectively, are in agreement with the results of control experiments where the Taylor dispersion of these two analytes was monitored optically. Due to the inherent selectivity and sensitivity of ESI-MS, it appears that the approach described in this work could become a valuable alternative to existing methods for studying diffusion processes, especially for experiments on multicomponent systems.     

Kinetics of disassembly of a DNA-bound porphyrin supramolecular array

trans-Bis(N-methylpyridinium-4-yl)diphenylporphine forms extended, organized assemblies on DNA templates under appropriate conditions of concentration, ionic strength, and temperature. Addition of beta-cyclodextrin to these arrays leads to their disassembly as evidenced by changes in extinction, circular dichroism, and resonance light scattering spectra. The structure or flexibility of the polymer template has an effect on the rate of disassembly; the reaction is faster on a poly(dG-dC)(2) surface than on ct DNA. The kinetic profiles for the disassembly process can be fit with great precision with a two-kinetic parameter equation in which the rate constant is itself a function of time. The reaction rate, studied in the presence of excess beta-CD, shows a dependence on the mode of detection. A model is presented to account for these observations in which the arrays become increasingly reactive with time due to beta-CD attack at the interior of the porphyrin assemblies as well as the ends.     

Ion-beam sculpting time scales

A study of ion sculpting dynamics in SiO2 and SiN using periodically pulsed ion beams reveals material transport that depends strongly on the time structure of the pulsed beams. It is found that significant nanoscale matter transport can occur over second long time scales after the ion beam has been extinguished. A simple phenomenological model described the dynamics of ion beam sculpting in terms of two material time scales. The model accounts for the surprising observation of enhanced matter transport affected by pulsed ion beams over continuous ion beam exposure.     

T-ray computed tomography

We demonstrate a tomographic imaging modality that uses pulsed terahertz (THz) radiation to probe the optical properties of three-dimensional (3D) structures in the far-infrared. This THz-wave computed tomography (T-ray CT) system provides sectional images of objects in a manner analogous to conventional CT techniques such as x-ray CT. The transmitted amplitude and phase of broadband pulses of THz radiation are measured at multiple projection angles. The filtered backprojection algorithm is then used to reconstruct the target object, including both its 3D structure and its frequency-dependent far-infrared optical properties.     

The platinum benzole acid blues — a new class of blue platinum compounds

Summary The preparation of platinum blues from Pt(NH₃)₂(H₂O) ₂ ²⁺ and benzoic or phthalic acids is described. The compounds were characterised by e.p.r., u.v./vis. and x-ray photoelectron spectroscopy. Unlike pyrimidine blues, the platinum blues reported here appear to be non-ionic.     

Return to equilibrium

The problem of return to equilibrium is phrased in terms of aC*-algebraU, and two one-parameter groups of automorphisms , ^P corresponding to the unperturbed and locally perturbed evolutions. The asymptotic evolution, under , of ^P -invariant, and ^P -K.M.S., states is considered. This study is a generalization of scattering theory and results concerning the existence of limit states are obtained by techniques similar to those used to prove the existence, and intertwining properties, of wave-operators. Conditions of asymptotic abelianness provide the necessary dispersive properties for the return to equilibrium. It is demonstrated that the ^P -equilibrium states and their limit states are coupled by automorphisms with a quasi-local property; they are not necessarily normal with respect to one another. An application to theX–Y model is given which extends previously known results and other applications, and examples, are given for the Fermi gas.     

The ground state of the Bose gas

The mathematical formalism describing the Bose gas at zero temperature is analysed with the aid of methods that have recently been successful in relativistic quantum field theory. First the spectrum conditions for an infinitely extended system are given and the algebra of observables and the algebra of field operators are defined. General properties of states over these algebras are discussed and theorems are given which connect the linked cluster property, translation invariance and the purity of the states. It is proved that pure states over the algebra of observables have the property of factorisable off-diagonal long range order. The class of quasi free states is defined and of these states those which are translation invariant and possess the linked cluster property are analysed. It is shown that this class of states contains a subclass of pure states of the Bogoliubov type and a subclass of states which are mixtures of non-translationally invariant pure states. The applications of these quasi free states to the interacting Bose gas are summarized.     

Empirical modeling of human face kinematics during speech using motion clustering

In this paper we present an algorithm for building an empirical model of facial biomechanics from a set of displacement records of markers located on the face of a subject producing speech. Markers are grouped into clusters, which have a unique primary marker and a number of secondary markers with an associated weight. Motion of the secondary markers is computed as the weighted sum of the primary markers of the clusters to which they belong. This model may be used to produce facial animations, by driving the primary markers with measured kinematic signals.