Adsorption of charged macromolecules at a gold electrode

Using an optical reflectometer with impinging-jet system, the adsorption from aqueous solution onto gold of three charged macromolecules has been studied: the strong linear-chain polyelectrolyte polyvinyl pyridine (PVP(+)), the fifth-generation poly(propylene imine) dendrimer DAB-64, which has a pH-dependent charge and a relatively fixed shape, and the protein lysozyme, of which both the charge and the structure-stability are dependent on solution composition. Experimental conditions that have been varied include the adsorbate concentration, electrolyte concentration, pH, and externally applied potential across the gold/solution interface. Making use of the earlier established dependency of the double layer potential of the gold substrate on solution conditions and externally applied potential, the results of measurements as a function of pH and as a function of external potential control are compared. The total set of results enables us to draw conclusions with respect to the relative importance of electrostatic interactions for the adsorption process. PVP(+) adsorption follows the electric potential of the gold/solution interface and is further determined by a rather strong nonelectrostatic affinity between segments and surface. The adsorption behavior of DAB-64 is not quite understood, but electrostatic interactions with the gold surface seem to play a minor role. For lysozyme, surface-induced conformational changes dominate the adsorption process. The extent of spreading of the molecules decreases with increasing polarity of the surface, resulting in a minimum in adsorbed amount around the point of zero potential of the gold.     

Chaos in thermal pulse combustion

An experimental thermal pulse combustor and a differential equation model of this device are shown to exhibit chaotic behavior under certain conditions. Chaos arises in the model by means of a progression of period-doubling bifurcations that occur when operating parameters such as combustor wall temperature or air/fuel flow are adjusted to push the system toward flameout. Bifurcation sequences have not yet been reproduced experimentally, but similarities are demonstrated between the dynamic features of pressure fluctuations in the model and experiment. Correlation dimension, Kolmogorov entropy, and projections of reconstructed attractors using chaotic time series analysis are demonstrated to be useful in classifying dynamical behavior of the experimental combustor and for comparison of test data to the model results. Ways to improve the model are suggested. (c) 1995 American Institute of Physics.     

Dynamics of Abelian Higgs vortices in the near Bogomolny regime

The aim of this paper is to give an analytical discussion of the dynamics of the Abelian Higgs multi-vortices whose existence was proved by Taubes ([JT82]). For a particular value of a parameter of the theory, , called the Higgs self-coupling constant, there is no force between two vortices and there exist static configurations corresponding to vortices centred at any set of points in the plane. This is known as the Bogomolny regime. We will develop some formal asymptotic expansions to describe the dynamics of these multi-vortices for close, but not equal to, this critical value. We shall then prove the validity of these asymptotic expansions. These expansions allow us to give a finite dimensional Hamiltonian system which describes the vortex dynamics. The configuration space of this system is the moduli space—the space of solutions of the static equations modulo gauge equivalence. The kinetic energy term in the Hamiltonian is obtained from the natural metric on the moduli space given by theL ² inner product of the tangent vectors. The potential energy gives the intervortex potential which is non-zero when is not given by its critical value. Thus the reduced equations for the evolution of the vortex parameters take the form of geodesics, with force terms to express the departure from the Bogomolny regime. The geodesics are geodesics on the moduli space with respect to the metric defined by theL ² inner product of the tangent vectors, in accordance with Manton's suggestion ([Man82]). This allows an understanding of the two main phenomenological issues—first of all there is the right angle scattering phenomenon, according to which two vortices passing through one another scatter through ninety degrees. Secondly there is the conjecture from numerical calculations that vortices repel for greater than the critical value, and attract for less than this value. The results of this paper allow a rigorous understanding of the right angle scattering phenomenon ([Sam92, Hit88]) and reduce the question of attraction or repulsion in the near Bogomolny regime to an understanding of the potential energy term in the Hamiltonian ([JR79]).     

Stereochemically controlled synthesis of unsaturated acids via diphenylphosphinoyl (Ph2PO) -ketoacids

Acylation of phosphine oxide anions with derivatives of cyclic anhydrides or oxidative cleavage of cyclic allyl phosphine oxides gives Ph₂PO-ketoacids: reduction, separation of diastereoisomers, and completion of the Horner-Wittig reaction gives single isomers ($\text{E}$) or ($\text{Z}$) of unsaturated acids.     

Inelastic incoherent neutron scattering measurements of intact cells and tissues and detection of interfacial water

We have previously used inelastic incoherent neutron scattering spectroscopy to investigate the properties of aqueous suspensions of biomolecules as a function of hydration. These experiments led to the identification of signals corresponding to interfacial (hydration) water at low water content. A prediction from these studies was that in the crowded environment inside living cells, a significant proportion of the water would be interfacial, with profound implications for biological function. Here we describe the first inelastic incoherent neutron scattering spectroscopy studies of living cells and tissues. We find that the interfacial water signal is similar to that observed for water interacting with purified biomolecules and other solutes, i.e., it is strongly perturbed in the librational and translational intermolecular optical regions of the spectrum at 20-150 meV. The ratio of interfacial water compared to total water in cells (approximately 30%) is in line with previous experimental data for hydration water and calculations based on simple assumptions.