Shape morphology of dipolar domains in planar and spherical monolayers.

We present a continuum theory for predicting the equilibrium shape and size of dipolar domains formed during liquid-liquid phase coexistence in planar and spherical monolayers. Our main objective is to assess the impact of the monolayer surface curvature on domain morphology. Following previous investigators, we base our analysis around minimizing the free energy, with contributions from line tension and electrostatic dipolar repulsions. Assuming a monodisperse system of circularly symmetric domains, we calculate self-energies and interaction energies for planar and spherical monolayers and determine the equilibrium domain size from the energy minima. We subsequently evaluate the stability of the circularly symmetric domain shapes to an arbitrary, circumferential distortion of the perimeter via a linear stability analysis. We find that the surface curvature generally promotes the formation of smaller, circularly symmetric domains instead of larger, elongated domains. We rationalize these results by examining the effect of the curvature on the intra- and inter-domain dipolar repulsions. We then present a phase diagram of domain shape morphologies, parameterized in terms of the domain area fraction and the monolayer curvature. For typical domain dimensions of 1-30 µm, our theoretical results are relevant to monolayers (and possibly also bilayers) in liquid-liquid phase coexistence with radii of curvature of 1-100 µm.

Interfacial rheology of coexisting solid and fluid monolayers.

Biologically relevant monolayer and bilayer films often consist of micron-scale high viscosity domains in a continuous low viscosity matrix. Here we show that this morphology can cause the overall monolayer fluidity to vary by orders of magnitude over a limited range of monolayer compositions. Modeling the system as a two-dimensional suspension in analogy with classic three-dimensional suspensions of hard spheres in a liquid solvent explains the rheological data with no adjustable parameters. In monolayers with ordered, highly viscous domains dispersed in a continuous low viscosity matrix, the surface viscosity increases as a power law with the area fraction of viscous domains. Changing the phase of the continuous matrix from a disordered fluid phase to a more ordered, condensed phase dramatically changes the overall monolayer viscosity. Small changes in the domain density and/or continuous matrix composition can alter the monolayer viscosity by orders of magnitude.

Active microrheology and simultaneous visualization of sheared phospholipid monolayers.

Two-dimensional films of surface-active agents-from phospholipids and proteins to nanoparticles and colloids-stabilize fluid interfaces, which are essential to the science, technology and engineering of everyday life. The 2D nature of interfaces present unique challenges and opportunities: coupling between the 2D films and the bulk fluids complicates the measurement of surface dynamic properties, but allows the interfacial microstructure to be directly visualized during deformation. Here we present a novel technique that combines active microrheology with fluorescence microscopy to visualize fluid interfaces as they deform under applied stress, allowing structure and rheology to be correlated on the micron-scale in monolayer films. We show that even simple, single-component lipid monolayers can exhibit viscoelasticity, history dependence, a yield stress and hours-long time scales for elastic recoil and aging. Simultaneous visualization of the monolayer under stress shows that the rich dynamical response results from the cooperative dynamics and deformation of liquid-crystalline domains and their boundaries.

Suppression of electro-osmotic flow by surface roughness.

We show that nanoscale surface roughness, which commonly occurs on microfabricated metal electrodes, can significantly suppress electro-osmotic flows when excess surface conductivity is appreciable. We demonstrate the physical mechanism for electro-osmotic flow suppression due to surface curvature, compute the effects of varying surface conductivity and roughness amplitudes on the slip velocities of a model system, and identify scalings for flow suppression in different regimes of surface conduction. We suggest that roughness may be one factor that contributes to large discrepancies observed between classical electrokinetic theory and modern microfluidic experiments.

Stability of a charged particle in a combined Penning-Ioffe trap.

The axial symmetry of a familiar Penning trap is broken by adding the radial magnetic field of an Ioffe trap. Despite the resulting loss of a confinement theorem, stable orbits related to adiabatic invariants are identified, expressions are given for their frequencies, and resonances that must be avoided are characterized. It seems feasible to experimentally realize the new Penning-Ioffe trap to test these theoretical predictions. It also may be possible to simultaneously confine cold positrons and antiprotons in a Penning-Ioffe trap, along with any cold antihydrogen they may form.

Inhibitors of abscisic acid 8'-hydroxylase.

Structural analogues of the phytohormone (+)-abscisic acid (ABA) have been synthesized and tested as inhibitors of the catabolic enzyme (+)-ABA 8'-hydroxylase. Assays employed microsomes from suspension-cultured corn cells. Four of the analogues [(+)-8'-acetylene-ABA, (+)-9'-propargyl-ABA, (-)-9'-propargyl-ABA, and (+)-9'-allyl-ABA] proved to be suicide substrates of ABA 8'-hydroxylase. For each suicide substrate, inactivation required NADPH, increased with time, and was blocked by addition of the natural substrate, (+)-ABA. The most effective suicide substrate was (+)-9'-propargyl-ABA (K(I) = 0.27 microM). Several analogues were competitive inhibitors of ABA 8'-hydroxylase, of which the most effective was (+)-8'-propargyl-ABA (K(i) = 1.1 microM). Enzymes in the microsomal extracts also hydroxylated (-)-ABA at the 7'-position at a low rate. This activity was not inhibited by the suicide substrates, showing that the 7'-hydroxylation of (-)-ABA was catalyzed by a different enzyme from that which catalyzed 8'-hydroxylation of (+)-ABA. Based on the results described, a simple model for the positioning of substrates in the active site of ABA 8'-hydroxylase is proposed. In a representative physiological assay, inhibition of Arabidopsis thaliana seed germination, (+)-9'-propargyl-ABA and (+)-8'-acetylene-ABA exhibited substantially stronger hormonal activity than (+)-ABA itself.

Hydrodynamic coupling of two brownian spheres to a planar surface.

We describe direct imaging measurements of the collective and relative diffusion of two colloidal spheres near a flat plate. The bounding surface modifies the spheres' dynamics, even at separations of tens of radii. This behavior is captured by a stokeslet analysis of fluid flow driven by the spheres' and wall's no-slip boundary conditions. In particular, this analysis reveals surprising asymmetry in the normal modes for pair diffusion near a flat surface.

Anthracenone ABA analogue as a potential photoaffinity reagent for ABA-binding proteins.

An anthracenone analogue of abscisic acid (ABA) was synthesized as a potential photoaffinity reagent and tested for biological activity. Reaction between 10,10'-dimethoxy-9-anthrone with two equivalents of the lithiated dianion of cis-3-methylpent-2-en-4-yn-1-ol afforded an acetylenic alcohol key intermediate. Subsequent reduction of the triple bond, functional group manipulation of the side chain alcohol and deprotection of the dimethoxy protected anthrone provided anthracenone ABA analogue 7 as a potential photoaffinity reagent for ABA-binding proteins. The effect of natural ABA and the potential photoaffinity anthracenone ABA 7 on corn cell growth was determined at various concentrations. The results show that anthracenone ABA 7 is perceived as ABA-like, although producing less inhibition than ABA itself. For example, 7 at 33 microM produces approximately the same inhibition as ABA at 10 microM.