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P J Collings

Publications and source records attributed to P J Collings.

6 recordsLinked to original sources

Premelting at defects within bulk colloidal crystals.

Premelting is the localized loss of crystalline order at surfaces and defects at temperatures below the bulk melting transition. It can be thought of as the nucleation of the melting process. Premelting has been observed at the surfaces of crystals but not within. We report observations of premelting at grain boundaries and dislocations within bulk colloidal crystals using real-time video microscopy. The crystals are equilibrium close-packed, three-dimensional colloidal structures made from thermally responsive microgel spheres. Particle tracking reveals increased disorder in crystalline regions bordering defects, the amount of which depends on the type of defect, distance from the defect, and particle volume fraction. Our observations suggest that interfacial free energy is the crucial parameter for premelting in colloidal and atomic-scale crystals.

Journal Article↗

Effective index of refraction, optical rotation, and circular dichroism in isotropic chiral liquid crystals.

This paper concerns optical properties of the isotropic phase above the isotropic-cholesteric transition and of the blue phase BP III. We introduce an effective index, which describes spatial dispersion effects such as optical rotation, circular dichroism, and the modification of the average index due to the fluctuations. We derive the wavelength dependence of these spatial dispersion effects quite generally without relying on an expansion in powers of the chirality and without assuming that the pitch of the cholesteric P is much shorter than the wavelength of the light lambda, an approximation that has been made in previous studies of this problem. The theoretical predictions are supported by comparing them with experimental spectra of the optical activity in the BP III phase.

Journal Article↗

Field-dependent tilt and birefringence of electroclinic liquid crystals: theory and experiment.

An unresolved issue in the theory of liquid crystals is the molecular basis of the electroclinic effect in the smectic-A phase. Recent x-ray scattering experiments suggest that, in a class of siloxane-containing liquid crystals, an electric field changes a state of disordered molecular tilt in random directions into a state of ordered tilt in one direction. To investigate this issue, we measure the optical tilt and birefringence of these liquid crystals as functions of field and temperature, and we develop a theory for the distribution of molecular orientations under a field. A comparison of theory and experiment confirms that these materials have a disordered distribution of molecular tilt directions that is aligned by an electric field, giving a large electroclinic effect. It also shows that the effective dipole moment, a key parameter in the theory, scales as a power law near the smectic-A--smectic-C transition.

Journal Article↗

Aggregation kinetics of extended porphyrin and cyanine dye assemblies.

The kinetics of J-aggregate formation has been studied for two chromophores, tetrakis-4-sulfonatophenylporphine in an acid medium and pseudoisocyanine on a polyvinylsulfonate template. The assembly processes differ both in their sensitivity to initiation protocols and in the reaction profiles they produce. The porphyrin's assembly kinetics, for example, displays an induction period unlike that of the cyanine dye. Two kinetic models are presented. For the porphyrin, an autocatalytic pathway in which the formation of an aggregation nucleus is rate-determining appears to be applicable; for the pseudoisocyanine dye, an equation derived for diffusion-limited aggregation of a fractal object satisfactorily fits the data. These models are shown to be useful for the analysis of kinetic data obtained for several biologically important aggregation processes.

Adsorption↗

Resonance light scattering: a new technique for studying chromophore aggregation.

Light scattering experiments are usually performed at wavelengths away from absorption bands, but for species that aggregate, enhancements in light scattering of several orders of magnitude can be observed at wavelengths characteristic of these species. Resonance light scattering is shown to be a sensitive and selective method for studying electronically coupled chromophore arrays. The approach is illustrated with several examples drawn from porphyrin and chlorin chemistry. The physical principles underlying resonance light scattering are discussed, and the advantages and limitations of the technique are reviewed.

Chlorophyll↗

High pressure volumetric measurements in dipalmitoylphosphatidylcholine bilayers.

The one previously reported high pressure volumetric experiment on a phospholipid bilayer investigated a region of pressure between 0 and 25 MPa and obtained isothermal compressibility values for the liquid crystal and intermediate phases which differed by more than a factor of ten. We report new volumetric measurements around the main transition in dipalmitoylphosphatidylcholine (DPPC) from 0 to 100 MPa. The isothermal compressibility data for the two phases are of the same order of magnitude, and the experimentally determined coexistence curve, specific volume dependence, and volume discontinuity values are compared with the predictions of the phenomenological theory according to Sugar and Tarjan ((1982) Sov. Phys. Crystallogr. 27, 4-5). Significant discrepancies between this theory and experiment are found. Finally, the data indicate that steric interactions play a more dominant role in the main transition of phospholipid bilayers than in transitions in most thermotropic liquid crystals.

Atmospheric Pressure↗