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Stephen J Picken

Publications and source records attributed to Stephen J Picken.

6 recordsLinked to original sources
PubMed2006

Ordered structures in proton conducting membranes from supramolecular liquid crystal polymers.

Highly sulfonated forms of poly(p-phenylene terephthalamide) (PPTA) have been prepared in three different molecular configurations; sulfonated diamine form (S-PPTA), sulfonated terephthalic acid form (S-invert-PPTA), and the bi-sulfonated form (S2-PPTA). All three polymers are water soluble to a certain degree and films were cast from solution for S-PPTA and S-invert-PPTA. S-PPTA films absorb less water than S-invert-PPTA (under controlled humidity conditions) and consequently, the conductivity for this polymer is also slightly lower. Although the conductivities are comparable to Nafion (of the order of 10(-2) to 10(-1) Scm(-1)), proton mobility is more restricted. X-ray diffraction showed that the rigid molecules are aligned in opposite directions for the two polymer films, being homeotropic in S-PPTA films and planar for S-invert-PPTA. SEM analysis demonstrated layering in the same direction as the alignment of the polymer chains. The variation in the polymer alignment is most likely the result of the differences in the solution properties and the film forming process. It is possible, however, that this alignment could be exploited to enhance proton transport and thus these films are of interest for fuel cell membranes.

Journal Article↗
PubMed2006

7-Dialkylamino-1-alkylquinolinium salts: highly versatile and stable fluorescent probes.

7-Dialkylamino- and 7-alkylsulfenyl-1-alkylquinolinium salts have been synthesized using a novel synthetic approach. The key intermediate, 7-fluoro-1-methylquinolinium iodide, was shown to possess high reactivity toward nitrogen and sulfur nucleophiles, and the kinetics of this nucleophilic aromatic substitution reaction was investigated. A wide variety of compounds were synthesized and characterized spectroscopically. High fluorescence quantum yields were observed, and this was attributed to the rigid molecular architecture. The thermal and photochemical stability of a number of compounds was investigated, and it was demonstrated that 7-dialkylamino-1-methylquinolinium salts have superior stability compared to a number of hemicyanine dyes and rigid charge-transfer probes. Based on the high quantum yields, the large Stokes shifts, and in particular, the high thermal and photochemical stability, it is concluded that 7-dialkylamino-1-methylquinolinium salts are excellent color-shifting, mobility-sensitive fluorescent probes for polymer characterization and other demanding applications.

Fluorescent Dyes↗
PubMed2006

Elasticity, viscosity, and deformation of orbital fat.

PURPOSE: For development of a finite element analysis model of orbital mechanics, it was necessary to determine the material properties of orbital fat and its degree of deformation in eye rotation. METHODS: Elasticity and viscosity of orbital fat of eight orbits of four calves and two orbits of one rhesus monkey were measured with a parallel-plate rheometer. The degree of deformation of orbital fat was studied in two human subjects by magnetic resonance imaging (MRI) through the optic nerve in seven (first subject) or fourteen positions of gaze from left to right. Bifurcations of veins in the fat were used as markers for displacement of the fat. RESULTS: The elastic shear modulus (G') of calf orbital fat was between 250 Pa and 500 Pa, and of monkey orbital fat it was between 500 Pa and 900 Pa. The viscous shear modulus (G'') of calf orbital fat was between 80 Pa and 150 Pa, and for monkey orbital fat it was between 300 Pa and 500 Pa. In the MRI scans, it was found that markers in the fat, 1 to 5 mm posterior to the sclera, rotated with the eye for 36% to 53% of eye rotation; the remainder was accounted for by sliding of the eye within the Tenon capsule and within the orbital fat. CONCLUSIONS: Elastic and viscous shear moduli of orbital fat are low. Little energy is dissipated in the fat. The required deformation of the fat during eye rotation is limited because the eye slides, to some extent, within the Tenon capsule.

Adipose Tissue↗
PubMed2004

A supramolecular nematic phase in sulfonated polyaramides.

A water-soluble polyaramide "sulfo-invert-PPTA" surprisingly, already at a molecular weight of 10,000 g mol(-1), exhibits a nematic liquid crystalline phase in water at very low polymer concentrations, around 1-2wt%, indicating that supramolecular assemblies of molecules are the building blocks of the nematic phase.

Journal Article↗
PubMed2003

Dynamics of a triphenylene discotic molecule, HAT6, in the columnar and isotropic liquid phases.

Discotic molecules have planar, disklike polyaromatic cores that can self-assemble into "molecular wires". Highly anisotropic charge transfer along the wires arises when there is sufficient intermolecular overlap of the pi-orbitals of the molecular cores. Discotic materials can be applied in molecular electronics, field-effect transistors, and-recently with record quantum efficiencies-photovoltaics (Schmidt-Mende, L.; Fechtenkötter, A.; Müllen, K.; Moons, E.; Frien, R. H.; MacKenzie, J. D. Science 2001, 293, 1119). A combination of quasielastic neutron scattering (QENS) measurements with molecular dynamics simulations on the discotic molecule hexakis(n-hexyloxy)triphenylene (HAT6) shows that the dynamics of the cores and tails of discotic molecules are strongly correlated. Core and tail dynamics are not separated, the system being characterized by overall in-plane motion, on a time scale of 0.2 ps, and softer out-of-plane motions at 7 ps. Because charge transfer between the molecules is on similar time scales, these motions are relevant for the conducting properties of the materials. Both types of motion are dominated by van der Waals interactions. Small-amplitude in-plane motions in which the disks move over each other are almost entirely determined by tail/tail interactions, these also playing an important role in the out-of-plane motion. The QENS measurements reveal that these motions are little changed by passing from the columnar phase to the isotropic liquid phase, just above the clearing temperature. The model of four HAT6 molecules in a column reproduces the measured QENS spectrum of the liquid phase, suggesting that correlations persist within the liquid phase over about this number of disks.

Journal Article↗