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Gary McPherson

Publications and source records attributed to Gary McPherson.

5 recordsLinked to original sources

31P and 1h NMR as probes of domain alignment in a rigid crystalline surfactant mesophase.

A viscous reverse hexagonal surfactant mesophase containing bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water, was characterized by Fourier transform (31)P and (1)H NMR spectroscopy. Shear alignment was reflected through both (31)P NMR and (1)H NMR spectra. A complicated (31)P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures become macroscopically aligned after Couette shear. (31)P NMR chemical shift anisotropy characteristics are used to elucidate orientation of the hexagonal phase. Interestingly, (1)H NMR spectra exhibit spectral changes upon shear alignment closely corresponding with that of (31)P NMR spectra. These observations complement the findings of mesophase alignment obtained using SANS and imply that (31)P and (1)H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis.

Journal Article↗

Biocatalysis in the development of functional polymer-ceramic nanocomposites.

Fluorescent silica/polymer nanocomposites have been synthesized by condensing tetramethyl orthosilicate (TMOS) around fluorescent polymer strands of poly(2-naphthol). The polymer is biocatalytically synthesized via peroxidase catalyzed polymerization in micelles of the cationic surfactant, cetyltrimethylammonium bromide (CTAB). Silica condensation at the micelle-water interface results in encapsulation of the polymer. Fluorescence spectroscopy and fluorescent light microscopy provide critical evidence that the polymer luminescence properties are conferred to the composite material. The fabrication of polymer entrapped in ordered, mesoporous materials represents a viable step toward the development of functional polymer-ceramic nanocomposites.

Catalysis↗

Structural evolution of a two-component organogel.

Dry reverse micelles of AOT in isooctane spontaneously undergo a microstructural transition to an organogel upon the addition of a phenolic dopant, p-chlorophenol. This microstructural evolution has been studied through a combination of light scattering, small-angle neutron scattering (SANS), NMR, and rheology. Several equilibrium stages between the system of dry reverse micelles of AOT and a 1:1 AOT/p-chlorophenol (molar ratio) gel in isooctane have been examined. To achieve this, p-chlorophenol is added progressively to the dilute solutions of AOT in isooctane, and this concentration series is then analyzed. The dry micelles of AOT in isooctane do not undergo any detectable structural change up to a certain p-chlorophenol concentration. Upon a very small increment in the concentration of p-chlorophenol beyond this "threshold" concentration, large strandlike aggregates are observed which then evolve to the three-dimensional gel network.

Chlorophenols↗

Shear-induced orientation of a rigid surfactant mesophase.

An optically clear, crystalline, gel-like mesophase is formed by the addition of water to a micellar solution consisting of a mixture of 0.85 M anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and a 0.42 M zwitterionic surfactant phosphatidylcholine (lecithin) in isooctane. At 25 degrees C and water to AOT molar ratio of 70, the system has a columnar hexagonal microstructure with randomly oriented domains. The shear-induced orientation and subsequent relaxation of this structure were investigated by rheological characterization and small-angle neutron scattering (SANS). The rheological response implies that the domains align under shear, and remain aligned for several hours after cessation of shear. Shear-SANS confirms this picture. The sheared gel mesophase retains its alignment as the temperature is increased to 57 degrees C, indicating the potential to conduct templated polymer and polymer-ceramic composite materials synthesis in aligned systems.

Journal Article↗

Freeze fracture direct imaging of a viscous surfactant mesophase.

Freeze fracture direct imaging (FFDI) has been used to image microstructures present in a highly viscous four-component mesophase containing water, isooctane, AOT [bis(2-ethylhexyl) sodium sulfosuccinate], and lecithin. As water is added to a fixed amount of a ternary solution of isooctane and the two surfactants, the microstructure evolves from a water-in-oil microemulsion, to a highly viscous columnar hexagonal, and then to multilamellar vesicles. Each of these microstructures is imaged directly. Previous small-angle neutron scattering measurements have identified the lamellar phase, but the FFDI technique demonstrates that these are onionlike curved multilamellar structures rather than planar bilayers. Freeze fracture direct imaging expands the range of cryo-transmission microscopy to highly viscous, high-organic-content systems that typically have been difficult to visualize.

Freeze Fracturing↗