Robert Knott

Composite Polymer Electrolyte Containing Ionic Liquid and Functionalized Polyhedral Oligomeric Silsesquioxanes for Anhydrous PEM Applications

A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

Strategies for data collection and calibration with a pinhole‐geometry SAXS instrument on a synchrotron beamline

Undulator X-ray sources on third-generation synchrotrons have pushed small-angle X-ray scattering (SAXS) to the forefront of techniques in nanoscience and technology. With higher X-ray fluxes and improved focusing, it is usually the scattered intensity detector that places the most serious limitations on the overall capabilities of the instrument. Incorporating relatively simple components like point detectors, scattering standards, masking filters and in-line sample visualization into the flight tube of a pinhole-geometry SAXS camera can do much to mitigate these limitations. How these enhancements can be incorporated into routine data collection is demonstrated on the ChemMatCARS SAXS instrument, which utilizes pinhole geometry with an undulator insertion device at sector 15 of the Advanced Photon Source. In addition, with an X-ray energy range of 6-32 keV (2.0-0.4 A) and an energy resolution of 10(-4) DeltaE/E, this instrument can measure anomalous SAXS over a wide variety of atom species, with reliable normalization of scattered data.

The structure of dopamine induced α-synuclein oligomers

Inclusions of aggregated α-synuclein (α-syn) in dopaminergic neurons are a characteristic histological marker of Parkinson’s disease (PD). In vitro, α-syn in the presence of dopamine (DA) at physiological pH forms SDS-resistant non-amyloidogenic oligomers. We used a combination of biophysical techniques, including sedimentation velocity analysis, small angle X-ray scattering (SAXS) and circular dichroism spectroscopy to study the characteristics of α-syn oligomers formed in the presence of DA. Our SAXS data show that the trimers formed by the action of DA on α-syn consist of overlapping worm-like monomers, with no end-to-end associations. This lack of structure contrasts with the well-established, extensive β-sheet structure of the amyloid fibril form of the protein and its pre-fibrillar oligomers. We propose on the basis of these and earlier data that oxidation of the four methionine residues at the C- and N-terminal ends of α-syn molecules prevents their end-to-end association and stabilises oligomers formed by cross linking with DA-quinone/DA-melanin, which are formed as a result of the redox process, thus inhibiting formation of the β-sheet structure found in other pre-fibrillar forms of α-syn.

A Genetically Engineered Protein Responsive to Multiple Stimuli

Smart protein: Careful design can yield novel biologically inspired materials that display advanced responsive behavior. A genetically engineered elastic protein displays both a lower and an upper critical solution temperature (LCST and UCST, see picture), and its photophysical behavior depends on solution pH value.

Hydration in protein crystallography.

Water in close proximity to the protein surface is fundamental to protein folding, stability, recognition and activity. Protein structures studied by diffraction methods show ordered water molecules around some charged, polar, and non-polar (hydrophobic) amino acids, although the later are only observed when they are at the interface between symmetry related molecules in the crystal. Water networks surrounding the protein have been observed for small proteins. Crystallographically observed water molecules are referred to as bound structural water molecules. During crystallographic data analysis, bound water molecules are often treated as though they belong to the protein. Recent developments in the treatment of the bulk solvent contribution to the low order diffraction data allow a better evaluation of the surface structure of the protein and a better localization of bound waters. The mobility of bound waters is studied by means of temperature and occupancy factors. The bulk solvent has relatively large disorder (liquid like) which is represented by liquidity factors. Within this context water layers surrounding the protein have little mobility.

The depressurization of an expanded solution into aqueous media for the bulk production of liposomes.

A new dense gas process for the formation of liposomes has been developed: depressurization of an expanded solution into aqueous media (DESAM). The technique provides a fast and simple process for bulk liposome formation. As an alternative to current dense gas technologies, the DESAM process reduces the pressure requirements for liposome formation. Liposomes with diameters between 50 and 200 nm were formed. For all samples produced using ethanol as the solvent, the average effective diameter ranged from 119 to 207 nm. When chloroform was used as the solvent, the average effective diameter increased to 387 nm. The residual solvent volume fraction in the liposomal product was less than 4% v/v, which is approximately one-quarter of the value reported for some other dense gas liposome formation methods. The liposomal samples were stored after formation at 5 degrees C for up to 8 months, with the average effective diameter and polydispersity increasing by only 13% and 7%, respectively, indicating high stability of the formulations.

Trishomocubanes, a new class of selective and high affinity ligands for the sigma binding site

Abstract The synthesis, receptor binding, and preliminary structural characterisation of trishomocubanes of types pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecylamines- and 4-azahexacyclo[5.4.1.0 2,6 .0 3,10 .0 5,9 .0 8,11 ]dodecanes are described. These ligands demonstrated high selectivity and affinity for the sigma binding site.

Near superhydrophobic fibrous scaffold for endothelialization: Fabrication, characterization and cellular activities

In this work, we have applied an electrospinning method to control wettability and further hydrophobic modification of a hydrophobic polymer mat of poly(vinylidene fluoride-co-hexafluoropropylene). A correlation between the processing parameters, rheological properties of polymer solutions, and electrospinning ability was made using the polymers critical entanglement concentration, the boundary between the semidilute unentangled regime and the semidilute entangled regime. The wetting behavior, structural and thermal characteristics of electrospun (ES) mats were evaluated and compared with solvent cast sample using advancing and receding contact angle analyses, differential scanning calorimetry, and small-angle X-ray scattering. To demonstrate the feasibility, the best optimized ES samples were examined for their potential and ability to support bone marrow derived endothelial cell seeding efficiency, adhesion and proliferation. Our studies show that, while different processing techniques can effectively modulate physical and morphological changes such as porosity and hydrophobicity, the cellular adhesion and proliferation are highly time-dependent and controlled by chemical factors. As such, these results suggest that it is the interplay of both physical and chemical factors that determine the endothelialization of porous near superhydrophobic scaffolds. The developed electrospun samples demonstrate their feasibility for endothelialization.

Nanostructure Evolution in High-Temperature Perfluorosulfonic Acid Ionomer Membrane by Small-Angle X-ray Scattering

The high-temperature morphology of supported liquid membranes (SLMs) prepared from perfluorinated membranes such as Nafion and Hyflon and hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-TFSI) has been investigated by small-angle X-ray scattering (SAXS). Proton conductivity results of SLMs before and after leaching show an increase in conductivity with temperature up to 160 °C in an anhydrous environment. DSC results show that crystallites within perfluorinated membranes are thermally stable up to 196 °C. High-temperature SAXS results have been used to correlate structure and morphology of supported liquid membranes with high-temperature conductivity data. The ionic liquid essentially acts as a proton solvent in a similar way to water in hydrated Nafion membranes and increases size of clusters, which allow percolation to be achieved more easily. The cation of the ionic liquid interacts with sulfonate groups within ionic domains through electrostatic interactions and displaces protons. Protons can associate with free anions of the ionic liquid, which are loosely associated with cations and can transport by hopping from anion sites within the membrane. The ionic liquid contributes to proton conductivity at high temperature through achievement of long-range ordering and subsequent percolation.

Formation of Liquid-Crystalline Structures in the Bile Salt–Chitosan System and Triggered Release from Lamellar Phase Bile Salt–Chitosan Capsules

Nanostructured capsules comprised of the anionic bile salt, sodium taurodeoxycholate (STDC), and the biocompatible cationic polymer, chitosan, were prepared to assess their potential as novel tailored release nanomaterials. For comparison, a previously studied system, sodium dodecyl sulfate (SDS), and polydiallyldimethylammonium chloride (polyDADMAC) was also investigated. Crossed-polarizing light microscopy (CPLM) and small-angle X-ray scattering (SAXS) identified the presence of lamellar and hexagonal phase at the surfactant-polymer interface of the respective systems. The hydrophobic and electrostatic interactions between the oppositely charged components were studied by varying temperature and salt concentration, respectively, and were found to influence the liquid-crystalline nanostructure formed. The hexagonal phase persisted at high temperatures, however the lamellar phase structure was lost above ca. 45 °C. Both mesophases were found to dissociate upon addition of 4% NaCl solution. The rate of release of the model hydrophilic drug, Rhodamine B (RhB), from the lamellar phase significantly increased in response to changes in the solution conditions studied, suggesting that modulating the drug release from these bile salt-chitosan capsules is readily achieved. In contrast, release from the hexagonal phase capsules had no appreciable response to the stimuli applied. These findings provide a platform for these oppositely charged surfactant and polymer systems to function as stimuli-responsive or sustained-release drug delivery systems.