Biomedical subjects
Publications and source records attributed to Richard K Heenan.
Employing photodestructible surfactants in gelatin-based aqueous gels presents novel possibilities for controlling colloidal and aggregation properties of surfactant gelatin complexes. Light-triggered breakdown of the gelatin-bound photosurfactant aggregates causes dramatic changes in viscosity and aggregation.
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Small-angle neutron-scattering measurements are presented for homogeneous mixtures of poly (methyl vinyl ether) (PVME) and deuterium oxide (D(2)O) at high polymer concentrations and for temperatures lower than the equilibrium melting point of the solvent. The experimental data are analyzed to give values for the second-order compositional derivative of the Gibbs energy and the Ornstein-Zernike correlation length. The experimental data together with earlier SANS data determined at higher temperatures cannot be represented with an extended Flory-Huggins (F-H) interaction function depending on composition and temperatures. The experimental data confirm the existence of a narrow upper critical solution temperature (UCST) miscibility gap at high concentrations in agreement with theoretical predictions of the Wertheim lattice thermodynamic perturbation theory (LTPT). The Wertheim LTPT incorporates the influence of hydrogen bonding and predicts not only the existence of bimodal lower critical solution temperature (LCST) phase behavior but also the occurrence of highly unconventional two narrow adjacent UCST miscibility gaps. Finally, the experimental data do not support the existence of a stable molecular complex at the investigated temperatures and compositions. Even at the lowest investigated temperature, the energy required to induce typical Ornstein-Zernike-like concentration fluctuations is smaller than the thermal energy. Also, in this case, the Wertheim LTPT provides a theoretical basis to understand the formation of polymer solvent associations in PVME/water.
Bioresponsive polymers are being developed as synthetic viral mimetics to enhance the intracellular delivery of macromolecular therapeutic agents such as genes, proteins and peptides. In this context we have designed pH-responsive, amphoteric polyamidoamines (PAAs) which change conformation on passing from a neutral pH (extracellular) to an acidic pH (endosomal and lysosomal) environments. PAAs have already demonstrated cytosolic delivery of genes and non-permeant toxins (e.g. gelonin and ricin A chain). The aim of this study was to use small-angle neutron scattering (SANS) to investigate the most likely shape of the hydrochloride salt form of one particular PAA (ISA23) in solution, under pH conditions that mimic those the polymer would be expected to encounter during endocytic internalisation (pH 7.4-3). It was shown that models based on a Gaussian coil representation of the polymer conformation described the SANS data better over this pH range than models based on a rod-like conformation. The conformation of ISA23 at 37 degrees C was expanded (radius of gyration approximately 80A) at pH approximately 3 but collapsed with an increase in pH (radius of gyration approximately 20A at pH 7.4), a conclusion also reached in a model-free analysis of the neutron data. Outside this pH range - at the extremes of high and low pH - the polymer coil collapsed and interpretation of the scattering was slightly complicated by the presence of a very weak structure factor indicating that the polymer coils are highly charged. The PAA concentration did not significantly affect the polymer size over the concentration range 10-50mg/ml. Characterisation of the dynamics of these polymer solutions - diffusion coefficients and viscosity -ostensibly suggest a very different conclusion with the polymer expanding as the pH is increased, but this arises due to weak aggregation of the amphoteric polymer coils.
Fluorosurfactants with several structural modifications have been synthesized, and the air/water interface and bulk aggregation properties investigated. The compounds were fluorinated ethylene oxide (EO) nonionics where the number and position of the hydrophilic group(s) has been radically altered to generate linear, bolaform, and Y-shaped analogues. A noticeable structure-interfacial packing relationship was observed via both tensiometric measurements and neutron reflection studies: the limiting molecular areas, a(cmc), and surface excesses, gamma(cmc), are strongly dependent on the number and position of the EO headgroups. Differing bulk aqueous properties were also observed. Small-angle neutron scattering shows an evolution of micelle structure from cylindrical to disk-like aggregates on changing from Y-shaped to bolaform molecular structure.
A novel approach of photoinduced phase separation has been demonstrated with a photolabile anionic surfactant, mixed with an inert nonionic surfactant in the presence of salting-out electrolyte. Breakdown of the photolyzable surfactant results in hydrophobic photoproducts, which are emulsified by the remaining inert surfactant; added electrolyte resolves the emulsion into macroscopic oily and aqueous phases. The initial micellar systems can disperse an insoluble additive marker dye (shown), which may be spatially segregated from the aqueous environment by the action of UV light.
Stable vesicles are formed in a 1.4 wt % solution comprising a 1:3 mixture of the anionic photodestructible surfactant sodium 4-hexylphenylazosulfonate (C6PAS) and inert cationic cetyltrimethylamonium bromide (CTAB). UV irradiation drives an irreversible breakdown of the mixed C6PAS/CATB vesicles, owing to the selective degradation of C6PAS. A light-induced transition from small spherical-like polydisperse vesicles to long needle-like aggregation is observed.
Properties are reported for new phenyl-tipped anionic surfactants, which are aromatic chain relatives of the normal aliphatic aerosol-OT (AOT, sodium bis(2-ethyl-1-hexyl)sulfosuccinate). Variations in chain length and branching with these aromatic surfactants have important effects on aqueous and water-in-oil (w/o) microemulsion phase properties. In dilute aqueous systems, chain structure affects the cmc and surface tension behavior: compared to linear chain analogues, the branched-chain surfactants display lower surface tensions but also reduced packing as measured by molecular area at the cmc a(cmc). Owing to the phenyl-tipped structure, water-in-oil microemulsions were stabilized with aromatic toluene as an oil but not with aliphatic heptane; the latter is commonly used with normal AOT. Contrast variation small-angle neutron scattering (SANS) was used to characterize the microemulsion aggregates and adsorbed films. These SANS data show that water-in-toluene microemulsions stabilized by aromatic-AOTs contain mildly polydisperse spherical nanodroplets of similar structure to those found in systems containing normal AOT. Molecular areas at the air-water and toluene-water interfaces are found to be of similar magnitude and follow a trend that correlates with variations in surfactant chain structure. The new results with aromatic surfactants build on extensive studies of aliphatic AOT analogues (Nave, S.; Eastoe, J.; Penfold, J. Langmuir 2000, 16, 8733. Nave, S.; Eastoe, J.; Heenan, R. K.; Steytler, D.; Grillo, I. Langmuir 2002, 16, 8741. Nave, S.; Eastoe, J.; Heenan, R. K.; Steytler, D.; Grillo, I. 2002, 18, 1505), suggesting that the versatility of normal AOT originates from an optimized head and chain spacer group rather than from any specific effects of the 2-ethyhexyl chain structure.
The structure of aggregates formed by eight surfactant [Ru(bipy)2(p,p'-dialkyl-2,2'-bipy)]Cl2 complexes-which we express as Ru(p)(q)Cn, where n (=12 or 19) is the alkyl chain length, p (=4 or 5) refers to the substitution position on the bipyridine ligand, and q (=1 or 2) is the number of substituted alkyl chains-in aqueous solutions has been examined using small-angle neutron scattering for a range of concentrations close to the critical micelle concentration and for several combinations of n, p, and q. A number of general results emerge. The double-chain surfactants possess a smaller headgroup charge but a larger aggregate size than their single-chain analogues. Over the concentration range studied, the micelles of the single-chain surfactants grow as the concentration is increased, whereas for the double-chain systems, the aggregate size remains unchanged. For both single- and double-chain surfactants, an increase in alkyl chain length is accompanied by an expected increase in aggregate size and an increase in average headgroup charge. The aggregates formed in solutions of resolved double-chain complexes are larger than those found in solutions of racemic mixtures. The Ru(4)(1)C12 and Ru(5)(1)C12 systems form aggregates with high water content. Variation of the substitution position for the single-chain surfactants produces dramatic changes in the structure of the micelles. The aggregates formed in solutions of Ru(4)(1)C19 and Ru(5)(1)C19 display particularly different structures. The Ru(4)(1)C19 system forms essentially spherical aggregates. In contrast, in the Ru(5)(1)C19 system, wormlike aggregates are formed in which the rigid rodlike sections appear to undergo a transition from a noninterdigitated to an interdigitated structure as the concentration is increased. For double-chain surfactants, the aggregation number for p = 4 surfactants is considerably larger than that for p = 5 surfactants.
Phase stability and small-angle neutron scattering (SANS) data show that surfactant-stabilized nanodomains of a typical ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4]) may be dispersed by the nonionic surfactant Triton-X100 in cyclohexane. Analyses of these SANS data are consistent with the formation of ionic liquid-in-oil microemulsion droplets.
In this paper we investigate the use of supercritical carbon dioxide (sc-CO(2)) for synthesizing calcined mesoporous silicas with tunable pore sizes, wall thickness, and d spacings. Small angle neutron scattering was used to probe the controlled swelling of the triblock copolymer surfactant templating agents, P123 (PEO(20)PPO(69)PEO(20)), P85 (PEO(26)PPO(39)PEO(26)), and F127 (PEO(106)PPO(70)PEO(106)), as a function of CO(2) pressure. The transition from the liquid crystal phase to the calcined mesoporous silicas, formed upon condensation and drying, was also studied in detail. Powder X-ray diffraction, transmission electron microscopy, and nitrogen adsorption techniques were used to establish pore diameters, silica wall widths, and the hexagonal packing of the pores within the calcined silicas. Using a direct templating method, the diameters of mesopores and the spacing between the pores could be tuned with a high level of precision. The swelling process was observed to have no detrimental effects on the quality of silica formed, a distinct advantage over conventional swelling techniques, and all of the silicas synthesized in this study were highly ordered over distances of at least 2000 A.
Light-induced stabilisation of water-in-heptane microemulsions has been achieved with a UV-sensitive gemini photo-surfactant.
Small-angle neutron-scattering (SANS) studies were performed on vesicles composed of 1,2-di-O-octadecyl-rac-glyceryl-3-(omega-methoxydodecaethylene glycol), in deuterium oxide (D2O) solutions with various ionic strengths of LiCl, NaCl and NaI. Gross vesicle morphologies, examined using freeze-fracture electron microscopy, showed that NaCl promoted the formation of multilamellar vesicles. Model fitting of the SANS data showed changes in bilayer parameters such as thickness and repeat spacings, in response to the presence of ions in the bulk solution. 2C18E12 vesicles in D2O are shown to exist as predominantly unilamellar structures with a bilayer thickness of approximately 51 A. Vesicles in increasing concentrations of LiCl and NaCl exhibit decreased layer thickness and increased lamelarity. Little change was observed for vesicles formed in NaI solutions. We suggest that these changes result from intrusion of E12 headgroups into the alkyl chain region of the vesicle bilayers, in response to the increase in concentration of ions present and their charge density.
Hybrid fluorocarbon-hydrocarbon (F-H) sulfate surfactants are shown to be efficient stabilizers in water-in-CO2 (w/c) microemulsions. The chain structure and F-H ratio affect the regions of P-T phase stability and aggregation structure in these w/c phases. High-pressure near-infrared spectroscopy and small-angle neutron scattering measurements of microemulsified water provide evidence for the stabilization of w/c microemulsion droplets. The relative lengths of the two chains were found to influence the favored aggregation structure: for symmetric chain surfactants (F8H8, F7H7) spherical reverse micelles are present, but for asymmetric chain surfactants (F7H4, F8H4) extended cylinder aggregates form. These changes in aggregation are consistent with different surfactant packing parameters owing to the controlled variations in molecular structure. Furthermore, the general order of w/c phase transition pressures (F8H8 < F7H7 and F8H4 < F7H4) is in line with estimations of surfactant fractional free volume, as proposed by Johnston et al. (J. Phys. Chem. B 2004, 108, 1962-1966). Studies of adsorption at the poly(dimethylsiloxane)-water interface are shown to be valuable for assessing the CO2-philicity of new surfactants. All in all, the symmetric F8H8 and F7H7 analogues are seen to be the most efficient compounds from this class for applications in CO2.
Six different hybrid fluorocarbon-hydrocarbon (F-H) sulfate and sulfonate surfactants, with variations in the relative F/H carbon chain length, have been synthesized and characterized in aqueous solution. These compounds have been targeted for potential activity in densified CO2. Tensiometric data and chemical analyses were consistent with surfactants of high chemical purity. Fluorination in terms of the F/H ratio exerts a strong control over all the surfactant physicochemical properties, including critical micelle concentrations (cmc's) and adsorption isotherms. One of these partially fluorinated surfactants (the sulfonate phi-F6H4) achieves very low surface tensions in water (gamma(cmc) approximately 19 mN m(-1)) more reminiscent of fully fluorinated double-chain compounds. Detailed 19F NMR studies revealed that omega'-CF3 groups can exhibit separate signals for monomeric and micellized forms, hence facilitating cmc determinations. Small-angle neutron scattering investigations confirmed the presence of ellipsoidal or extended disklike micelles, depending on the F-H chain asymmetry. For example, a symmetric hybrid F8H8 generates disklike micelles, whereas chain asymmetry in F8H4 or phi-F6H4 tends to drive cylindrical aggregation structures. These changes are consistent with variations in the surfactant packing parameter caused by the different chain F/H ratios. Hence, adsorption and aggregation are shown to respond in a predictable way to the molecular structure of these unusual surfactants.
Surface pressure-area isotherm, neutron specular reflection, and small-angle neutron scattering studies have been carried out to determine the effects of added cholesterol and distearoylphosphatidylcholine (DSPC), on the molecular structures of monolayers and vesicles containing the dialkyl polyoxyethylene ether surfactant, 1,2-di-O-octadecyl-rac-glyceryl-3-(alpha-dodecaethylene glycol) (2C18E12). Previous neutron reflectivity studies on 2C18E12 monolayers at the air/water interface have shown them to possess a thickness of approximately 24 angstoms and highly disordered structure with significant intermixing of the polymer headgroups and alkyl chains. SANS studies of 2C18E12 vesicles gave a bilayer thickness of approximately 51 angstroms. Addition of cholesterol to 2C18E12 monolayers (1:1 molar ratio), produced a marked condensing effect coupled with an increased the layer thickness of approximately 7 angstroms, and in vesicles, increased bilayer thickness by approximately 16 angstroms. Monolayers consisting of 2C18E12:DSPC:cholesterol (1:1:2 molar ratio), showed a layer thickness of approximately 31 angstroms, whereas in vesicles, three-component bilayer was found to be only approximately 9 angstroms thicker than those possessed by vesicles composed solely of 2C18E12. Mixing between the molecules in three-component monolayers was shown to be ideal through analysis of the neutron reflectivity data. These findings are discussed in relation to increased ordering and decreased headgroup/hydrophobe intermixing within both monolayers and vesicle bilayers containing 2C18E12. The inferred increase in molecular order within vesicles composed of 2C18E12 with additional cholesterol and phospholipid is used as a model for explaining theoretical differences in bilayer permeability.
A photo-responsive organogel has been made by addition of a novel stilbene-containing photo-surfactant to toluene: exposure to UV light led to a gel-to-sol transition with spatial control.
Aqueous mixtures of photosensitive and inert surfactants have been prepared; photoreactions and changes in aggregation after irradiation have been characterized. The photosensitive component was a stilbene-containing gemini photosurfactant (E-SGP), and the inert surfactants were either DTAB (dodecyltrimethylammonium bromide) or one of two different gemini surfactants, 12-4-12 or 16-4-16 (butanediyl-1,4-bis(dodecyldimethylammonium bromide) or butanediyl-1,4-bis(hexadecyldimethylammonium bromide)). Small-angle neutron scattering (SANS) studies revealed that in general the initial nonirradiated mixed systems form vesicle-type aggregates (100-200 angstroms radius), in equilibrium with some smaller charged spheroidal or ellipsoidal micelles (approximately 20 angstroms radius). In all cases, UV irradiation resulted in disruption of these vesicles and the formation of charged micelles. 1H NMR showed that the main photoproduct is the cis, anti, cis dimer of E-SGP (ZEZ-DiSGP); hence, photochemically induced changes in the reactive SGP drive significant changes in the preferred aggregation structure. These results demonstrate the utility of photoactive surfactants in mixtures with inert analogues.