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Calum J Drummond

Publications and source records attributed to Calum J Drummond.

10 recordsLinked to original sources

Many protic ionic liquids mediate hydrocarbon-solvent interactions and promote amphiphile self-assembly.

A large number of protic ionic liquids (PILs) have been found to mediate solvent-hydrocarbon interactions and promote amphiphile self-assembly. Hexagonal, cubic, and lamellar lyotropic liquid crystalline phases were observed in PIL-hexadecyltrimethylammonium bromide systems. The driving force for the formation of the self-assembled aggregate structures has been attributed to an entropic contribution to the free energy of association, analogous to the hydrophobic effect in water. The specific aggregate structures formed depend upon the cationic and anionic components of the PIL and their interactions with the amphiphiles.

Anions↗

Protic ionic liquids: solvents with tunable phase behavior and physicochemical properties.

The phase behavior, including glass, devitrification, solid crystal melting, and liquid boiling transitions, and physicochemical properties, including density, refractive index, viscosity, conductivity, and air-liquid surface tension, of a series of 25 protic ionic liquids and protic fused salts are presented along with structure-property comparisons. The protic fused salts were mostly liquid at room temperature, and many exhibited a glass transition occurring at low temperatures between -114 and -44 degrees C, and high fragility, with many having low viscosities, down to as low as 17 mPa.s at 25 degrees C, and ionic conductivities up to 43.8 S/cm at 25 degrees C. These protic solvents are easily prepared through the stoichiometric combination of a primary amine and Brønsted acid. They have poor ionic behavior when compared to the far more studied aprotic ionic liquids. However, some of the other physicochemical properties possessed by these solvents are highly promising and it is anticipated that these, or analogous protic solvents, will find applications beyond those already identified for aprotic ionic liquids. This series of protic fused salts was employed to determine the effect of structural changes on the physicochemical properties, including the effect of hydroxyl groups, increasing alkyl chain lengths, branching, and the differences between inorganic and organic anions. It was found that simple structural modifications provide a mechanism to manipulate, over a wide range, the temperature at which phase transitions occur and to specifically tailor physicochemical properties for potential end-use applications.

Amines↗

Positional isomers of linear sodium dodecyl benzene sulfonate: solubility, self-assembly, and air/water interfacial activity.

Commercial linear alkyl benzene sulfonates (ABS) are a very important class of anionic surfactants that are employed in a wide variety of applications, especially those involving wetting and detergency. Linear ABS surfactants generally consist of a complex mixture of different chain lengths and positional isomers. This diversity and level of complexity makes it difficult to develop fundamental structure-property correlations for the commercial surfactants. In this work, six monodisperse headgroup positional isomers of sodium para-dodecyl benzene sulfonate (Na-x-DBS, x = 1-6) have been studied. The influence of headgroup position and added electrolyte (NaCl) on the solubility and self-assembly (micellar and vesicular aggregation and lyotropic liquid crystalline phase behavior) in the temperature range from 10 to 90 degrees C have been investigated. Additionally, the air-aqueous solution interfacial adsorption at 25 (no added NaCl) and 50 degrees C (from 0 to 1.0 M added NaCl) has been examined. The observed physicochemical behavior is interpreted in terms of local molecular packing constraints, and in the case of the lyotropic liquid crystalline behavior global aggregate packing constraints as well.

Air↗

Ordered 2-D and 3-D nanostructured amphiphile self-assembly materials stable in excess solvent.

Amphiphile lyotropic liquid crystalline self-assembly materials are being used for a diverse range of applications. Historically, the most studied lyotropic liquid crystalline phase is probably the one-dimensional (1-D) lamellar phase, which has been employed as a model system for biomembranes and for drug delivery applications. In recent years, the structurally more complex 2-D and 3-D ordered lyotropic liquid crystalline phases, of which reversed hexagonal (H(2)) and reversed cubic phases (v(2)) are two prominent examples, have received growing interest. As is the case for the lamellar phase, these phases are frequently stable in excess water, which facilitates the preparation of nanoparticle dispersions and makes them suitable candidates for the encapsulation and controlled release of drugs. Integral membrane protein crystallization media and templates for the synthesis of inorganic nanostructured materials are other applications for 2-D and 3-D amphiphile self-assembly materials. The number of amphiphiles identified as forming nanostructured reversed phases stable in excess solvent is rapidly growing. In this article, different classes of amphiphiles that form reversed phases in excess solvent are reviewed, with an emphasis on linking phase behavior to amphiphile structure. The different amphiphile classes include: ethylene oxide-, monoacylglycerol-, glycolipid-, phosphatidylethanolamine-, and urea-based amphiphiles.

Chemistry, Physical↗

Multi-scale Cryptosporidium/sand interactions in water treatment.

Owing to its widespread occurrence in drinking water supplies and its significant resistance to environmental stresses, Cryptosporidium parvum is regarded as one of the most important waterborne microbial parasites. Accordingly, a substantial research effort has been aimed at elucidating the physical, chemical and biological factors controlling the transport and removal of Cryptosporidium oocysts in natural subsurface environments and drinking water treatment facilities. In this review, a multi-scale approach is taken to discuss the current state-of-knowledge on Cryptosporidium-sand interactions at a nano-scale, bench-scale and field-scale relevant to water treatment operations. Studies conducted at the nano-scale and bench-scale illustrate how techniques based on the principles of colloid and surface chemistry are providing new insights about oocyst-sand interactions during transport of Cryptosporidium oocysts in granular porous media. Specifically, atomic force microscopy and impinging jet experiments reveal the importance of oocyst surface biomolecules in controlling Cryptosporidium/sand interactions by a mechanism of steric hindrance. Traditional bench-scale column transport studies conducted over a broad range of experimental conditions highlight the role of physicochemical filtration and physical straining in the removal of oocysts from the pore fluid. Such experiments have also been used to evaluate the influence of biofilms formed on grain surfaces and the presence of natural organic matter on oocyst-sand interactions. Whilst filtration studies conducted at the plant-scale have been useful for evaluating the effectiveness of various materials as surrogates for Cryptosporidium oocysts, at this macro-scale, little could be learnt about the fundamental mechanisms controlling oocyst-sand interactions. This review of the literature on Cryptosporidium-sand interactions at different length scales points to the importance of combining studies at the plant-scale with well-controlled investigations conducted at the nano- and bench-scales. Furthermore, because oocyst surface properties play an important role in controlling the extent of interaction with sand surfaces, a thorough discussion of Cryptosporidium oocyst characteristics and electrical properties is presented.

Animals↗

Nonionic urea surfactants: formation of inverse hexagonal lyotropic liquid crystalline phases by introducing hydrocarbon chain unsaturation.

The homo-interaction between urea moieties residing in close proximity to each other generally results in very strong intermolecular hydrogen bonding. The bifurcated hydrogen bonding exhibited by n-alkyl substituted ureas means that for those urea surfactants possessing medium and long hydrocarbon chain substituents the crystal to isotropic liquid melting point is high and the solubility in water is very low, compared to other similar chain length nonionic surfactants. In addition, saturated n-alkyl urea surfactants do not form lyotropic liquid crystalline phases in water. In this work the strong intermolecular hydrogen bonding of the urea headgroup has been ameliorated through the introduction of unsaturated hydrocarbon chains, viz., oleyl (cis-octadec-9-enyl), linoleyl (cis, cis-octadec-9,12-dienyl), and linolenyl (cis, cis, cis-octadec-9,12,15-trienyl) with one, two, and three carbon double bonds, respectively. Unsaturation in the C18 urea surfactants lowers the melting point and promotes an inverse hexagonal phase, in oleyl urea-water and linoleyl urea-water systems, which is thermodynamically stable in excess water. As the degree of unsaturation is increased to three in linolenyl urea, there is a tendency for autoxidation/polymerization. The occurrence of an inverse hexagonal phase in the nonionic urea surfactant-water systems has been rationalized in terms of both local molecular and global self-assembled aggregate packing constraints.

Journal Article↗

Nonionic urea surfactants: influence of hydrocarbon chain length and positional isomerism on the thermotropic and lyotropic phase behavior.

The thermotropic and lyotropic phase behavior of 1- and 5-decyl urea, and 1-, 2-, 4-, and 6-dodecyl urea have been studied. This allowed the effect of positional isomerism to be examined. Intermolecular hydrogen bonding by the urea moiety is the dominant factor in determining the solid-state thermal behavior and crystal solubility boundary of these linear nonionic surfactants. The positional isomers where the urea moiety was not situated at the terminus of the hydrocarbon chain exhibited higher melting points than the 1-alkyl ureas. This has been rationalized by postulating interdigitated chains in the solid state. In the urea surfactant-water systems, three phases are observed, viz. crystalline solid, a dilute aqueous solution of the alkyl urea, and an isotropic liquid. The last two phases coexist in the low-surfactant, high-temperature region of the binary phase diagram. An overview of structure-property correlations for linear nonionic urea surfactants is presented in light of the new physicochemical data obtained for the decyl urea and dodecyl urea positional isomers.

Journal Article↗

Effects of degassing on the long-range attractive force between hydrophobic surfaces in water.

The long-ranged attractions between hydrophobic amorphous fluoropolymer surfaces are measured in water with and without dissolved air. An atomic force microscope is used to obtain more than 500 measured jump-in distances, which yields statistically reliable results. It is found that the range of the attraction and its variability is generally significantly decreased in deaerated water as compared to normal, aerated water. However, the range and strength of the attraction in deaerated water remain significantly greater than the van der Waals attraction for this system. The experimental observations are consistent with (1) nanobubbles being primarily responsible for the long-ranged attraction in normal water, (2) nanobubbles not being present in deaerated water when the surfaces are not in contact, and (3) the attraction in the absence of nanobubbles being most probably due to the approach to the separation-induced spinodal cavitation of the type identified by Bérard et al. [J. Chem. Phys. 1993, 98, 7236]. It is argued that the measurements in deaerated water reveal the bare or pristine hydrophobic attraction unobscured by nanobubbles.

Polymers↗

A molecular dynamics study of monolayers of nonionic poly(ethylene oxide) based surfactants.

Molecular dynamics simulations of monolayers of nonionic, poly(ethylene oxide) based surfactants are reported. Specifically, alcohol ethoxylates and alkylphenol ethoxylates are compared in terms of the varying architecture of the molecules for the development of a structure-behavior relationship. Interfacial density profiles are used to assess the structure of the monolayers, the penetration of water and oil into the monolayers, and the solvation of the hydrophiles and hydrophobes. Chain conformational descriptors are used to examine the molecular structure of the surfactants. The simulations revealed that monolayers of alcohol ethoxylates are considerably more diffuse than their alkylphenol counterparts, with the packing being governed by the size of the hydrophile. With the exception of the branched alcohol ethoxylate, the intermixing of the bulk phases within monolayers of alcohol ethoxylates increases with increasing hydrophile length. By comparison, the packing of alkylphenol ethoxylates within the monolayer is governed by the aromatic nucleus in the molecule. No specific interaction is observed between the aromatic rings of neighboring molecules. Monolayers of alkylphenol ethoxylates are more compact than their alcohol counterparts, resulting in more effective separation of the bulk water and oil phases.

Journal Article↗

Oocysts of Cryptosporidium parvum and model sand surfaces in aqueous solutions: an atomic force microscope (AFM) study.

Oocysts of C. parvum have been associated with several waterborne outbreaks of gastro-enteric disease. Currently, one of the main barriers to oocyst contamination of drinking waters is provided by sand-bed filtration. In this study an atomic force microscope (AFM) has been used to measure the force of interaction between oocysts of C. parvum and a model sand surface (silicate glass). The AFM force curves have been compared and contrasted with the corresponding electrical potentials obtained from electrophoretic measurements (zeta). It has been found that the surface of C. parvum oocysts possesses a hairy layer, most likely a result of surface proteins extending into solution. The hairy layer imposes a steric repulsion between the oocyst and sand surface, in addition to any electrostatic repulsion. The hairy layer collapsed to varying extents in the presence of dissolved calcium and dissolved organic carbon, indicating that the oocysts may be more readily adsorbed onto the model sand surface under these conditions. Conversely, as the two surfaces are pulled apart, the occasional attachment of oocyst surface proteins to the model sand surface can result in adhesion. The AFM results offer new insights into the oocyst surface of C. parvum, and the mechanism of interaction with model sand surfaces under conditions relevant to sand-bed filtration.

Animals↗