Cationic gemini surfactants have been used for delivery of DNA into cells. These cationic surfactants are known to strongly bind to DNA to form a complex. In the dilute regimen, when the gemini-DNA complexes are mixed with helper neutral lipids, they undergo spontaneous assembly to form particles that are able to transfect DNA into the cells. In this study, the structure of several gemini surfactants, gemini-DNA complexes and gemini-DNA-neutral lipids complexes were systematically examined by small angle x-ray scattering (SAXS). The gemini surfactants were found to form micelles of varying shapes and arrangements modulated by the nature of spacer region and tail lengths. This includes ellipsoidal and worm-like micelles (as in the case of the 12- s-12 series) and disk-shaped hexagonally packed micelles (as in the case of 16-3-16). In addition to the study of the gemini surfactants, the effect of varying the DNA: gemini charge ratio on the DNA-gemini assembly was studied. The scattering pattern has shown that in the presence of excess gemini surfactants, free unbound surfactants exist in the solution. Upon the addition of neutral lipids, DNA-gemini-neutral lipid complexes are formed. The scattering patterns of the latter showed evidence of a strong interaction of the neutral lipids with the free gemini surfactants and the overcharged DNA-gemini complexes. Effectively, overcharging DNA-gemini complexes seem to aid in its incorporation into the neutral lipid matrix. These findings shed the light on the structure of DNA-gemini-neutral lipid systems and provide insights into the factors that influence the spontaneity of the self-assembly process. More importantly, the presented work provides a general strategy that can be applied to the study of similar systems using small angle x-ray scattering. A helium and vacuum chambers were made to enable testing the feasibility of the technique at the Canadian Light Source. Further, a pipeline was written to automate the reduction and analysis of SAXS data.

No description available.

This work studies the ability to produce effective surfactant and adhesive formulations using surface active biological material extracted from different biomass sources using alkaline extraction methods. Two urban waste biomass sources were used to produce surfactants, Return Activated Sludge (RAS), and solid Urban Refuse (UR). The third biomass source investigated was isolated mustard protein (MP). RAS and MP extracts were investigated for adhesive production. The results indicate that extracts from the waste biomass sources, RAS and UR, can be combined with a commercial surfactant, sodium dioctyl sulfosuccinate (AOT), to produce surfactants with low interfacial tensions against various oils. These highly surface-active formulations were shown to be useful in the removal of bitumen from contaminated sand. RAS and MP showed potential as protein-based wood adhesives. These sources were used in adhesive formulations to produce a strong bond strength under low-pressure, ambient pressing conditions.

This work studies the ability to produce effective surfactant and adhesive formulations using surface active biological material extracted from different biomass sources using alkaline extraction methods. Two urban waste biomass sources were used to produce surfactants, Return Activated Sludge (RAS), and solid Urban Refuse (UR). The third biomass source investigated was isolated mustard protein (MP). RAS and MP extracts were investigated for adhesive production. The results indicate that extracts from the waste biomass sources, RAS and UR, can be combined with a commercial surfactant, sodium dioctyl sulfosuccinate (AOT), to produce surfactants with low interfacial tensions against various oils. These highly surface-active formulations were shown to be useful in the removal of bitumen from contaminated sand. RAS and MP showed potential as protein-based wood adhesives. These sources were used in adhesive formulations to produce a strong bond strength under low-pressure, ambient pressing conditions.

Surfactant flooding in carbonate matrix acidizing treatment has been widely used for changing the wettability of the rock and to achieve low IFT values. Optimizing the type of surfactant and concentration for the specific oil field is very important in order to avoid formation damage and to reduce the treatment cost. We built an experimental procedure for screening the right surfactant to alter the wettability and aid in acidizing of Pekisko formation, Canada, which is strongly oil-wet and has high viscosity oil. Five surfactants were tested out of which three are cationic, one amphoteric and the other one was a fluoro-surfactant. Measurements were made of interfacial tension with different surfactant types/concentrations in brine with the oil and xylene, critical micelle concentration of each surfactant, solubility characteristics of the surfactants, compatibility of the chemical additives, wettability of the core after treating with surfactants, and core flooding in the laboratory to simulate matrix acidizing. From the results obtained we noted that the fluoro-surfactant can cause formation damage due to precipitation in the brine. So the compatibility of every chemical additive should be tested first. The use of xylene as a pre-flush solution lowered the CMC and hence reduced the cost of the surfactant treatment. Aromox, an amine based surfactant was best suited for matrix acidizing treatment of the Pekisko formation.

In recent years there has been increasing interest in novel forms of surfactants. Of particular interest are gemini surfactants, which consist of two conventional surfactants joined by a spacer at the head groups, as they exhibit lower critical micelle concentrations than can be achieved by conventional surfactants. In this work, the self-assembly behaviour of several nonionic gemini surfactants with polyethylene oxide head groups (GemnEm, where n (= 20) is the number of carbons per tail and m (= 10, 15, 20 and 30) is the number of ethylene oxides per head group) were investigated. The Critical Micelle Concentrations (CMCs) were measured using a fluorescence probe technique. The CMCs are all ~2 x 10?7 M, with almost no variation with m. The CMCs are several orders of magnitude lower than conventional C12Em nonionic surfactants. The mixing behaviour of the gemini surfactants with conventional surfactants was also studied. They obeyed ideal mixing behaviour with both ionic and nonionic surfactants. Micelle morphologies were studied using Small Angle Neutron Scattering. The gemini surfactants with the larger head groups (i.e. Gem20E20 and Gem20E30) formed spherical micelles. Gem20E15 showed strong scattering at low Q, characteristic of elongated micelles. As the temperature was increased towards the cloud point, the scattering approached the Q-1 dependence predicted for infinite, straight rods. The existence of anisotropic micelles was supported by the viscosity of Gem20E15, which increases by several orders of magnitude on heating towards its cloud point. Phase behaviour was determined using Diffusive Interfacial Transport coupled to near-infrared spectroscopy. Much of the behaviour of these systems is similar to conventional nonionic surfactants. For example, Gem20E10 forms a dilute liquid isotropic phase (W) coexisting with a concentrated lamellar phase (La) at around room temperature and forms a sponge phase at higher temperatures. This is similar to the behaviour of C12E3 and C12E4. The other surfactants studied are all quite soluble in water and form liquid isotropic and hexagonal phases from room temperature. At higher concentrations Gem20E15 formed a cubic and then a lamellar phase while Gem20E20 formed a cubic phase and then an intermediate phase. This is also comparable to the phase behaviour of conventional nonionic surfactants except the intermediate phase, which is often only observed for surfactant systems with long alkyl tails.

Doctor of Philosophy (PhD) / Oligomeric surfactants, sometimes referred to as gemini surfactants, consist of two or more amphiphilic ‘monomer’ units linked together by spacer groups. The chemical identity of the spacer group is unconstrained, and it joins the individual units at or near the hydrophilic headgroups. Oligomeric surfactants display a range of interesting properties, including very low critical micelle concentrations, high surface activity and unusual rheology and self-assembly. Consequently they have many potential applications, both scientific and industrial. Until now, their use has been limited by the cost of their synthesis, which in some cases involve long and difficult procedures. This project developed from the idea that a synthesis based on polymerization could prove a useful and versatile method for producing these surfactants. The chemical starting point for this project was a series of polymerizable surfactants (‘surfmers’), upon which polymerization was performed. Two families of surfmers were investigated, both cationic and based on methacrylate and vinylpyridinium moieties respectively. The physical behaviour of these surfactants – a number of which are new – was investigated using standard techniques; these included the determination of the critical micelle concentration, characterization of phase behaviour, neutron scattering and surface adsorption. In producing oligomers, the initial focus was on free-radical polymerization, with control of molecular weight to be achieved by chain-transfer techniques. Due largely to analysis problems, this work proved unsuccessful. In its place a new reaction, not based on conventional polymerization methods, has been developed. The vinylpyridinium surfmers mentioned above readily undergo addition across the double bond to produce alkyl ring substituents. Under basic conditions, these alkylpyridiniums undergo an elimination/addition reaction in which they link together to form oligomers. This reaction can be started or stopped by raising or lowering the pH of the reaction solution, and has been performed in both organic and aqueous solutions. It is referred to in this thesis as LELA(Linkage by ELimination/Addition). The LELA reaction was used to produce mixtures of oligomers, the phase behaviour and surface adsorption of which were examined. Small-angle neutron scattering was used to monitor the reaction in real time and identify changes in self-assembly as the average oligomer length increased. Progress was also made towards a chromatographic protocol that would allow mixtures to be separated into their components and the pure oligomers to be studied. Finally, some of the compounds studied display interesting pH-dependent chromophoric properties which were also found to occur with other simple alkylpyridinium species. They are tentatively ascribed to inter- and intramolecular charge-transfer complexes, and evidence towards this conclusion was collected and is presented along with relevant calculations.

Thesis (M. Sc. ) - niversity of the Western Cape, 2009. / Includes bibliographical references (leaves 72-79)

Diss.Teknillinen korkeakoulu, 2006.

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Abraham M. Lenhoff, Dept. of Chemical Engineering. Includes bibliographical references.