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Title: A structural study on the solubilisation of pesticides into surfactant micelles
Author: Padia, Faheem Noorahmed
ISNI:       0000 0004 2729 8732
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2012
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The ability of surfactants to form micelles and solubilise hydrophobic substances in aqueous environments has been widely exploited in formulation science. In spite of extensive studies over the past few decades by both experimental and theoretical methods, however, it remains difficult to predict key micellar parameters such as their size, shape and nanostructure which is essential for their successful implementation in the solubilisation of active ingredients. This is partly due to the vast number of surfactants commercially available but, in addition, the fragmentation of the field of surfactant science, over recent years, has made it more difficult to identify general trends and properties of surfactant systems. A further challenge is in characterising systems of heavily mixed surfactants since our knowledge on pure surfactant systems may not allow us to predict the behaviour of these systems. The broad aim of this thesis was to contribute to these aspects of surfactant science. The first part of the thesis reports a systematic study of the surfactant structure-micellar structure relationship of pure alkyl ethoxylate (CmEn) surfactants. This was done by independently varying the lengths of the alkyl chain and ethoxylate group and measuring the micellar structural properties. The next part of the thesis reports the effects of solubilisation of two model pesticides, Cyprodinil and Diuron, on the size, shape and internal structure of these surfactant micelles. These pesticides were chosen because they were structurally representative of different features of those widely used in agrochemicals. The final part of the thesis reports the work on binary surfactant mixtures that rationalise the general structural features of mixed micelles and their impact on pesticide solubilisation. Various experimental techniques were used including small angle neutron scattering (SANS), nuclear magnetic resonance (NMR), nuclear Overhauser effect spectroscopy (NOESY NMR), dynamic light scattering (DLS) and UV spectroscopy. The key findings of the thesis were that the micellar core volumes could be predicted with reasonable accuracy using the hydrophilic-lipophilic balance (HLB) of the surfactants in pure micelles. NOESY results revealed protrusions of the terminal methylene groups into the ethoxylate shell, thus providing evidence for the theoretically predicted phenomenon referred to as the-shell interface. SANS revealed that solubilisation of both pesticides caused micellar growth, with the long axial lengths of the micelles growing much longer. These structural changes were associated with the dehydration of the ethoxylate shells. Although a partitioning experiment predicted that the pesticides would be solubilised in the hydrated ethoxylate micellar shell, NOESY measurements revealed that the solubilisation occurred predominantly in the micellar cores. The discrepancy was caused by alkyl chain-ethoxylate mixing leading to the formation of dehydrated palisade regions that entrapped the pesticides towards the cores. The results from the binary mixed micelles showed some signs of synergistic behaviour but no enhancement of pesticide solubilisation.
Supervisor: Lu, Jian Sponsor: Syngenta
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Micelles ; surfactant ; non-ionic ; nonionic ; SANS ; NMR ; DLS ; Solubilisation ; Pesticide