Dissertation

The co-crystallisation of sugars by the supersaturation process

Geary, Peter Michael

2008

Overview

Co-crystallising sugars by the supersaturation process was investigated using sucrose and lactose as the matrix sugars. The components to be cocrystallised with either sucrose or lactose were a variety of mono- and disaccharides along with sweeteners such as saccharin. Analysis of the materials yielded from the supersaturation process was done primarily by differential scanning Calorimetry (DSC) and powder x-ray diffraction (PXRD). DSC analysis allowed information to be obtained on the thermal behaviour of the various co-crystalline materials, whilst PXRD permitted information on the structural aspects of the materials to be gained. These two forms of analysis were complimentary to each other, each revealed unique characteristics of the co-crystalline materials. To unambiguously differentiate the difference between a material that is co-crystalline and one that is not, physical blends of the sugars to be cocrystallised were analysed by DSC and PXRD. This approach allowed for identification of all the components in the mixture, more importantly, this identification was achievable at all levels of the second component in the mixture. Co-crystallising either sucrose or lactose, with various sugars, yielded solely co-crystalline material up to a certain level of the added sugar. Once this level has been reached, two distinct phases appear in both DSC and PXRD analysis. A co-crystallised and a phase relating to the added sugar can be observed. The formation of a potentially co-crystalline material appears to result from a direct inclusion of the added sugar into the matrix sugar. DSC analysis of the co-crystallised material revealed thermal behaviour that is suggestive of a doping of the matrix sugar by the added component. PXRD analysis did provide some data to further this argument, axis elongation for co-crystallised material is suggestive of a sopping of the main phase. However, determination of the unit cell volumes did not yield conclusive evidence to help prove this hypothesis though. This behaviour in both forms of analysis was generally proportional to the quantity of the second component that has become included into the matrix sugar. The formation of solely co-crystalline materials appears to rely on the structural similarity between the matrix sugar and the component to be included. A higher degree of similarity is reflected by a high level of inclusion of the added component. Co-crystallisation appears to rely on a degree of intermolecular sugar-sugar recognition. The inclusion of a second component is not solely down to structural similarities between materials however. It appears that there are kinetic factors potentially involved to. Varying the method of co-crystallisation allowed for higher, or lower, amounts of various second components to be included within a matrix sugar. The appearance of co-crystalline materials may be due to the inclusion of the second component in an amorphous state. Analysis by Autosorb of various co-crystalline materials has dispelled this idea. All co-crystalline materials behaved in a manner that was indicative of a crystalline material. During the course of the work with sucrose, it was noted that a unique melting point was observed. From previous work, this unique phase was thought to be a hydrated form of sucrose. Further analysis on this material has allowed for further postulation on its formation and on new methods of its synthesis.

• Publisher: ProQuest Dissertations & Theses
• Subject: Organic chemistry