Bambara groundnut (Vigna subterranean L.) is considered a good source of protein in some parts of sub Saharan African countries. Long cooking time of about three hours contributed to its limited consumption and utilisation. Micronisation is an infrared heating process. It can reduce the cooking time of pre-moisture conditioned legume small seeds size such as cowpea and lentil, but mostly tempering of seeds has been used as the pre-conditioning techniques. The resulting flour from the pre-conditioned micronised cowpea can reduce pasting viscosity and has potentials in food systems as an instant product. This study aimed at (1) determining the effects of micronisation of pre-soaked whole and dehulled bambara groundnut seeds on their cooking characteristics, (2) determining the effects of micronisation and dehulling treatment of pre-soaked bambara groundnut on physicochemical, microstructure and functional properties of the resulting flours and (3) determining the effects of micronisation of pre-soaked whole and dehulled bambara groundnut seeds on the viscosity, nutritional and health benefits of the cooked samples in order to produce a quick cooked bambara groundnut with functional, nutritional and health benefits. Micronisation (130 ºC) at a different time (0, 5, 10 and 15 min) was used to optimise the process for pre-soaked (53% moisture) bambara groundnuts. Micronisation (130 ºC) reduced cooking time of pre-soaked (53% moisture) bambara groundnut (whole and dehulled) following cooking. Micronisation reduced the 162 min cooking of raw bambara groundnut to 109, 83, 75 and 62 min when micronized for 0, 5, 10 and 15 min. Micronisation (53% moisture, 130 ºC) caused molecular changes such as solubilisation of pectin which was responsible for the disruption of the middle lamella and separation of parenchyma cell observed by light microscopy and scanning electron microscopy (SEM). It also caused disruption in the structure of starch granule, protein matrix in the cotyledon. These changes in seeds structure and molecular properties of starch, protein and pectin, facilitate water hydration rate and cell separation during cooking, leading to the shorter cooking time of the bambara groundnuts. Micronisation of pre-soaked (53% moisture) bambara groundnuts caused molecular changes such as partial starch gelatinisation and reduced protein solubility in the resulting flours. The changes in the starch and proteins modified the resulting flours functional properties such asincrease swelling of the resulting flours, while reducing the water solubility. The pasting viscosities of resulting flours of pre-soaked bambara groundnut reduced following micronisation due to the denatured protein matrix preventing embedded starch hydration, dispersibility and molecular entanglement during pasting.This was evident by light and confocal laser scanning microscopy (CLSM) that showed the aggregates of denatured protein matrix surrounding embedded pre-gelatinised starch granules increase with micronisation in the resulting flours and cooked soft porridge of bambara groundnut. Micronisation has an effect on the apparent viscosity, nutritional, bioactive compound such as phenolics and hence the antioxidant properties of cooked soft porridge of bambara groundnut. All cooked soft porridge of bambara groundnut exhibited a shear thinning behavior and micronised bambara groundnut had lower viscosity increased in the starch and protein digestibility of cooked soft porridge of bambara groundnut. It also increased the phenolic content and antioxidant properties of cooked soft porridge of whole bambara groundnut, but these were reduced in cooked soft porridge of dehulled bambara groundnut due to seed coat absence. Thus, micronisation of pre-soaked bambara groundnut (whole and dehulled) would contribute towards increased utilisation of bambara groundnut as well as improving house hold nutrition and health promoting properties.Micronisation of bambara groundnut has potential to produce a quick paste with low viscosity which depend on the pre-soaking and micronisation time of the bambara groundnut. Flours from micronised bambara groundnut can therefore be used as instant flour ingredient in food products. / Thesis (PhD)--University of Pretoria, 2016. / National Research Foundation (NRF) of South Africa / Food Science / PhD (Food Science) / Unrestricted

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Cowpeas (Vigna unguiculata L. Walp) are legumes recognised as a good source of proteins in developing countries. Cowpeas are mostly utilised as cooked whole seeds. This is often achieved only after boiling for up to 2 hours, resulting in high energy consumption and a long time for food preparation. Micronisation of pre-conditioned cowpeas (± 41 % moisture at 153 °C) reduces their cooking time. During micronisation, cowpea seeds are exposed to electromagnetic radiation with a wavelength range of 1.8 to 3.4μm. For biological materials, the penetration of infrared rays into the food material causes intermolecular vibration, this result in a rapid increase in temperature and water vapour pressure within the seed. Micronisation changes physico-chemical properties of cowpea seeds that may affect sensory properties of cooked cowpeas. Micronisation may also affect cowpea bioactive components such as phenolic compounds and hence their antioxidant properties and bioactive properties. This study aimed at (1) determining the effects of micronisation of pre-conditioned cowpeas on sensory properties of cooked cowpeas and (2) determining the effects of mironisation of pre-conditioned cowpeas on the phenolic compounds, radical scavenging properties and their protective effects against oxidative damage of biomolecules (i.e. low density lipoproteins (LDL), deoxyribonucleic acid (DNA) and red blood cells (RBC). © University of Pretoria vi Micronisation significantly reduced cowpea cooking time by 28 to 49 %, depending on cowpea type. There were significant (P<0.05) increases in roasted aroma and flavour, mushy texture and splitting in all micronised samples. Bechuana white, a light brown cowpea type, was more mushy and split than others. There were significant decreases in firmness, mealiness and coarseness after micronisation for all cowpea types. Micronised cowpeas were darker (lower L* values) than unmicronised cooked cowpeas. Darkening was more evident in light coloured than dark coloured cowpea types. Although micronisation reduces cowpea cooking time, it also affects sensory properties of cowpeas. This might have an influence on consumer acceptance of micronised cowpeas. Twenty seven phenolic compounds were identified in the cowpea types studied: 6 phenolic acids, 14 flavonols and 7 flavan-3-ols. Protocatechuic acid, p-coumaric acid, 4- hydroxybenzoic acid and ferulic acid were the major phenolic acids in cowpeas. Catechin, catechin-3-O-glucoside, myricetin, rutin, quercetin and its mono and diglycosides were present in all cowpea types analysed. Dr Saunders (701.7−849.2 μg/g) (red in colour) and Glenda (571.9−708.1 μg/g) (dark brown in colour) contained the highest total phenolic contents, followed by Bechuana white (361.5−602.3 μg/g) (light brown in colour) and Blackeye (152.0−224.5 μg/g) (cream in colour). More of the flavonols were identified in red and dark brown compared to light brown and cream cowpea types. The red cowpea type contained all the dimers and oligomeric flavan-3-ol species identified in this study. In all cowpea types, extracts from unmicronised (uncooked) cowpeas inhibited copperinduced LDL oxidation in a dose dependent manner. Extracts from all samples analysed exhibited protective effects against AAPH (2, 2'-azobis (2-amidinopropane) hydrochloride) induced RBC haemolysis and DNA damage. Extracts from more pigmented cowpeas, i.e. Dr Saunders, Glenda and Bechuana white, had significantly (P<0.05) higher levels of total phenolics, total flavonoids and radical scavenging properties than Blackeye (less pigmented). Extracts from more pigmented cowpeas also offered higher protection against AAPH-induced DNA and copper-induced LDL oxidation damage than extracts from less pigmented cowpeas. These results indicate protection of biomolecules e.g. DNA, LDL and RBC) from oxidative damage and have a potential to reduce oxidative stress implicated in the development of chronic diseases. This is because cowpea phenolic compounds possess the ability to reduce oxidative damage associated with development of these diseases. © University of Pretoria vii Pigmented cowpea types may be recommended for health applications as they show more potential as source of antioxidants compared to the less pigmented cowpeas. Extracts from micronised (uncooked and cooked) samples of Dr Saunders and Glenda cowpeas had significantly higher concentrations of ferulic acid and p-coumaric acid compared with unmicronised samples. Para-coumaric acid concentrations were higher in all micronised samples of Blackeye cowpeas than in unmicronised samples. The micronisation process could release cell wall bound ferulic acid and p-coumaric, increasing their concentrations in micronised samples. On the contrary, extracts from all micronised samples of Bechuana white and Glenda cowpeas had lower concentrations of catechin than unmicronised samples. Results indicated that total extractable phenolics were lower in micronised samples of cowpea types than unmicronised samples. Futhermore, extracts from micronised samples of all cowpea types showed less protective effect against LDL oxidation than extracts from unmicronised samples. However, for most cowpea types there was no significant difference in total flavonoid contents (TFC) and Trolox equivalent antioxidant capacity (TEAC) values of cooked samples of both micronised and unmicronised. Micronisation did not affect the protective effects of cowpeas against AAPH-induced RBC haemolysis and oxidative DNA damage. Micronisation, followed by cooking, may have generated heat-induced antioxidants such as Maillard reaction products contributing to radical scavenging properties in micronised (cooked) cowpea samples. Though micronised samples had lower concentrations of some phenolic compounds and total extractable phenolics than unmicronised samples, micronised cowpea samples still exhibited radical scavenging properties and offered protective effects against oxidative damage of LDL, DNA and RBC and therefore may offer potential health benefits to consumers. / Thesis (PhD)--University of Pretoria, 2013. / gm2013 / Food Science / Unrestricted

Micronisation of active pharmaceutical ingredients (APIs) to achieve desirable quality attributes for formulation preparation and drug delivery remains a major challenge in the pharmaceutical sciences. It is therefore important that the relationships between crystal structure, the mechanical properties of powders and their subsequent influence on processing behaviour are well understood. The aim of this project was therefore to determine the relative importance of particle attributes including size, crystal quality and morphology on processing behaviour and the characteristics of micronised materials. It was then subsequently intended to link this behaviour back to crystal structure and the nature of molecular packing and intermolecular interactions within the crystal lattice enabling the identification of some generic rules which govern the quality of size reduced powders. In this regard, different sieve fractions of lactose monohydrate and crystal variants of ibuprofen and salbutamol sulphate (size, morphology and crystal quality) were investigated in order to determine those factors with greatest impact on post-micronisation measures of particle quality including particle size, degree of crystallinity and surface energy. The results showed that smaller sized feedstock should typically be used to achieve ultrafine powders with high crystallinity. This finding is attributed to the reduced number of fracture events necessary to reduce the size of the particles leading to decreases in milling residence time. However the frequency of crystal cracks is also important, with these imperfections being implicated in crack propagation and brittle fracture. Ibuprofen crystals with a greater number of cracks showed a greater propensity for comminution. Salbutamol sulphate with a high degree of crystal dislocations however gave highly energetic powders, with reduced degree of crystallinity owing to the role dislocations play in facilitating plastic deformation, minimising fragmentation and extending the residence of particles in the microniser. Throughout these studies, morphology was also shown to be critical, with needle like morphology giving increased propensity for size reduction for both ibuprofen and salbutamol sulphate, which is related to the small crack propagation length of these crystals. This behaviour is also attributed to differences in the relative facet areas for the different morphologies of particles, with associated alternative deformation behaviour and slip direction influencing the size reduction process. Molecular modelling demonstrated a general relationship between low energy slip planes, d-spacing and brittleness for a range of materials, with finer particle size distributions achieved for APIs with low value of highest d-spacings for identified slip planes. The highest d-spacing for any material can be readily determined by PXRD (powder x-ray diffraction) which can potentially be used to rank the milling behaviour of pharmaceutical materials and provides a rapid assessment tool to aid process and formulation design. These studies have shown that a range of crystal properties of feedstock can be controlled in order to provide micronised powders with desirable attributes. These include the size, morphology and the density of defects and dislocations in the crystals of the feedstock. Further studies are however required to identify strategies to ensure inter-batch consistency in these attributes following crystallisation of organic molecules.

Micronisation of active pharmaceutical ingredients (APIs) to achieve desirable quality attributes for formulation preparation and drug delivery remains a major challenge in the pharmaceutical sciences. It is therefore important that the relationships between crystal structure, the mechanical properties of powders and their subsequent influence on processing behaviour are well understood. The aim of this project was therefore to determine the relative importance of particle attributes including size, crystal quality and morphology on processing behaviour and the characteristics of micronised materials. It was then subsequently intended to link this behaviour back to crystal structure and the nature of molecular packing and intermolecular interactions within the crystal lattice enabling the identification of some generic rules which govern the quality of size reduced powders. In this regard, different sieve fractions of lactose monohydrate and crystal variants of ibuprofen and salbutamol sulphate (size, morphology and crystal quality) were investigated in order to determine those factors with greatest impact on post-micronisation measures of particle quality including particle size, degree of crystallinity and surface energy. The results showed that smaller sized feedstock should typically be used to achieve ultrafine powders with high crystallinity. This finding is attributed to the reduced number of fracture events necessary to reduce the size of the particles leading to decreases in milling residence time. However the frequency of crystal cracks is also important, with these imperfections being implicated in crack propagation and brittle fracture. Ibuprofen crystals with a greater number of cracks showed a greater propensity for comminution. Salbutamol sulphate with a high degree of crystal dislocations however gave highly energetic powders, with reduced degree of crystallinity owing to the role dislocations play in facilitating plastic deformation, minimising fragmentation and extending the residence of particles in the microniser. Throughout these studies, morphology was also shown to be critical, with needle like morphology giving increased propensity for size reduction for both ibuprofen and salbutamol sulphate, which is related to the small crack propagation length of these crystals. This behaviour is also attributed to differences in the relative facet areas for the different morphologies of particles, with associated alternative deformation behaviour and slip direction influencing the size reduction process. Molecular modelling demonstrated a general relationship between low energy slip planes, d-spacing and brittleness for a range of materials, with finer particle size distributions achieved for APIs with low value of highest d-spacings for identified slip planes. The highest d-spacing for any material can be readily determined by PXRD (powder x-ray diffraction) which can potentially be used to rank the milling behaviour of pharmaceutical materials and provides a rapid assessment tool to aid process and formulation design. These studies have shown that a range of crystal properties of feedstock can be controlled in order to provide micronised powders with desirable attributes. These include the size, morphology and the density of defects and dislocations in the crystals of the feedstock. Further studies are however required to identify strategies to ensure inter-batch consistency in these attributes following crystallisation of organic molecules.

The process of milling drugs to obtain samples with a desirable particle size range has been widely used in the pharmaceutical industry, especially for the production of drugs for inhalation. However by subjecting materials to milling techniques surfaces may become thermodynamically activated which may in turn lead to formation of amorphous material. Polymorphic conversions have also been noted after milling of certain materials. Salt and cocrystal formation is a good way of enhancing the properties of an API but little or no work has been published which investigates the stability of these entities when subjected to milling. Different milling techniques (ball and jet) and temperatures (ambient and cryogenic) were used to investigate the milling behaviour of polymorphs, salts and cocrystals. All materials were analysed by XRPD and DSC to investigate any physical changes, i.e. changes in melting point and by inverse gas chromatography (IGC) to investigate whether any changes in the surface energetics occurred as a result of milling. Another aim of this thesis was to see if it was possible to predict the milling behaviour of polymorphs by calculating the attachment energies of the different crystal facets using Materials Studio 4.0. These results were compared to the IGC data to see if the predicted surface changes had occurred. The data collected in this study showed that different milling techniques can have a different effect on the same material. For example ball milling at ambient temperature and jet micronisation of the SFZ tosylate salt caused a notable increase in the melting point of the material whereas ball milling at cryogenic temperatures did not cause this to happen. The IGC data collected for this form also showed a contrast between cryomilling and the other two techniques. The study also showed that the formation of salts and cocrystals does not necessarily offer any increased stability in terms of physical properties or surface energetics. Changes in melting point were observed for the SFZ tosylate salt and the IMC:Benzamide cocrystal. Changes in the specific surface energies were also observed indicating that the nature of the surfaces was also changing. The materials which appeared to be affected the least were the two stable polymorphs, gamma IMC and SFZ III. The computational approach used has many limitations. The software does not allow for conversion to the amorphous form or polymorphic conversions. Such conversions were seen to occur, particularly for the metastable polymorphs used, meaning that this computational approach may only be suitable for stable polymorphs.

The process of milling drugs to obtain samples with a desirable particle size range has been widely used in the pharmaceutical industry, especially for the production of drugs for inhalation. However by subjecting materials to milling techniques surfaces may become thermodynamically activated which may in turn lead to formation of amorphous material. Polymorphic conversions have also been noted after milling of certain materials. Salt and cocrystal formation is a good way of enhancing the properties of an API but little or no work has been published which investigates the stability of these entities when subjected to milling. Different milling techniques (ball and jet) and temperatures (ambient and cryogenic) were used to investigate the milling behaviour of polymorphs, salts and cocrystals. All materials were analysed by XRPD and DSC to investigate any physical changes, i.e. changes in melting point and by inverse gas chromatography (IGC) to investigate whether any changes in the surface energetics occurred as a result of milling. Another aim of this thesis was to see if it was possible to predict the milling behaviour of polymorphs by calculating the attachment energies of the different crystal facets using Materials Studio 4.0. These results were compared to the IGC data to see if the predicted surface changes had occurred. The data collected in this study showed that different milling techniques can have a different effect on the same material. For example ball milling at ambient temperature and jet micronisation of the SFZ tosylate salt caused a notable increase in the melting point of the material whereas ball milling at cryogenic temperatures did not cause this to happen. The IGC data collected for this form also showed a contrast between cryomilling and the other two techniques. The study also showed that the formation of salts and cocrystals does not necessarily offer any increased stability in terms of physical properties or surface energetics. Changes in melting point were observed for the SFZ tosylate salt and the IMC:Benzamide cocrystal. Changes in the specific surface energies were also observed indicating that the nature of the surfaces was also changing. The materials which appeared to be affected the least were the two stable polymorphs, gamma IMC and SFZ III. The computational approach used has many limitations. The software does not allow for conversion to the amorphous form or polymorphic conversions. Such conversions were seen to occur, particularly for the metastable polymorphs used, meaning that this computational approach may only be suitable for stable polymorphs.