Cellulose composite structures – by design

The aim of the work presented in this thesis was to investigate different mechanical and chemical pre-treatments which can dramatically change the properties of native cellulose and add alternative routes to structure formation. Ball milled cellulose, which had a reduced crystallinity, degree of polymerisation and degradation temperature, was rehydrated in excess water resulting in recrystallisation. Fully amorphous samples recrystallised to the more thermodynamically stable type II polymorphic crystal structure. Flash differential scanning calorimetry (DSC), which allows thermal transitions to be scanned at much higher rates than conventional DSC, was able to register a glass transition temperature for amorphous cellulose. The next stage of the study focussed on the production of freeze dried galactomannan foams. Cellulose fibres provided reinforcement to the foams. The level of reinforcement was related to fibre content, size, crystallinity and surface roughness. Microfibrillated cellulose (MFC) provided the greatest reinforcement due to its much higher surface area and fibrillated structure. Extrusion was found to be a useful alternative to homogenisation for the production of MFC and to create foams using alternative processing to the freeze drying routes. A novel molten salt hydrate, LiCl/urea/water, was found to swell native cellulose and reduce its crystallinity. A weak gel-like structure was formed at ambient temperature. Micro DSC results showed that this structure was melted out at 60oC but the process was reversible indicating hydrophilic to hydrophobic conformational changes on the surface of the cellulose fibres, although these were likely to be dependent on the celluloses having a low degree of polymerisation. In these solvent conditions starch granules were eroded from the outside rather than being swollen as has been found for some ionic liquids and underwent total dissolution in LiCl/urea/water. Fenugreek and xyloglucan, which are both highly branched, were found to increase in viscosity in LiCl/urea/water relative to water, possibly due to the breakage of all intramolecular associations whereas the viscosity of konjac which is predominantly unbranched did not change. Locust bean gum (LBG) had a lower viscosity in LiCl/urea/water compared to water due to the disruption of aggregates. Confocal microscopy showed that fenugreek and LBG are able to bind to cellulose in water, however, the conformational change of fenugreek in these solvent conditions inhibited it from binding to cellulose in LiCl/urea/water whereas conformational change allowed xyloglucan to bind to cellulose in LiCl/urea/water whilst it was unable to bind in water. Konjac did not bind to cellulose in either solvent system. The pre-treatments shown in this work will enable the creation of novel cellulose composites

Cellulose composite structures – by design

The aim of the work presented in this thesis was to investigate different mechanical and chemical pre-treatments which can dramatically change the properties of native cellulose and add alternative routes to structure formation. Ball milled cellulose, which had a reduced crystallinity, degree of polymerisation and degradation temperature, was rehydrated in excess water resulting in recrystallisation. Fully amorphous samples recrystallised to the more thermodynamically stable type II polymorphic crystal structure. Flash differential scanning calorimetry (DSC), which allows thermal transitions to be scanned at much higher rates than conventional DSC, was able to register a glass transition temperature for amorphous cellulose. The next stage of the study focussed on the production of freeze dried galactomannan foams. Cellulose fibres provided reinforcement to the foams. The level of reinforcement was related to fibre content, size, crystallinity and surface roughness. Microfibrillated cellulose (MFC) provided the greatest reinforcement due to its much higher surface area and fibrillated structure. Extrusion was found to be a useful alternative to homogenisation for the production of MFC and to create foams using alternative processing to the freeze drying routes. A novel molten salt hydrate, LiCl/urea/water, was found to swell native cellulose and reduce its crystallinity. A weak gel-like structure was formed at ambient temperature. Micro DSC results showed that this structure was melted out at 60oC but the process was reversible indicating hydrophilic to hydrophobic conformational changes on the surface of the cellulose fibres, although these were likely to be dependent on the celluloses having a low degree of polymerisation. In these solvent conditions starch granules were eroded from the outside rather than being swollen as has been found for some ionic liquids and underwent total dissolution in LiCl/urea/water. Fenugreek and xyloglucan, which are both highly branched, were found to increase in viscosity in LiCl/urea/water relative to water, possibly due to the breakage of all intramolecular associations whereas the viscosity of konjac which is predominantly unbranched did not change. Locust bean gum (LBG) had a lower viscosity in LiCl/urea/water compared to water due to the disruption of aggregates. Confocal microscopy showed that fenugreek and LBG are able to bind to cellulose in water, however, the conformational change of fenugreek in these solvent conditions inhibited it from binding to cellulose in LiCl/urea/water whereas conformational change allowed xyloglucan to bind to cellulose in LiCl/urea/water whilst it was unable to bind in water. Konjac did not bind to cellulose in either solvent system. The pre-treatments shown in this work will enable the creation of novel cellulose composites

Foliar Expression of Candidate Genes Involved in Condensed Tannin Biosynthesis in White Clover (\u3cem\u3eTrifolium Repens\u3c/em\u3e)

Bloat disease in cattle and sheep is caused by the rapid microbial degradation of protein-rich fodder in the rumen. This leads to the production of protein foams that trap gases, causing bloat, a condition that is often fatal to livestock and costly to farmers. Condensed tannins (CTs) are phenolic polymers produced by the phenylpropanoid pathway of plants (Figure 1). CTs bind to proteins under acidic to neutral conditions, such as those present in the rumen, slowing their breakdown. A diet with a CT content of between 2% and 4% by dry weight, which is provided by some pasture legumes (e.g. Lotus corniculatus), protects livestock against bloat and improves the absorption of amino acids from the diet. White clover (Trifolium repens L.), a protein rich legume widely used in temperate regions, has virtually no CTs in leaves, although they are present in flowers

Production and Analysis of Transgenic White Clover (\u3cem\u3eTrifolium Repens\u3c/em\u3e) Plants Over-Expressing Organic Acid Biosynthetic Genes

Aluminium (Al) toxicity is a major environmental limitation for plant production in acid soils, which represent more than one third of the world’s agricultural land. Al-induced secretion in roots of organic acids (OA), such as malate and citrate, chelates the toxic Al cation excluding it from the root. This mechanism of Al-tolerance appears also to be associated with enhanced P-use efficiency. The development of transgenic plants for enhanced synthesis and secretion of OA from roots is a promising approach to confer Al-tolerance and enhanced P-acquisition efficiency. In order to understand the association between OA biosynthesis and secretion from roots in white clover (Trifolium repens L.), the physiological consequences of over-expressing 3 key white clover OA biosynthetic genes, individually and in combination, were assessed in transgenic plants

Barriers and facilitators to implementing community outreach work, and inter-professional collaboration with regional partners

Abstract : Objective. Community outreach workers support individuals in accessing the health and community services they require through various forms of proximity approaches. Even though community outreach has been available in the province of Quebec (Canada) for the past 40 years, it is still difficult to implement and sustain, especially with families of young children. The aim of this study was to document barriers and facilitators to implementing community outreach practices, and to describe how such workers collaborate with sectoral (e.g. health care) and inter-sectoral (e.g. municipalities, community organizations, schools) partners. Methodology. We performed a content analysis on 55 scientific and grey literature documents, and transcriptions of 24 individual interviews and 3 focus groups with stakeholders including parents, community outreach workers, health care employees, and inter-sectoral partners. Results. This study reveals four categories of barriers and facilitators to the implementation of community outreach work (i.e. organizational factors, nature of the work and worker-related factors, family-related factors, external factors). With regards to collaboration, community outreach workers deal with various partners. Good inter-professional collaboration is achieved through positive interactions and communication, shared or co-developed activities for the families, co-intervention with families, and strategies to enhance role awareness and inter-sectoral meetings. Conclusion. Results highlighted that many factors interact and can either influence, positively or negatively, the opportunity to implement community outreach work. The collaborative practices identified may help to maximize facilitators and overcome barriers. Advocacy and a better understanding of how to integrate community outreach work within health services while maintaining the workers’ flexibility are needed to sustain this practice

Multilocus Genotyping of Human Giardia Isolates Suggests Limited Zoonotic Transmission and Association between Assemblage B and Flatulence in Children

Giardia intestinalis is a protozoan parasite found world-wide and it is a major cause of diarrhea in humans and other mammals. The genetic variability within G. intestinalis is high with eight distinct genotypes or assemblages (A-H). Here we performed sequence-based multilocus genotyping of around 200 human Giardia isolates. We found evidence of limited zoonotic transmission of certain A subtypes and an association between flatulence and assemblage B infection in children. This shows that it is important to investigate different assemblages and sub-assemblages of G. intestinalis in human infections in order to understand the clinical significance, zoonotic potential, sequence divergence, and transmission pathways of this parasite

On the genome constitution and evolution of intermediate wheatgrass (Thinopyrum intermedium: Poaceae, Triticeae)

<p>Abstract</p> <p>Background</p> <p>The wheat tribe Triticeae (Poaceae) is a diverse group of grasses representing a textbook example of reticulate evolution. Apart from globally important grain crops, there are also wild grasses which are of great practical value. Allohexaploid intermediate wheatgrass, <it>Thinopyrum intermedium </it>(2n = 6x = 42), possesses many desirable agronomic traits that make it an invaluable source of genetic material useful in wheat improvement. Although the identification of its genomic components has been the object of considerable investigation, the complete genomic constitution and its potential variability are still being unravelled. To identify the genomic constitution of this allohexaploid, four accessions of intermediate wheatgrass from its native area were analysed by sequencing of chloroplast <it>trn</it>L-F and partial nuclear GBSSI, and genomic <it>in situ </it>hybridization.</p> <p>Results</p> <p>The results confirmed the allopolyploid origin of <it>Thinopyrum intermedium </it>and revealed new aspects in its genomic composition. Genomic heterogeneity suggests a more complex origin of the species than would be expected if it originated through allohexaploidy alone. While <it>Pseudoroegneria </it>is the most probable maternal parent of the accessions analysed, nuclear GBSSI sequences suggested the contribution of distinct lineages corresponding to the following present-day genera: <it>Pseudoroegneria</it>, <it>Dasypyrum</it>, <it>Taeniatherum</it>, <it>Aegilops </it>and <it>Thinopyrum</it>. Two subgenomes of the hexaploid have most probably been contributed by <it>Pseudoroegneria </it>and <it>Dasypyrum</it>, but the identity of the third subgenome remains unresolved satisfactorily. Possibly it is of hybridogenous origin, with contributions from <it>Thinopyrum </it>and <it>Aegilops</it>. Surprising diversity of GBSSI copies corresponding to a <it>Dasypyrum</it>-like progenitor indicates either multiple contributions from different sources close to <it>Dasypyrum </it>and maintenance of divergent copies or the presence of divergent paralogs, or a combination of both. <it>Taeniatherum</it>-like GBSSI copies are most probably pseudogenic, and the mode of their acquisition by <it>Th. intermedium </it>remains unclear.</p> <p>Conclusions</p> <p>Hybridization has played a key role in the evolution of the Triticeae. Transfer of genetic material via extensive interspecific hybridization and/or introgression could have enriched the species' gene pools significantly. We have shown that the genomic heterogeneity of intermediate wheatgrass is higher than has been previously assumed, which is of particular concern to wheat breeders, who frequently use it as a source of desirable traits in wheat improvement.</p