Determination of structural and mechanical properties, diffractometry, and thermal analysis of chitosan and hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol

In this work, the structural, mechanical, diffractometric, and thermal parameters of chitosan-hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol were studied. Solutions of HPMC (2% w/v) in water and chitosan (2% w/v) in 2% acetic acid solution were prepared. The concentration of sorbitol used was 10% (w/w) to both polymers. This solutions were mixed at different proportions (100/0; 70/30; 50/50; 30/70, and 0/100) of chitosan and HPMC, respectively, and 20 mL was cast in Petri dishes for further analysis of dried films. The miscibility of polymers was assessed by X-ray diffraction, scanning electronic microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The results obtained indicate that the films are not fully miscible at a dry state despite the weak hydrogen bonding between the polymer functional groups.

Effect of preparation practices and the cowpea cultivar Vigna unguiculata L.Walp on the quality and content of myo-inositol phosphate in akara (fried bean paste)

Akara is one of Brazil's national treasures prepared from cowpea (Vigna unguiculata L.Walp), grated onions and salt and deep-fried in crude palm oil. The results of this study on akara preparation methods showed that, in general, cowpeas were soaked for up 3 hours at room temperature, and the seed coats were then removed. The akara makers preferred the olho de pombo cultivar, because of its cream hue, or the macassar cultivar because it produces a crispier paste. The seeds purchased from street markets had lower ranges of InsP6, InsP5, and InsP4 (1.03-7.62 ∝mol.g- 1; 0.14-1.31 ∝mol.g- 1; and 0.0-0.10 ∝mol.g- 1, respectively) than both the paste and akara (6.72-19.24 ∝mol.g- 1; 1.29-4.57 ∝mol.g- 1; 0.0-0.76 ∝mol.g- 1; 3.31-13.71 ∝mol.g- 1; 0.0-4.48 ∝mol.g- 1; and 0.0-1.32 ∝mol.g- 1). These results suggest that other beans or cowpea varieties have been used in the preparation of akara and that the phytate levels do not affect its nutritional quality.

Phylogenetic Analysis of Avidins and Expression of Novel Avidins from Lactrodectus hesperus and Hoeflea phototrophica

Avidins (Avds) are homotetrameric or homodimeric glycoproteins with typically less than 130 amino acid residues per monomer. They form a highly stable, non-covalent complex with biotin (vitamin H) with Kd = 10-15 M (for chicken Avd). The best-studied Avds are the chicken Avd from Gallus gallus and streptavidin from Streptomyces avidinii, although other Avd studies have also included Avds from various origins, e.g., from frogs, fishes, mushrooms and from many different bacteria. Several engineered Avds have been reported as well, e.g., dual-chain Avds (dcAvds) and single-chain Avds (scAvds), circular permutants with up to four simultaneously modifiable ligand-binding sites. These engineered Avds along with the many native Avds have potential to be used in various nanobiotechnological applications. In this study, we made a structure-based alignment representing all currently available sequences of Avds and studied the evolutionary relationship of Avds using phylogenetic analysis. First, we created an initial multiple sequence alignment of Avds using 42 closely related sequences, guided by the known Avd crystal structures. Next, we searched for non-redundant Avd sequences from various online databases, including National Centre for Biotechnology Information and the Universal Protein Resource; the identified sequences were added to the initial alignment to expand it to a final alignment of 242 Avd sequences. The MEGA software package was used to create distance matrices and a phylogenetic tree. Bootstrap reproducibility of the tree was poor at multiple nodes and may reflect on several possible issues with the data: the sequence length compared is relatively short and, whereas some positions are highly conserved and functional, others can vary without impinging on the structure or the function, so there are few informative sites; it may be that periods of rapid duplication have led to paralogs and that the differences among them are within the error limit of the data; and there may be other yet unknown reasons. Principle component analysis applied to alternative distance data did segregate the major groups, and success is likely due to the multivariate consideration of all the information. Furthermore, based on our extensive alignment and phylogenetic analysis, we expressed two novel Avds, lacavidin from Lactrodectus Hesperus, a western black widow spider, and hoefavidin from Hoeflea phototrophica, an aerobic marine bacterium, the ultimate aim being to determine their X-ray structures. These Avds were selected because of their unique sequences: lacavidin has an N-terminal Avd-like domain but a long C-terminal overhang, whereas hoefavidin was thought to be a dimeric Avd. Both these Avds could be used as novel scaffolds in biotechnological applications.

Spectral Analysis of Symmetric and Anti-Symmetric Pairwise Kernels

This work investigates theoretical properties of symmetric and anti-symmetric kernels. First chapters give an overview of the theory of kernels used in supervised machine learning. Central focus is on the regularized least squares algorithm, which is motivated as a problem of function reconstruction through an abstract inverse problem. Brief review of reproducing kernel Hilbert spaces shows how kernels define an implicit hypothesis space with multiple equivalent characterizations and how this space may be modified by incorporating prior knowledge. Mathematical results of the abstract inverse problem, in particular spectral properties, pseudoinverse and regularization are recollected and then specialized to kernels. Symmetric and anti-symmetric kernels are applied in relation learning problems which incorporate prior knowledge that the relation is symmetric or anti-symmetric, respectively. Theoretical properties of these kernels are proved in a draft this thesis is based on and comprehensively referenced here. These proofs show that these kernels can be guaranteed to learn only symmetric or anti-symmetric relations, and they can learn any relations relative to the original kernel modified to learn only symmetric or anti-symmetric parts. Further results prove spectral properties of these kernels, central result being a simple inequality for the the trace of the estimator, also called the effective dimension. This quantity is used in learning bounds to guarantee smaller variance.

A performance analysis of conventional and fundamental exchange traded funds: ETFs and their risk-return characteristics in relation to building institutional investor’s passive portfolio

An exchange traded fund (ETF) is a financial instrument that tracks some predetermined index. Since their initial establishment in 1993, ETFs have grown in importance in the field of passive investing. The main reason for the growth of the ETF industry is that ETFs combine benefits of stock investing and mutual fund investing. Although ETFs resemble mutual funds in many ways, also many differences occur. In addition, ETFs not only differ from mutual funds but also differ among each other. ETFs can be divided into two categories, i.e. market capitalisation ETFs and fundamental (or strategic) ETFs, and further into subcategories depending on their fundament basis. ETFs are a useful tool for diversification especially for a long-term investor. Although the economic importance of ETFs has risen drastically during the past 25 years, the differences and risk-return characteristics of fundamental ETFs have yet been rather unstudied area. In effect, no previous research on market capitalisation and fundamental ETFs was found during the research process. For its part, this thesis seeks to fill this research gap. The studied data consist of 50 market capitalisation ETFs and 50 fundamental ETFs. The fundaments, on which the indices that the fundamental ETFs track, were not limited nor segregated into subsections. The two types of ETFs were studied at an aggregate level as two different research groups. The dataset ranges from June 2006 to December 2014 with 103 monthly observations. The data was gathered using Bloomberg Terminal. The analysis was conducted as an econometric performance analysis. In addition to other econometric measures, the methods that were used in the performance analysis included modified Value-at-Risk, modified Sharpe ratio and Treynor ratio. The results supported the hypothesis that passive market capitalisation ETFs outperform active fundamental ETFs in terms of risk-adjusted returns, though the difference is rather small. Nevertheless, when taking into account the higher overall trading costs of the fundamental ETFs, the underperformance gap widens. According to the research results, market capitalisation ETFs are a recommendable diversification instrument for a long-term investor. In addition to better risk-adjusted returns, passive ETFs are more transparent and the bases of their underlying indices are simpler than those of fundamental ETFs. ETFs are still a young financial innovation and hence data is scarcely available. On future research, it would be valuable to research the differences in risk-adjusted returns also between the subsections of fundamental ETFs.

Intellectual capital, knowledge management practices and firm performance

Researchers have widely recognised and accepted that firm performance is increasingly related to knowledge-based issues. Two separately developed literature streams, intellectual capital (IC) and knowledge management (KM), have been established as the key discussions related to knowledge-based competitive advantage of the firm. Intellectual capital has provided evidence on the strategic key intangible resources of the firm, which could be deployed to create competitive advantage. Knowledge management, in turn, has focused on the managerial processes and practices which can be used to leverage IC to create competitive advantage. Despite extensive literature on both issues, some notable research gaps remain to be closed. In effect, one major gap within the knowledge management research is the lack of understanding related to its influence on firm performance, while IC researchers have articulated a need to utilise more finegrained conceptual models to better understand the key strategic value-creating resources of the firm. In this dissertation, IC is regarded as the entire intellectual capacity, knowledge and competences of the firm that can be leveraged to achieve sustained competitive advantage. KM practices are defined as organisational and managerial activities that enable the firm to leverage its IC to create value. The objective of this dissertation is to answer the research question: “What is the relationship between intellectual capital, knowledge management practices and firm performance?” Five publications have addressed the research question using different approaches. The first two publications were systematic literature reviews of the extant empirical IC and KM research, which established the current state of understanding regarding the relationship between IC, KM practices and firm performance. Publications III and IV were empirical research articles that assessed the developed conceptual model related to IC, KM practices and firm performance. Finally, Publication V was among the first research papers to merge IC and KM disciplines in order to find out which configurations could yield organisational benefits in terms of innovation and market performance outcomes.

Examining current facilitative practices and projections of activity-based physical education degree programs regarding the participation of individuals with disabilties /

Individuals with disabiliiies are increasingly accessing post secondary education opportunities to further develop their educational and career goals. This study examines the current facilitative practices of Canadian university activity-based physical education degree programs on the participation of individuals with disabilities. A critical orientation and descriptive/interpretative approach allows insight into unique stories and experiences of physical education practitioners and special needs professionals as they attempt to provide equitable educational experiences within a least restrictive environment. Leading practitioners are used to triangulate and strengthen the validity of the data while providing direction and advocacy for future development and inclusion of individuals with disabilities. The study concludes with seven recommendations, each providing university activity-based physical education degree programs with viable opportunities for helping create equitable opportunities for individuals with disabilities.

Parental goals among Italian-Canadian and Anglo-Canadian families : their connection to socialization practices and the quality of parent-young adult relationship /

Parenting goals are the behavioral, cognitive, and affective outcomes that parents implicitly or explicitly strive to achieve during specific interactions with their children. In the present study, intergenerational parenting practices and goals in Italian-Canadian and Anglo-Canadian families were examined. The association between parenting goals, parents' socialization practices, and the quality of relationship between parent and child were investigated. Participants included individuals ranging in age from 1 8-26 years and their mothers from Anglo-Canadian (n= 31) and Italian-Canadian families (n= 50). The young adults and their mothers were asked to imagine how their respective parents would have reacted to five hypothetical vignettes depicting difficult parent-child interactions. Young adults and their mothers were also asked to rate the importance of parenting goals within these parent-child situations. In addition, young adults assessed the perceived quality of their present relationships with each parent. Cultural differences were revealed such that Italian-Canadian parents endorsed more authoritarian parenting strategies and relationship-centered goals than Anglo-Canadian parents. However, Italian-Canadian and Anglo-Canadian parents were not found to differ on their endorsement of parent-centered goals. Italian-Canadian parents' who did use authoritarian strategies were found to have young-adult children who perceived their relationship with their parents as less satisfying, intimate, affectionate and having relatively high levels of conflict than parents who did not use authoritarian strategies. Anglo-Canadian parents' authoritative strategies were correlated with a better perceived relationship quality by young-adult children.

An in-depth analysis of real and perceived barriers to speech and language program participation for children with speech and language delays : a question of barriers to service?

The current study investigated the effects that barriers (both real and perceived) had on participation and completion of speech and language programs for preschool children with communication delays. I compared 36 families of preschool children with an identified communication delay that have completed services (completers) to 13 families that have not completed services (non-completers) prescribed by Speech and Language professionals. Data findings reported were drawn from an interview with the mother, a speech and language assessment of the child, and an extensive package of measures completed by the mother. Children ranged in age from 32 to 71 mos. These data were collected as part of a project funded by the Canadian Language and Literacy Research Networks of Centres of Excellence. Findings suggest that completers and non-completers shared commonalities in a number of parenting characteristics but differed significantly in two areas. Mothers in the noncompleting group were more permissive and had lower maternal education than mothers in the completing families. From a systemic standpoint, families also differed in the number of perceived barriers to treatment experienced during their time with Speech Services Niagara. Mothers in the non-completing group experienced more perceived barriers to treatment than completing mothers. Specifically, these mothers perceived more stressors and obstacles that competed with treatment, perceived more treatment demands and they perceived the relevance of treatment as less important than the completing group. Despite this, the findings suggest that non-completing families were 100% satisfied with services. Contrary to predictions, there were no significant differences in child characterisfics and economic characteristics between completers and non-completers. The findings in this study are considered exploratory and tentative due to the small sample size.

Anomalous carbonate preservation in the abyssal North Pacific, ODP sites 882 and 1179: planktonic foraminiferal analysis, climate change and palaeogeomagnetism /

Thesis (M.Sc.)--Brock University, 2004.

The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halide molecules /

TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.

Anti-Oedipus en-procés : a comparative analysis of Kristeva and Deleuze & Guattari

The present thesis is an attempt to bring into dialogue what appear to be two radically different approaches of negotiating subjectivity in late Western Modernity. Here the thought of Julia Kristeva as well as Gilles Deleuze and Felix Guattari are fully engaged. These thinkers, the latter two being considered as one, have until now remained strangers to one another. Consequently much confusion has amassed concerning their respective philosophical, as well as social/political projects. I take up the position that Deleuze and Guattari's account of subjectivity is a commendable attempt to understand a particular type of historical subject: late modern Western man. However I claim that their account comes up short insofar as I argue that they lack the theoretical language in order to fully, and successfully, make their point. Thus I argue that their system does not stand up to its own claims. On the contrary, by embracing the psychoanalytic tradition - staying rather close to the Freudian and Kleinian schools of thought - I argue that it is in fact Kristeva that is better equipped to provide an account of this particular subject. Considerable time is invested in fleshing out the notion of the Other insofar as this Other is central to the constitution of subjectivity. This Other - insofar as this Other is to be found in Kristeva's notion of the chora -- is something I claim that Deleuze and Guattari simply undervalued.

A Foucauldian Analysis of Power and Representation in an Attempt to Run a Photovoice Project with Youth

This project evolved out of a search for ways to conduct research on “others” in a way that does not exploit, stigmatize or misrepresent their experience. This thesis is an ethnographic study in leisure research and youth work and an experiment in running a photovoice project. Photovoice is a participatory visual method that embodies the emancipatory ideal of empowering others through self-representation. The literature on photovoice lacks a comprehensive discussion on the complexity of power and representation. Postmodern theorists have proposed that participatory methods are not benign and that initiatives are acts of power in themselves that produce effects (Cook & Kothari, 2001). A Foucauldian analysis of power is used to deconstruct the researcher’s practice and reflect on why and how youth are “engaged”. This project seeks to embrace the principle of working “with” others, but also work from a postmodern perspective that acknowledges power and representation as ongoing problems.

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.