Anthocyanins standards (cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside) isolation from freeze-dried açaí (Euterpe oleraceae Mart.) by HPLC

Availability of analytical standards is a critical aspect in developing methods for quantitative analysis of anthocyanins. The anthocyanins cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside were isolated from samples of freeze-dried açaí (Euterpe oleraceae Mart.), which is a round and purple well-known palm fruit in Brazil, and then used as standards. The isolation of the anthocyanins was performed by High Performance Liquid Chromatography (HPLC), using an adapted six-channel selection valve. The identification of anthocyanin pigments in açaí was based on mass spectrometric data for molecular ions and MS-MS product ions and on previous published data. After the collection procedure, standards with a high purity grade were obtained and an external standard curve of each anthocyanin was plotted.

Characterization and classification of pequi trees (Caryocar brasiliense Camb.) based on the profile of volatile constituents using headspace solid-phase microextraction - gas chromatography - mass spectrometry and multivariate analysis

In order to determine the variability of pequi tree (Caryocar brasiliense Camb.) populations, volatile compounds from fruits of eighteen trees representing five populations were extracted by headspace solid-phase microextraction and analyzed by gas chromatography-mass spectrometry. Seventy-seven compounds were identified, including esters, hydrocarbons, terpenoids, ketones, lactones, and alcohols. Several compounds had not been previously reported in the pequi fruit. The amount of total volatile compounds and the individual compound contents varied between plants. The volatile profile enabled the differentiation of all of the eighteen plants, indicating that there is a characteristic profile in terms of their origin. The use of Principal Component Analysis and Cluster Analysis enabled the establishment of markers (dendrolasin, ethyl octanoate, ethyl 2-octenoate and β-cis-ocimene) that discriminated among the pequi trees. According to the Cluster Analysis, the plants were classified into three main clusters, and four other plants showed a tendency to isolation. The results from multivariate analysis did not always group plants from the same population together, indicating that there is greater variability within the populations than between pequi tree populations.

Analysis and guidelines for implementation of EN 1090-2 Standard to assist execution class assignment of steel structures

Finnish design and consulting companies are delivering robust and cost-efficient steel structures solutions to a large number of manufacturing companies worldwide. Recently introduced EN 1090-2 standard obliges these companies to specify the execution class of steel structures for their customers. This however, requires clarifying, understanding and interpreting the sophisticated procedure of execution class assignment. The objective of this research is to provide a clear explanation and guidance through the process of execution class assignment for a given steel structure and to support the implementation of EN 1090-2 standard in Rejlers Oy, one of Finnish design and consulting companies. This objective is accomplished by creating a guideline for designers that elaborates on the four-step process of the execution class assignment for a steel structure or its part. Steps one to three define the consequence class (projected consequences of structure failure), the service category (hazards associated with the service use exploitation of steel structure) and the production category (manufacturing process peculiarities), based on the ductility class (capacity of structure to withstand deformations) and the behaviour factor (corresponds to structure seismic behaviour). The final step is the execution class assignment taking into account results of previous steps. Main research method is indepth literature review of European standards family for steel structures. Other research approach is a series of interviews of Rejlers Oy representatives and its clients, results of which have been used to evaluate the level of EN 1090-2 awareness. Rejlers Oy will use the developed novel coherent standard implementation guideline to improve its services and to obtain greater customer satisfaction.

Exploring the impact of celebrity endorsement and product class involvement on advertising effectiveness: an eye tracking approach

Celebrity endorsement has increased in popularity over the past decades and companies are willing to spend increasingly excessive amounts of money into it. Even though multiple studies support celebrity endorsement, further research on its impact on advertising effectiveness is called for. Fur-ther, the role of consumers’ product class involvement in advertising needs to be further studied. The purpose of this study is to explore if consumers’ product class involvement and exposure to celebrity endorsers affect consumers brand recall. Supported by earlier studies, brand recall was used as a measure for advertising effectiveness in this study. In general, a psychological approach was chosen for building the theoretical framework. Concept of classical conditioning was presented in order to understand why people act how they do. Balanced theory and meaning transfer model were presented in order to study how celebrities can be used effectively in advertising context. Further, the importance of product class involvement in advertising effectiveness was evaluated. Hypotheses were formulated based on a literature review of the existing research. Because of the versatility of the research design, a mixed methods approach for this study was adopted. Empirical part of the study was conducted in three stages. First, a pre-test was conducted in order to choose suitable product endorsers for the advertisement stimuli used in the experiment. Second, an eye-tracking experiment with 30 test subjects was conducted in order to study how people view advertisements and whether the familiarity of the product endorser and consumers’ product class involvement affects brand recall. For the experiment, a fictional brand was created in order to avoid bias on brand recall. Third, qualitative interviews for 15 test subjects were conducted in the post-experiment stage in order to gain deeper understating of the phenomenon and to make sense of the findings from the experiment. Findings from this study support celebrity endorsement by suggesting that a famous spokesperson does not steal attention from brand information more than a non-celebrity product endorser. As a result, the use of a celebrity endorser did not decrease brand recall. Results support earlier research as consumer’ higher product class involvement resulted in a better brand recall. Findings from the interviews suggest that consumers have positive perceptions of celebrity endorsement in general. However, the celebrity–brand congruence is a crucial factor when creating attitudes towards the advertisement. Future research ideas were presented based on the limitations and results of this study

Value co-creation in bio-based chemicals value network

The purpose of this Master’s thesis is to study value co-creation in emerging value network. The main objective is to examine how value is co-created in bio-based chemicals value network. The study provides insights to different actors’ perceived value in the value network and enlightens their motivations to commit to the collaborative partnerships with other actors. Empirical study shows that value co-creation is creation of mutual value for both parties of the relationship by combining their non-competing resources to achieve a common goal. Value co-creation happens in interactions, and trust, commitment and information sharing are essential prerequisites for value co-creation. Value co-creation is not only common value creation, but it is also value that emerges for each actor because of the co-operation with the other actor. Even though the case companies define value mainly in economic terms, the other value elements like value of the partnership, knowledge transfer and innovation are more important for value co-creation.

Development of a bovine adenovirus type 2-based gene delivery vector /

ABSTRACT Recombinant adenoviruses are currently under intense investigation as potential gene delivery and gene expression vectors with applications in human and veterinary medicine. As part of our efforts to develop a bovine adenovirus type 2 (BAV2) based vector system, the nucleotide sequence of BAV2 was determined. Sixty-six open reading frames (ORFs) were found with the potential to encode polypeptides that were at least 50 amino acid (aa) residue long. Thirty-one of the BAV2 polypeptide sequences were found to share homology to already identified adenovirus proteins. The arrangement of the genes revealed that the BAV2 genomic organization closely resembles that of well-characterized human adenoviruses. In the course of this study, continuous propagation of BAV2 over many generations in cell culture resulted in the isolation of a BAV2 spontaneous mutant in which the E3 region was deleted. Restriction enzyme, sequencing and PCR analyses produced concordant results that precisely located the deletion and revealed that its size was exactly 1299 bp. The E3-deleted virus was plaque-purified and further propagated in cell culture. It appeared that the replication of such a virus lacking a portion of the E3 region was not affected, at least in cell culture. Attempts to rescue a recombinant BAV2 virus with the bacterial kanamycin resistance gene in the E3 region yielded a candidate as verified with extensive Southern blotting and PCR analyses. Attempts to purify the recombinant virus were not successful, suggesting that such recombinant BAV2 was helper-dependent. Ten clones containing full-length BAV2 genomes in a pWE15 cosmid vector were constructed. The infectivity of these constructs was tested by using different transfection methods. The BAV2 genomic clones did appear to be infectious only after extended incubation period. This may be due to limitations of various transfection methods tested, or biological differences between virus- and E. co//-derived BAV2 DNA.

Modernizing human resource management : the importance of values-based leadership in the Canadian federal public service /

Over the past several decades, many theories have been advanced as to why efforts to reform the public service have met with only limited success. Clearly, the role of leadership with respect to reform must be examined, since successful organizational leaders should be extremely accomplished in the promotion and protection of the values that underlie decision-making. The issue of effective leadership is particularly significant for the future of the public service of Canada. Large numbers of public servants in the executive ranks are due to retire within the next five years. Given their central role, it is vital that there be enough dedicated and committed public servants to staff future vacancies. It is also essential that future public service leaders possess the competencies and values associated with a world-class public service and, a new type of public organization. Related to this point is the importance of people-management skills. People management in the public service is an issue that has historically faced - and will continue to face - major challenges with respect to recruiting and retaining the leaders it requires for its continued success. It is imperative that the public service not only be revitalized and be seen as an employer of choice, but also that the process by which it accomplishes this goal - the practice of human resource management - be modernized. To achieve the flexibility needed to remain effective, the public service requires the kind ofleadership that supports new public service values such as innovation and which emphasizes a "people- first" approach. This thesis examines the kind of public service leadership needed to modernize the human resource management regime in the federal public service. A historical examination of public service values is presented to help determine the values that are important for public service leaders with respect to modernizing human resource management. Since replenishing the 2 ranks of public service leaders is crucial to ensure the quality of service to Canadians, leadership that supports career planning will be a major focus of this paper. In addition, this thesis demonstrates that while traditional public service values continue to endure, innovative leaders must effectively reconcile new public service values with traditional values in order to increase the possibilities for successful reform as well as achieve business objectives. Much of the thesis is devoted to explaining the crucial role of post-bureaucratic leadership to successful reform. One of the major findings of the thesis is that leaders who demonstrate a blending of new public service values and traditional values are critical to creating effective employment relationships, which are key to modernizing human resource management in the federal public service. It will be apparent that public service leaders must ensure that an appropriate accountability framework is in place before embarking on reform. However, leaders who support new public service values such as innovation and empowerment and who emphasize the importance of people are essential to successful reform.

Web based content and hybrid teaching: student perceptions of the effectiveness of using web based content and hyper-linked teaching units in teaching hybrid business and marketing post secondary classes /

This exploratory, descriptive action research study is based on a survey of a sample of convenience consisting of 172 college and university marketing students, and 5 professors who were experienced in teaching in an internet based environment. The students that were surveyed were studying e-commerce and international business in 3^^ and 4*'' year classes at a leading imiversity in Ontario and e-commerce in 5^ semester classes at a leading college. These classes were taught using a hybrid teaching style with the contribution of a large website that contained pertinent text and audio material. Hybrid teaching employs web based course materials (some in the form of Learning Objects) to deliver curriculimi material both during the attended lectures and also for students accessing the course web page outside of class hours. The survey was in the form on an online questionnaire. The research questions explored in this study were: 1. What factors influence the students' ability to access and learn from web based course content? 2. How likely are the students to use selected elements of internet based curriculum for learning academic content? 3. What is the preferred physical environment to facilitate learning in a hybrid environment? 4. How effective are selected teaching/learning strategies in a hybrid environment? The findings of this study suggest that students are very interested in being part of the learning process by contributing to a course web site. Specifically, students are interested in audio content being one of the formats of online course material, and have an interest in being part of the creation of small audio clips to be used in class.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

The evaluation of a predialysis class on client knowledge and attitude toward compliant behaviours

In this quasi-experimental study, the theory of reasoned action was used as a conceptual framework to assess the outcome effect of a predialysis class. A pretest, posttest design was used to determine changes in client knowledge about their condition and its treatment, and their intention, attitudes and social norm towards compliant behaviours. The related compliant behaviours were following a low-salt diet and taking medications as proscribed. Thirty-eight End Stage Renal Diseases (ESRD) clients were self-selected into the treatment or control groups. Both groups received the standard predialysis education from members of the multidisciplinary renal team. In addition, the treatment group also attended the predialysis class. Subjects' health locus of control, anxiety and demographic variables were measured as possible extraneous variables. Study subjects from both groups demonstrated a high internal and powerful others health locus of control and a normal range of anxiety. Although not statistically significant ill = .64), the experimental group demonstrated higher knowledge level and greater intention to follow a low salt diet UL= .73). They developed more significantly positive attitudes towards following a low salt diet and increased subjective norm influence after attending the predialysis class. Attending the predialysis class did not have an effect on subjects' intentions, attitudes or subjective norm towards taking medications as prescribed. Conclusion: The predialysis class was only marginally effective in increasing client knowledge, but influenced clients' attitudes towards following a low-salt diet. Based on the results, recommendations for improvements to the class have been suggested.

The versatility and utilization of phosphorus based compounds in classic carbon-carbon bond forming and esterification reactions

The phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) has been employed as an efficient reusable media for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts ofwater and toluene (single phase) using potassium phosphate and 1% Pd2(dba)3'CHCI3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and were all complete within 1 hour at 50°C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70°C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system, from which the catalyst was then recycled by removing the top (hexanes) and bottom (aqueous) layers and adding the reagents to the ionic liquid which was heated again at 50°C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences. IL ESTERIFICATIONREACTION A new class oftrialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence oftriethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and stenc nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.

Isolation and characterization of genomic DNA sequences that enhance the stability of plasmid DNA in mammalian cells /

The ease of production and manipulation has made plasmid DNA a prime target for its use in gene transfer technologies such as gene therapy and DNA vaccines. The major drawback of plasmid however is its stability within mammalian cells. Plasmid DNA is usually lost by cellular mechanisms or as a result of mitosis by simple dilution. This study set out to search for mammalian genomic DNA sequences that would enhance the stability of plasmid DNA in mammalian cells.Creating a plasmid based genomic DNA library, we were able to screen the human genome by transfecting the library into Human Embryonic Kidney (HEK 293) Cells. Cells that contained plasmid DNA were selected, using G418 for 14 days. The resulting population was then screened for the presence of biologically active plasmid DNA using the process of transformation as a detector.A commercially available plasmid DNA isolation kit was modified to extract plasmid DNA from mammalian cells. The standardized protocol had a detection limit of -0.6 plasmids per cell in one million cells. This allowed for the detection of 45 plasmids that were maintained for 32 days in the HEK 293 cells. Sequencing of selected inserts revealed a significantly higher thymine content in comparison to the human genome. Sequences with high A/T content have been associated with Scaffold/Matrix Attachment Region (S/MAR) sequences in mammalian cells. Therefore, association with the nuclear matrix might be required for the stability of plasmids in mammalian cells.

The reliability of an isometric test based on constant perception of effort

To date there is no documented procedure to extrapolate findings of an isometric nature to a whole body performance setting. The purpose of this study was to quantify the reliability of perceived exertion to control neuromuscular output during an isometric contraction. 21 varsity athletes completed a maximal voluntary contraction and a 2 min constant force contraction at both the start and end of the study. Between pre and post testing all participants completed a 2 min constant perceived exertion contraction once a day for 4 days. Intra-class correlation coefficient (R=O.949) and standard error of measurement (SEM=5.12 Nm) concluded that the isometric contraction was reliable. Limits of agreement demonstrated only moderate initial reliability, yet with smaller limits towards the end of 4 training sessions. In conclusion, athlete's na"ive to a constant effort isometric contraction will produce reliable and acceptably stable results after 1 familiarization sessions has been completed.

Testing Mean-Variance Efficiency in CAPM with Possibly Non-Gaussian Errors : An Exact Simulation-Based Approach

In this paper we propose exact likelihood-based mean-variance efficiency tests of the market portfolio in the context of Capital Asset Pricing Model (CAPM), allowing for a wide class of error distributions which include normality as a special case. These tests are developed in the frame-work of multivariate linear regressions (MLR). It is well known however that despite their simple statistical structure, standard asymptotically justified MLR-based tests are unreliable. In financial econometrics, exact tests have been proposed for a few specific hypotheses [Jobson and Korkie (Journal of Financial Economics, 1982), MacKinlay (Journal of Financial Economics, 1987), Gib-bons, Ross and Shanken (Econometrica, 1989), Zhou (Journal of Finance 1993)], most of which depend on normality. For the gaussian model, our tests correspond to Gibbons, Ross and Shanken’s mean-variance efficiency tests. In non-gaussian contexts, we reconsider mean-variance efficiency tests allowing for multivariate Student-t and gaussian mixture errors. Our framework allows to cast more evidence on whether the normality assumption is too restrictive when testing the CAPM. We also propose exact multivariate diagnostic checks (including tests for multivariate GARCH and mul-tivariate generalization of the well known variance ratio tests) and goodness of fit tests as well as a set estimate for the intervening nuisance parameters. Our results [over five-year subperiods] show the following: (i) multivariate normality is rejected in most subperiods, (ii) residual checks reveal no significant departures from the multivariate i.i.d. assumption, and (iii) mean-variance efficiency tests of the market portfolio is not rejected as frequently once it is allowed for the possibility of non-normal errors.

Responsibility and Cross-Subsidization in Cost Sharing

We propose two axiomatic theories of cost sharing with the common premise that agents demand comparable -though perhaps different- commodities and are responsible for their own demand. Under partial responsibility the agents are not responsible for the asymmetries of the cost function: two agents consuming the same amount of output always pay the same price; this holds true under full responsibility only if the cost function is symmetric in all individual demands. If the cost function is additively separable, each agent pays her stand alone cost under full responsibility; this holds true under partial responsibility only if, in addition, the cost function is symmetric. By generalizing Moulin and Shenker’s (1999) Distributivity axiom to cost-sharing methods for heterogeneous goods, we identify in each of our two theories a different serial method. The subsidy-free serial method (Moulin, 1995) is essentially the only distributive method meeting Ranking and Dummy. The cross-subsidizing serial method (Sprumont, 1998) is the only distributive method satisfying Separability and Strong Ranking. Finally, we propose an alternative characterization of the latter method based on a strengthening of Distributivity.