Advanced analysis and design methods for preparative chromatographic separation processes

Preparative liquid chromatography is one of the most selective separation techniques in the fine chemical, pharmaceutical, and food industries. Several process concepts have been developed and applied for improving the performance of classical batch chromatography. The most powerful approaches include various single-column recycling schemes, counter-current and cross-current multi-column setups, and hybrid processes where chromatography is coupled with other unit operations such as crystallization, chemical reactor, and/or solvent removal unit. To fully utilize the potential of stand-alone and integrated chromatographic processes, efficient methods for selecting the best process alternative as well as optimal operating conditions are needed. In this thesis, a unified method is developed for analysis and design of the following singlecolumn fixed bed processes and corresponding cross-current schemes: (1) batch chromatography, (2) batch chromatography with an integrated solvent removal unit, (3) mixed-recycle steady state recycling chromatography (SSR), and (4) mixed-recycle steady state recycling chromatography with solvent removal from fresh feed, recycle fraction, or column feed (SSR–SR). The method is based on the equilibrium theory of chromatography with an assumption of negligible mass transfer resistance and axial dispersion. The design criteria are given in general, dimensionless form that is formally analogous to that applied widely in the so called triangle theory of counter-current multi-column chromatography. Analytical design equations are derived for binary systems that follow competitive Langmuir adsorption isotherm model. For this purpose, the existing analytic solution of the ideal model of chromatography for binary Langmuir mixtures is completed by deriving missing explicit equations for the height and location of the pure first component shock in the case of a small feed pulse. It is thus shown that the entire chromatographic cycle at the column outlet can be expressed in closed-form. The developed design method allows predicting the feasible range of operating parameters that lead to desired product purities. It can be applied for the calculation of first estimates of optimal operating conditions, the analysis of process robustness, and the early-stage evaluation of different process alternatives. The design method is utilized to analyse the possibility to enhance the performance of conventional SSR chromatography by integrating it with a solvent removal unit. It is shown that the amount of fresh feed processed during a chromatographic cycle and thus the productivity of SSR process can be improved by removing solvent. The maximum solvent removal capacity depends on the location of the solvent removal unit and the physical solvent removal constraints, such as solubility, viscosity, and/or osmotic pressure limits. Usually, the most flexible option is to remove solvent from the column feed. Applicability of the equilibrium design for real, non-ideal separation problems is evaluated by means of numerical simulations. Due to assumption of infinite column efficiency, the developed design method is most applicable for high performance systems where thermodynamic effects are predominant, while significant deviations are observed under highly non-ideal conditions. The findings based on the equilibrium theory are applied to develop a shortcut approach for the design of chromatographic separation processes under strongly non-ideal conditions with significant dispersive effects. The method is based on a simple procedure applied to a single conventional chromatogram. Applicability of the approach for the design of batch and counter-current simulated moving bed processes is evaluated with case studies. It is shown that the shortcut approach works the better the higher the column efficiency and the lower the purity constraints are.

Brain tissue segmentation using q-entropy in multiple sclerosis magnetic resonance images

The loss of brain volume has been used as a marker of tissue destruction and can be used as an index of the progression of neurodegenerative diseases, such as multiple sclerosis. In the present study, we tested a new method for tissue segmentation based on pixel intensity threshold using generalized Tsallis entropy to determine a statistical segmentation parameter for each single class of brain tissue. We compared the performance of this method using a range of different q parameters and found a different optimal q parameter for white matter, gray matter, and cerebrospinal fluid. Our results support the conclusion that the differences in structural correlations and scale invariant similarities present in each tissue class can be accessed by generalized Tsallis entropy, obtaining the intensity limits for these tissue class separations. In order to test this method, we used it for analysis of brain magnetic resonance images of 43 patients and 10 healthy controls matched for gender and age. The values found for the entropic q index were 0.2 for cerebrospinal fluid, 0.1 for white matter and 1.5 for gray matter. With this algorithm, we could detect an annual loss of 0.98% for the patients, in agreement with literature data. Thus, we can conclude that the entropy of Tsallis adds advantages to the process of automatic target segmentation of tissue classes, which had not been demonstrated previously.

Organization of the marketing communication activities after fusion - the integration and the decision making processes

This master’s thesis was made in order to gain answers to the question of how the integration of the marketing communications and the decision making related to it in a geographically dispersed service organization could be improved in a situation where an organization has gone through a merger. The effects of the organizational design dimensions towards the integration of the marketing communications and the decision making related to it was the main focus. A case study as a research strategy offered a perfect frames for an exploratory study and the data collection was conducted by semi-structured interviews and observing. The main finding proved that from the chosen design dimensions, decentralization, coordination and power, could be found specific factors that in a geographically dispersed organization are affecting the integration of the marketing communications negatively. The effects can be seen mostly in the decision making processes, roles and in the division of responsibility, which are affecting the other dimensions and by this, the integration. In a post-merger situation, the coordination dimension and especially the information asymmetry and the information flow seem to have a largest affect towards the integration of the marketing communications. An asymmetric information distribution with the lack of business and marketing education resulted in low self-assurance and at the end in fragmented management and to the inability to set targets and make independent decisions. As conclusions it can be stated, that with the organizational design dimensions can the effects of a merger towards the integration process of the marketing communications to be evaluated.

Fiber-reinforced composite fixed dental prostheses: Studies of the materials used as pontics

Fiber-reinforced composite fixed dental prostheses – Studies of the materials used as pontics University of Turku, Faculty of Medicine, Institute of Dentistry, Department of Biomaterials Science, Finnish Doctoral Program in Oral Sciences – FINDOS, Annales Universitatis Turkuensis, Turku, Finland 2015 Fiber-reinforced composites (FRC), a non-metallic biomaterial, represent a suitable alternative in prosthetic dentistry when used as a component of fixed dental prostheses (FDPs). Some drawbacks have been identified in the clinical performance of FRC restorations, such as delamination of the veneering material and fracture of the pontic. Therefore, the current series of studies were performed to investigate the possibilities of enhancing the mechanical and physical properties of FRC FDPs by improving the materials used as pontics, to then heighten their longevity. Four experiments showed the importance of the pontic design and surface treatment in the performance of FRC FDPs. In the first, the load-bearing capacities of inlay-retained FRC FDPs with pontics of various materials and thicknesses were evaluated. Three different pontic materials were assessed with different FRC framework vertical positioning. Thicker pontics showed increased load-bearing capacities, especially ceramic pontics. A second study was completed investigating the influence of the chemical conditioning of the ridge-lap surface of acrylic resin denture teeth on their bonding to a composite resin. Increased shear bond strength demonstrated the positive influence of the pretreatment of the acrylic surfaces, indicating dissolution of the denture surfaces, and suggesting potential penetration of the monomer systems into the surface of denture teeth. A third study analyzed the penetration depth of different monomer systems on the acrylic resin denture teeth surfaces. The possibility of establishing a durable bond between acrylic pontics and FRC frameworks was demonstrated by the ability of monomers to penetrate the surface of acrylic resin denture teeth, measured by a confocal scanning type microscope. A fourth study was designed to evaluate the load-bearing capacities of FRC FDPs using the findings of the previous three studies. In this case, the performance of pre-shaped acrylic resin denture teeth used as pontics with different composite resins as filling materials was evaluated. The filling material influenced the load-bearing capacities, providing more durable FRC FDPs. It can be concluded that the mechanical and physical properties of FRC FDPs can be improved as has been shown in the development of this thesis. The improvements reported then might provide long lasting prosthetic solutions of this kind, positioning them as potentially permanent rehabilitation treatments. Key words: fiber-reinforced composite, fixed dental prostheses, inlay-retained bridges, adhesion, acrylic resin denture teeth, dental material.

Moisture adsorption characteristics of ginger slices

The moisture adsorption characteristics of dried ginger slices was studied to determine the effect of storage conditions on moisture adsorption for the purpose of shelf life prediction, selection of appropriate packaging materials, evaluate the goodness-of-fit of sorption models, and determine the thermodynamics of moisture adsorption for application in drying. There was a highly significant effect (p < 0.05) of water activity (a w), temperature, and pre-treatment on the equilibrium moisture content (EMC) of the dried ginger slices. At constant a w, the EMC decreased as temperature increased. The EMC of all samples increased as the a w increased at constant temperature. The sorbed moisture of the unpeeled ginger slices was higher than the peeled while those of unblanched samples were higher than the blanched. Henderson equation allows more accurate predictions about the isotherms with the lowest %RMS, and therefore, it describes best the adsorption data followed by GAB, Oswin, and Halsey models in that order. The monolayer moisture generally decreased with temperature for all samples. The isosteric heat decreased with moisture content approaching the asymptotic value or the latent heat of vaporization of pure water (∆Hst = 0) while the entropy of sorption was observed to increase with moisture content.

Production of pizza dough with reduced fermentation time

The aim of this study was to reduce the fermentation time of pizza dough by evaluating the development of the dough during fermentation using a Chopin® rheofermentometer and verifying the influence of time and temperature using a 2² factorial design. The focus was to produce characteristic soft pizza dough with bubbles and crispy edges and soft in the center. These attributes were verified by the Quantitative Descriptive Analysis (QDA). The dough was prepared with the usual ingredients, fermented at a temperature range from 27 to 33 ºC for 30 to 42 minutes, enlarged, added with tomato sauce, baked, and frozen. The influence of the variables time and temperature on the release of carbon dioxide (H'm) was confirmed with positive and significant effect, using a rheofermentometer, which was not observed for the development or maximum height of the dough (Hm). The same fermentation conditions of the experimental design were used for the production of the pizza dough in the industrial process; it was submitted to Quantitative Descriptive Analysis (QDA), in which the samples were described by nine attributes. The results showed that some samples had the desired characteristics of pizza dough, demonstrated by the principal component analysis (PCA), indicating a 30 % fermentation time reduction when compared to the conventional process.

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

Grass-endophyte coevolution and ploidy levels in fescues

ABSTRACT Fescues consist of wild and cultivated grasses that have adapted to a wide range of environmental conditions. They are an excellent model species for evolutionary ecology studies that investigate symbiosis and polyploidization and their effects on plant performance. First, they are frequently infected with symbiotic endophytic fungi known to affect a plant’s ability to cope with biotic and abiotic environmental factors. Second, fescue species have been reported to have substantial intraspecific variation in their ploidy level and morphology. In my thesis, I examined large-scale generalizations for frequency of polyploidy and endophyte infections and their effects on plant morphology. As a model species, I selected red (Festuca rubra) and viviparous sheep’s (F. vivipara) fescues. They are closely related, but they differ in terms of distribution and endophyte infection frequency. I investigated the biogeographic pattern and population biology of 29 red and 12 viviparous sheep’s fescue populations across ≈300 latitudes in Europe (400-690 N). To examine plant ploidy levels, I implemented time- and cost-efficient plate-based high throughput flow cytometric analysis. This efficient procedure enabled me to analyze over 1000 red fescue individuals. I found three ploidy levels among them: overall 84 %, 9 % and 7 % of the red fescue plants were hexaploid, tetraploid and octoploid, respectively. However, all viviparous sheep’s fescue plants were tetraploid. Ploidy level of red fescue appeared to some extent follow gradients in latitude and primary production as suggested by previous studies, but these results could be explained better by taking the sampling design and local adaptation into account. Three Spanish populations were mostly tetraploids and one high elevation population in northernmost Finland (Halti) was octoploid, while most other populations (25 sites) were dominated by hexaploids. Endophyte infection frequencies of wild fescue populations varied from 0 to 81 % in red fescue populations and from 0 to 30 % in viviparous sheep’s fescue populations. No gradients with latitude or primary production of the sites were detected. As taxonomy of red fescues is somewhat unclear, I also studied morphology, ploidy variation and endophyte status of proposed subspecies of European red fescues. Contrary to previous literature, different ploidy levels occurred in the same subspecies. In addition to wild fescues, I also used two agronomically important cultivars of meadow and tall fescue (Schedonorus phoenix and S. pratensis). As grass-legume mixtures have an agronomic advantage over monocultures in meadows, I carried out a mixture/competition experiment with fescues and red clover to find that species composition, nutrient availability and endophyte status together determined the total biomass yield that was higher in mixtures compared to monocultures. The results of this thesis demonstrate the importance of local biotic and abiotic factors such as grazing gradients and habitat types, rather than suggested general global geographical or environmental factors on grass polyploidization or its association with symbiotic endophytic fungi. I conclude that variation in endophyte infection frequencies and ploidy levels of wild fescues support the geographic mosaic theory of coevolution. Historical incidents, e.g., glaciation and present local factors, rather than ploidy or endophyte status, determine fescue morphology.

Developmental patterns of individiuals within a sensory-based learning environment in art education : insights emerging from a case study /

My research permitted me to reexamine my recent evaluations of the Leaf Project given to the Foundation Year students during the fall semester of 1997. My personal description of the drawing curriculum formed part of the matrix of the Foundation Core Studies at the Ontario College of Art and Design. Research was based on the random selection of 1 8 students distributed over six of my teaching groups. The entire process included a representation of all grade levels. The intent of the research was to provide a pattern of alternative insights that could provide a more meaningful method of evaluation for visual learners in an art education setting. Visual methods of learning are indeed complex and involve the interplay of many sensory modalities of input. Using a qualitative method of research analysis, a series of queries were proposed into a structured matrix grid for seeking out possible and emerging patterns of learning. The grid provided for interrelated visual and linguistic analysis with emphasis in reflection and interconnectedness. Sensory-based modes of learning are currently being studied and discussed amongst educators as alternative approaches to learning. As patterns emerged from the research, it became apparent that a paradigm for evaluation would have to be a progressive profile of the learning that would take into account many of the different and evolving learning processes of the individual. A broader review of the student's entire development within the Foundation Year Program would have to have a shared evaluation through a cross section of representative faculty in the program. The results from the research were never intended to be conclusive. We realized from the start that sensory-based learning is a difficult process to evaluate from traditional standards used in education. The potential of such a process of inquiry permits the researcher to ask for a set of queries that might provide for a deeper form of evaluation unique to the students and their related learning environment. Only in this context can qualitative methods be used to profile their learning experiences in an expressive and meaningful manner.

What happens in the first 200 ms of word reading : ERP studies on visual word recognition with top-down and bottom-up approaches /

In this thesis, three main questions were addressed using event-related potentials (ERPs): (1) the timing of lexical semantic access, (2) the influence of "top-down" processes on visual word processing, and (3) the influence of "bottom-up" factors on visual word processing. The timing of lexical semantic access was investigated in two studies using different designs. In Study 1,14 participants completed two tasks: a standard lexical decision (LD) task which required a word/nonword decision to each target stimulus, and a semantically primed version (LS) of it using the same category of words (e.g., animal) within each block following which participants made a category judgment. In Study 2, another 12 participants performed a standard semantic priming task, where target stimulus words (e.g., nurse) could be either semantically related or unrelated to their primes (e.g., doctor, tree) but the order of presentation was randomized. We found evidence in both ERP studies that lexical semantic access might occur early within the first 200 ms (at about 170 ms for Study 1 and at about 160 ms for Study 2). Our results were consistent with more recent ERP and eye-tracking studies and are in contrast with the traditional research focus on the N400 component. "Top-down" processes, such as a person's expectation and strategic decisions, were possible in Study 1 because of the blocked design, but they were not for Study 2 with a randomized design. Comparing results from two studies, we found that visual word processing could be affected by a person's expectation and the effect occurred early at a sensory/perceptual stage: a semantic task effect in the PI component at about 100 ms in the ERP was found in Study 1 , but not in Study 2. Furthermore, we found that such "top-down" influence on visual word processing might be mediated through separate mechanisms depending on whether the stimulus was a word or a nonword. "Bottom-up" factors involve inherent characteristics of particular words, such as bigram frequency (the total frequency of two-letter combinations of a word), word frequency (the frequency of the written form of a word), and neighborhood density (the number of words that can be generated by changing one letter of an original word or nonword). A bigram frequency effect was found when comparing the results from Studies 1 and 2, but it was examined more closely in Study 3. Fourteen participants performed a similar standard lexical decision task but the words and nonwords were selected systematically to provide a greater range in the aforementioned factors. As a result, a total of 18 word conditions were created with 18 nonword conditions matched on neighborhood density and neighborhood frequency. Using multiple regression analyses, we foimd that the PI amplitude was significantly related to bigram frequency for both words and nonwords, consistent with results from Studies 1 and 2. In addition, word frequency and neighborhood frequency were also able to influence the PI amplitude separately for words and for nonwords and there appeared to be a spatial dissociation between the two effects: for words, the word frequency effect in PI was found at the left electrode site; for nonwords, the neighborhood frequency effect in PI was fovind at the right elecfrode site. The implications of otir findings are discussed.

Education in the halls : students' perspectives on cultural expression and resistance

This research is a qualitative study of cultural reproduction and resistance from students' perspectives. Thirteen teenagers (eight in attendance in regular high schools and five drop-outs) were recruited to take part and were involved to varying degrees through interviews, journal writing, and group interactive sessions. A purposive sampling design was used initially to recruit individuals known to the researcher through contacts in an alternate education setting. Other participants were recruited throughout the research phase. The theoretical aspects are premised on the work of Paul Willis, Michel Foucault, and Pierre Bourdieu. The reflexive praxeology of Bourdieu reflects the position taken as one way of understanding how students construct and respond to the situations of cultural dominance they experience in schools. The same reflexivity is offered for suggestions as to how teachers can respond to their own position in the education system.

The effect of motor-encoding activities on memory and performance in a grade one reading program

This study examined the effectiveness of motor-encoding activities on memory and performance of students in a Grade One reading program. There were two experiments in the study. Experiment 1 replicated a study by Eli Saltz and David Dixon (1982). The effect of motoric enactment (Le., pretend play) of sentences on memory for the sentences was investigated. Forty Grade One students performed a "memory-for-sentences" technique, devised by Saltz and Dixon. Only the experimental group used motoric enactment of the sentences. Although quantitative findings revealed no significant difference between the mean scores of the experimental group versus the control group, aspects of the experimental design could have affected the results. It was suggested that Saltz and Dixon's study could be replicated again, with more attention given to variables such as population size, nature of the test sentences, subjects' previous educational experience and conditions related to the testing environment. The second experiment was an application of Saltz and Dixon's theory that motoric imagery should facilitate memory for sentences. The intent was to apply this theory to Grade One students' ability to remember words from their reading program. An experimental gym program was developed using kinesthetic activities to reinforce the skills of the classroom reading program. The same subject group was used in Experiment 2. It was hypothesized that the subjects who experienced the experimental gym program would show greater signs of progress in reading ability, as evidenced by their scores on Form G of the Woodcock Reading Mastery Test--Revised. The data from the WRM--R were analyzed with a 3-way split-plot analysis of variance in which group (experimental vs. control) and sex were the between subjects variables and test-time (pre-test vs. post-test) was the within-subjects variable. Findings revealed the following: (a) both groups made substantial gains over time on the visual-auditory learning sub-test and the triple action of group x sex x time also was significant; (b) children in the experimental and control groups performed similarly on both the pre- and post-test of the letter identification test; (c) time was the only significant effect on subjects' performance on the word identification task; (d) work attack scores showed marked improvement in performance over time for both the experimenta+ and control groups; (e) passage comprehension scores indicated an improvement in performance for both groups over time. Similar to Experiment 1, it is suggested that several modifications in the experimental design could produce significant results. These factors are addressed with suggestions for further research in the area of active learning; more specifically, the effect of motor-encoding activities on memory and academic performance of children.

Sustainability, Fashion Design, and Consumerism: Undergraduate Entry Level Fashion Students' Knowledge, Attitudes, and Habits

This qualitative inquiry explored 7 undergraduate students' attitudes, habits, and knowledge of consumerism, fashion design, and sustainability. The postmodern study employed crystallization as its methodological framework to gain insight into how participants' knowledge is manifested in their daily habits, and used 4 methods of data gathering: semistructured interviews, visual exercises, journal entries, and the researcher's own reflections. Four major themes emerged: Knowledge-Concepts Linked and Fragmented; Dissonance Between Knowledge Versus Attitudes and Consumer Habits; Surrendering to the Unsustainable Structures; Design Process and Caring Attitude. Findings indicate that participants possessed some knowledge of sustainability but lacked a well-rounded understanding of environmental and humanitarian implications of Western consumer society. Findings also reveal a dissonance between participants' knowledge and attitudes-affecting how their knowledge influences their behaviour-and how reflection, creative thinking, and drawing initiate change in participants' underlying attitudes. Recommendations are made to merge a variety of theoretical frameworks into the educational system in order to create curricula that offer a holistic overview and unique insights into sustainability challenges, particularly in specialized areas of the fashion industry.

Synthesis of unnatural analogues of pancratistatin and narciclasine

Described herein is the chemoenzymatic synthesis of several different types of unnatural analogues of Amaryllidaceae constituents. Development and refinement of existing and design and execution of new approaches towards the synthesis of C-1 analogues of pancratistatin and A-ring heterocyclic analogues of narciclasine are discussed. Evaluation of the new analogues as cancer growth inhibitory agents is also described

Rethinking Fiscal Decentralization Policies in Developing Economies: A Case Study of Ghana

This thesis invites geographers to pay more attention to public policy research by addressing the need to rethink fiscal decentralization policies in Ghana. By applying “Simandan’s wise stance in human geography” and “Grix’s building blocks of social research design”, I developed a conceptual framework that unites two incommensurable ontological and epistemological research positions in geography—the positive and normative positions. I used the framework to investigate two key research questions. First, does fiscal decentralization actually work in Ghana? Through quantitative analysis of empirical revenue and expenditure data (1994-2011) of local governments in Ghana, this study reveals significant issues of inefficiency, inequity, and unaccountability. Local governments generate less revenue, and therefore depend largely on central government transfers for developing their jurisdictions. Worse yet, these transfers are highly unpredictable in terms of amount and timing. Even though a multivariate regression analysis revealed that these transfers are apolitical, the actual disbursement formula tends to focus on equality instead of equity. Additionally, the unclear expenditure assignments in each locality make accountability difficult. In view of these problems, I addressed the question: why is fiscal decentralization held out as a good thing in Ghana? By drawing lessons from Foucault’s and Escobar’s critical discourse analysis, I traced a genealogy of Ghana’s fiscal decentralization. I found that the policy is held out as a good thing in Ghana because of the triangular operation of multiplicities of power, knowledge, and truth regimes at the local, national and international scale. I concluded that although nation-states remains a necessary causal link in fiscal decentralization policy process in Ghana, direct and indirect international involvement have profound effect on these policies. Therefore, rethinking fiscal decentralization involves acknowledging the complex intermingling effects that global, national, and local territories produce.