Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Prodrug strategies of antiviral nucleotides: Studies on enzymatically and thermally removable phosphate protecting groups

Antiviral nucleosides are compounds that are used against viruses, such as human immunodeficiency virus (HIV) and hepatitis C virus (HCV). To act as therapeutic agent, the antiviral nucleoside needs to be phosphorylated to nucleotide in the body in three consecutive phosphorylation steps by cellular or viral enzymes. The first phosphorylation to the nucleoside monophosphate is often inefficient and leads to poor antiviral activity. The antiviral efficacy can be improved by applying a prodrug strategy and delivering the antiviral nucleoside directly as its monophosphate. In prodrug strategies of antiviral nucleotides, the negative charges on the phosphate moiety are temporarily masked with protecting groups. Once inside the cell, the protecting groups are removed by enzymatic or chemical processes. Many prodrug strategies apply biodegradable protecting groups, the removal of which is triggered by esterase enzymes. Several studies have, however, demonstrated that the removal rate of the second and subsequent esterase labile protecting groups significantly slows down after the first protecting group is removed due to the negative charge on the phosphodiester intermediate, which disturbs the catalytic site of the enzyme. In this thesis, esterase labile protecting group strategies where the issue of retardation could be avoided were studied. Prodrug candidates of antiviral nucleotides were synthesized and kinetic studies on the chemical and enzymatic stability were carried out. In the synthesized compounds, the second protecting group is cleaved from the monophosphate some other mechanism than esterase triggered activation or the structure of prodrug requires only one protecting group. In addition, esterase labile protecting group which is additionally thermally removable was studied. This protecting group was cleaved from oligomeric phosphodiesters both enzymatically and thermally and seems most attractive of the studied phosphate protecting groups. However, the rate of the thermal removal still is too slow to allow efficient protection of longer oligonucleotides and needs optimization. Key words: antiviral, nucleotide, prodrug, protecting group, biodegradable

Bio and chemocatalysis for stereo and regioselective one-pot reaction applications

The development of cost efficient, selective and sustainable chemical processes for production of chiral building blocks is of great importance in synthetic and industrial organic chemistry. One way to reach these objectives is to carry out several reactions steps in one vessel at one time. Furthermore, when this kind of one-pot multi step reactions are catalyzed by heterogeneous chemo- and bio-catalysts, which can be separated from the reaction products by filtration, practical access to chiral small molecules for further utilization can be obtained. The initial reactions studied in this thesis are the two step dynamic kinetic resolution of rac-2-hydroxy-1-indanone and the regioselective hydrogenation of 1,2-indanedione. These reactions are then combined in a new heterogeneously catalyzed one-pot reaction sequence enabling simple recovery of the catalysts by filtration, facilitating simple reaction product isolation. Conclusively, the readily available 1,2-indanedione is by the presented one-pot sequence, utilizing heterogeneous enzyme and transition metal based catalysts, transferred with high regio- and stereoselectivity to a useful chiral vicinal hydroxyl ketone structure. Additional and complementary investigation of homogeneous half-sandwich ruthenium complexes for catalyzing the epimerization of chiral secondary alcohols of five natural products containing additional non-functionalized stereocenters was conducted. In principle, this kind of epimerization reactions of single stereocenters could be utilized for converting inexpensive starting materials, containing other stereogenic centers, into diastereomeric mixtures from which more valuable compounds can be isolated by traditional isolation techniques.

Analysis of Phase Separator Design Criteria Using Computational Fluid Dynamics

Gravitational phase separation is a common unit operation found in most large-scale chemical processes. The need for phase separation can arise e.g. from product purification or protection of downstream equipment. In gravitational phase separation, the phases separate without the application of an external force. This is achieved in vessels where the flow velocity is lowered substantially compared to pipe flow. If the velocity is low enough, the denser phase settles towards the bottom of the vessel while the lighter phase rises. To find optimal configurations for gravitational phase separator vessels, several different geometrical and internal design features were evaluated based on simulations using OpenFOAM computational fluid dynamics (CFD) software. The studied features included inlet distributors, vessel dimensions, demister configurations and gas phase outlet configurations. Simulations were conducted as single phase steady state calculations. For comparison, additional simulations were performed as dynamic single and two-phase calculations. The steady state single phase calculations provided indications on preferred configurations for most above mentioned features. The results of the dynamic simulations supported the utilization of the computationally faster steady state model as a practical engineering tool. However, the two-phase model provides more truthful results especially with flows where a single phase does not determine the flow characteristics.

Effects of different packaging techniques on the microbiological and physicochemical properties of coated pumpkin slices

Abstract In this study the effects of zein film coating along with benzoic acid on the quality of sliced pumpkin samples, which were packaged with different techniques were investigated. The samples were allocated into different groups and were treated with different processes. Following processing, the samples were stored at +4 °C for twenty days. Physicochemical and microbiological analyses were carried out on the samples once every five days during the storage period. According to color analysis, the L* value was observed to have significantly decreased in the processed and packaged samples in comparison with the control group. Besides, a* and b* values increased in all groups. It was determined that zein film alone did not exhibit the expected effectiveness against moisture loss in the samples. According to the results of microbiological analysis, a final decrease at approximately 1.00 log level was determined in total count of mesophilic aerobic bacteria (TMAB) in the group which was vacuum packaged in PVDC with zein coating when compared with the initial TMAB. Furthermore, no molding occurred in zein-coated group on the last day of the storage period, while massive mold growth was noted in the group which was packaged without any pretreatment procedure.

Modelling the simultaneous effects of intellectual capital and knowledge management on the organisational performance of Finnish companies

The aim of this study was to contribute to the current knowledge-based theory by focusing on a research gap that exists in the empirically proven determination of the simultaneous but differentiable effects of intellectual capital (IC) assets and knowledge management (KM) practices on organisational performance (OP). The analysis was built on the past research and theoreticised interactions between the latent constructs specified using the survey-based items that were measured from a sample of Finnish companies for IC and KM and the dependent construct for OP determined using information available from financial databases. Two widely used and commonly recommended measures in the literature on management science, i.e. the return on total assets (ROA) and the return on equity (ROE), were calculated for OP. Thus the investigation of the relationship between IC and KM impacting OP in relation to the hypotheses founded was possible to conduct using objectively derived performance indicators. Using financial OP measures also strengthened the dynamic features of data needed in analysing simultaneous and causal dependences between the modelled constructs specified using structural path models. The estimates were obtained for the parameters of structural path models using a partial least squares-based regression estimator. Results showed that the path dependencies between IC and OP or KM and OP were always insignificant when analysed separate to any other interactions or indirect effects caused by simultaneous modelling and regardless of the OP measure used that was either ROA or ROE. The dependency between the constructs for KM and IC appeared to be very strong and was always significant when modelled simultaneously with other possible interactions between the constructs and using either ROA or ROE to define OP. This study, however, did not find statistically unambiguous evidence for proving the hypothesised causal mediation effects suggesting, for instance, that the effects of KM practices on OP are mediated by the IC assets. Due to the fact that some indication about the fluctuations of causal effects was assessed, it was concluded that further studies are needed for verifying the fundamental and likely hidden causal effects between the constructs of interest. Therefore, it was also recommended that complementary modelling and data processing measures be conducted for elucidating whether the mediation effects occur between IC, KM and OP, the verification of which requires further investigations of measured items and can be build on the findings of this study.

Path Analysis of Online Users Using Clickstream Da-ta: Case Online Magazine Website

This paper explores behavioral patterns of web users on an online magazine web-site. The goal of the study is to first find and visualize user paths within the data generated during collection, and to identify some generic behavioral typologies of user behavior. To form a theoretical foundation for processing data and identifying behavioral ar-chetypes, the study relies on established consumer behavior literature to propose typologies of behavior. For data processing, the study utilizes methodologies of ap-plied cluster analysis and sequential path analysis. Utilizing a dataset of click stream data generated from the real-life clicks of 250 ran-domly selected website visitors over a period of six weeks. Based on the data collect-ed, an exploratory method is followed in order to find and visualize generally occur-ring paths of users on the website. Six distinct behavioral typologies were recog-nized, with the dominant user consuming mainly blog content, as opposed to editori-al content. Most importantly, it was observed that approximately 80% of clicks were of the blog content category, meaning that the majority of web traffic occurring in the site takes place in content other than the desired editorial content pages. The out-come of the study is a set of managerial recommendations for each identified behavioral archetype.

Big Datan liiketoiminnalliset mahdollisuudet ja haasteet

Tämän kandidaatintutkielman tarkoituksena oli selvittää minkälaisia liiketoiminnallisia mahdollisuuksia ja haasteita Big Dataan ja sen ominaispiirteisiin liittyy, ja miten Big Data määritellään nykyaikaisesti ja ajankohtaisesti. Tutkimusongelmaa lähestyttiin narratiivisen kirjallisuuskatsauksen keinoin. Toisin sanoen tutkielma on hajanaisen tiedon avulla koostettu yhtenäinen katsaus nykytilanteeseen. Lähdeaineisto koostuu pääosin tieteellisistä artikkeleista, mutta käytössä oli myös oppikirjamateriaalia, konferenssijulkaisuja ja uutisartikkeleja. Tutkimuksessa käytetyt akateemisen kirjallisuuden lähteet sisälsivät keskenään paljon samankaltaisia näkemyksiä tutkimusaihetta kohtaan. Niiden perusteella muodostettiin kaksi taulukkoa havaituista mahdollisuuksista ja haasteista, ja taulukoiden rivit nimettiin niitä kuvaavien ominaispiirteiden mukaan. Tutkimuksessa liiketoiminnalliset mahdollisuudet ja haasteet jaettiin viiteen pääkategoriaan ja neljään alakategoriaan. Tutkimus toteutettiin liiketoiminnan näkökulmasta, joten siinä sivuutettiin monenlaisia Big Datan teknisiä aspekteja. Tutkielman luonne on poikkitieteellinen, ja sen avulla pyritään havainnoimaan tämän hetken yhtä uusinta tietojenkäsittelykäsittelytieteiden termiä liiketoiminnallisessa kontekstissa. Tutkielmassa Big Dataan liittyvillä ominaispiirteillä todettiin olevan mahdollisuuksia, jotka voitiin jaotella korrelaatioiden havaitsemisen perusteella markkinoiden tarkemman segmentoinnin mahdollisuuksiin ja päätöksenteon tukena toimimiseen. Reaaliaikaisen seurannan mahdollisuudet perustuvat Big Datan nopeuteen ja kokoon, eli sen jatkuvaan kasvuun. Ominaispiirteisiin liittyvät haasteet voidaan jakaa viiteen kategoriaan, joista osa liittyy toimintaympäristöön ja osa organisaation sisäiseen toimintaan.

The nature of the highly artistic student in visual arts at secondary school /

This qualitative investigation examined the nature of 7 highly artistic visual arts students at 2 secondary schools in southcentral Ontario. Through interviews, questionnaires, observations, and artwork documents, this study attempted to understand these highly artistic students in terms of creativity, motivation, social and emotional perspectives, and cognitive processes. Data collection occuned over a 3-monlh period. and the data analysis program NVivo 7 was used for coding to develop themes and categories for organizing data. The findings of this study illustrate the significant place that \ isual arts can lake in the growth and development for the youth of today. Participants idcniificd dcxclopnig critical thinking and problem-solving skills, taking risks, and meeting challenges ilirouuh their engagement in the creative process. The transferability of these skills \\ as referenced to numerous aspects of their lives. By enhancing individual perspectives through the study of visual arts, their local and world connections were extended, and environmental and societal concerns evolved. In addition, the communicative opportunities that visual arts provided for these students in terms of personal expression provided emotional health and paths of personal discovery. Through the participants' production of artwork with the many stages this involves, combined with insight into their needs, the participants relayed miportant suggestions for programming enhancements and educational settmgs lor \ isiial arts classrooms. These suggestions are meaningful for educators and curriculum developers of the future.

Implementation of hospital-wide computer information system :a case study of this change process

This case study examines the impact of a computer information system as it was being implemented in one Ontario hospital. The attitudes of a cross section of the hospital staff acted as a barometer to measure their perceptions of the implementation process. With The Mississauga Hospital in the early stages of an extensive computer implementation project, the opportunity existed to identify staff attitudes about the computer system, overall knowledge and compare the findings with the literature. The goal of the study was to develop a greater base about the affective domain in the relationship between people and the computer system. Eight exploratory questions shaped the focus of the investigation. Data were collected from three sources: a survey questionnaire, focused interviews, and internal hospital documents. Both quantitative and qualitative data were analyzed. Instrumentation in the study consisted of a survey distributed at two points in time to randomly selected hospital employees who represented all staff levels.Other sources of data included hospital documents, and twenty-five focused interviews with staff who replied to both surveys. Leavitt's socio-technical system, with its four subsystems: task, structure, technology, and people was used to classify staff responses to the research questions. The study findings revealed that the majority of respondents felt positive about using the computer as part of their jobs. No apparent correlations were found between sex, age, or staff group and feelings about using the computer. Differences in attitudes, and attitude changes were found in potential relationship to the element of time. Another difference was found in staff group and perception of being involved in the decision making process. These findings and other evidence about the role of change agents in this change process help to emphasize that planning change is one thing, managing the transition is another.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3

Nurses' attitudes toward computers before and two months after training

This study examined nurses' attitudes toward computers before training and 2 months after training. A quantitative approach and a nonexperimental survey design were used in this study. Stronge and Brodt's (1985) instrument, Nurses' Attitudes Toward Computerization Questionnaire, was used to assess 27 nurses' attitudes prior to and 2 months after computer training. Demographic variables also were collected on the questionnaires. The results of this study showed that, overall, nurses had positive attitudes towards computers in both questionnaires. The results of the first questionnaire were consistent with other studies. There were no studies that involved a follow-up questionnaire using Stronge and Brodt's (1985) instrument. Attitude scores of Questionnaire 2 were higher than attitude scores of Questionnaire 1. More time for nursing tasks, less time for quality patient care, and threat to job security questions were found to be statistically significant. This study found no statistical significance between attitudes and demographic variables. Younger nurses a~d nurses with fewer years of computer experience were most likely to exhibit positive attitudes. Implications for practice and future research were discussed. Some limitations were identified and discussed.

Development and characterization of concentric capillary nebulizer used in inductively coupled plasma analysis /

A simple, low-cost concentric capillary nebulizer (CCN) was developed and evaluated for ICP spectrometry. The CCN could be operated at sample uptake rates of 0.050-1.00 ml min'^ and under oscillating and non-oscillating conditions. Aerosol characteristics for the CCN were studied using a laser Fraunhofter diffraction analyzer. Solvent transport efficiencies and transport rates, detection limits, and short- and long-term stabilities were evaluated for the CCN with a modified cyclonic spray chamber at different sample uptake rates. The Mg II (280.2nm)/l\/lg 1(285.2nm) ratio was used for matrix effect studies. Results were compared to those with conventional nebulizers, a cross-flow nebulizer with a Scott-type spray chamber, a GemCone nebulizer with a cyclonic spray chamber, and a Meinhard TR-30-K3 concentric nebulizer with a cyclonic spray chamber. Transport efficiencies of up to 57% were obtained for the CCN. For the elements tested, short- and long-term precisions and detection limits obtained with the CCN at 0.050-0.500 ml min'^ are similar to, or better than, those obtained on the same instrument using the conventional nebulizers (at 1.0 ml min'^). The depressive and enhancement effects of easily ionizable element Na, sulfuric acid, and dodecylamine surfactant on analyte signals with the CCN are similar to, or better than, those obtained with the conventional nebulizers. However, capillary clog was observed when the sample solution with high dissolved solids was nebulized for more than 40 min. The effects of data acquisition and data processing on detection limits were studied using inductively coupled plasma-atomic emission spectrometry. The study examined the effects of different detection limit approaches, the effects of data integration modes, the effects of regression modes, the effects of the standard concentration range and the number of standards, the effects of sample uptake rate, and the effect of Integration time. All the experiments followed the same protocols. Three detection limit approaches were examined, lUPAC method, the residual standard deviation (RSD), and the signal-to-background ratio and relative standard deviation of the background (SBR-RSDB). The study demonstrated that the different approaches, the integration modes, the regression methods, and the sample uptake rates can have an effect on detection limits. The study also showed that the different approaches give different detection limits and some methods (for example, RSD) are susceptible to the quality of calibration curves. Multicomponents spectral fitting (MSF) gave the best results among these three integration modes, peak height, peak area, and MSF. Weighted least squares method showed the ability to obtain better quality calibration curves. Although an effect of the number of standards on detection limits was not observed, multiple standards are recommended because they provide more reliable calibration curves. An increase of sample uptake rate and integration time could improve detection limits. However, an improvement with increased integration time on detection limits was not observed because the auto integration mode was used.

Sex Talk: A Multiple Case Study to Explore and Understand Parent-Child Sexual Health Communication in Chinese Immigrant Families

Parent-child sexual health communication can be beneficial. Many factors affect such communication in Chinese immigrant families. This qualitative study explored the influences of acculturation, parenting, and parental participation in the Raising Sexually Healthy Children Program (RSHC) on such communication. With a hermeneutic framework, the purpose was to develop understanding based on the topic, context, and researcher interpretations. Twelve interviews elicited data from six parent-child dyads, three from the RSHC. Analysis involved coding processes; data were compared repeatedly and organized into themes. Perceived personality differences between generations were confounded with cultural communicative differences. Parents used implicitness observed in Chinese culture to establish "open" communication; children expected explicitness observed in Western culture. Post- RSHC, parents perceived themselves as more open to talking about sex; children did not perceive such parental changes. Future research should include joint interviews and longitudinal program evaluation. Future practice should focus on cross-cultural communication and involving children in RSHC.

Automatic evolution of conceptual building architectures

This thesis describes research in which genetic programming is used to automatically evolve shape grammars that construct three dimensional models of possible external building architectures. A completely automated fitness function is used, which evaluates the three dimensional building models according to different geometric properties such as surface normals, height, building footprint, and more. In order to evaluate the buildings on the different criteria, a multi-objective fitness function is used. The results obtained from the automated system were successful in satisfying the multiple objective criteria as well as creating interesting and unique designs that a human-aided system might not discover. In this study of evolutionary design, the architectures created are not meant to be fully functional and structurally sound blueprints for constructing a building, but are meant to be inspirational ideas for possible architectural designs. The evolved models are applicable for today's architectural industries as well as in the video game and movie industries. Many new avenues for future work have also been discovered and highlighted.