Enzymatic Synthesis, Recovery, and Purification of Ethyl β-ᴅ-glucopyranoside

A method to synthesize ethyl β-ᴅ-glucopyranoside (BEG) was searched. Feasibility of different ion exchange resins was examined to purify the product from the synthetic binary solution of BEG and glucose. The target was to produce at least 50 grams of 99 % pure BEG with a scaled up process. Another target was to transfer the batch process into steady-state recycle chromatography process (SSR). BEG was synthesized enzymatically with reverse hydrolysis utilizing β-glucosidase as a catalyst. 65 % of glucose reacted with ethanol into BEG during the synthesis. Different ion exchanger based resins were examined to separate BEG from glucose. Based on batch chromatography experiments the best adsorbent was chosen between styrene based strong acid cation exchange resins (SAC) and acryl based weak acid cation exchange resins (WAC). CA10GC WAC resin in Na+ form was chosen for the further separation studies. To produce greater amounts of the product the batch process was scaled up. The adsorption isotherms for the components were linear. The target purity was possible to reach already in batch without recycle with flowrate and injection size small enough. 99 % pure product was produced with scaled-up batch process. Batch process was transferred to SSR process utilizing the data from design pulse chromatograms and Matlab simulations. The optimal operating conditions for the system were determined. Batch and SSR separation results were compared and by using SSR 98 % pure products were gained with 40 % higher productivity and 40 % lower eluent consumption compared to batch process producing as pure products.

The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

Screening and kinetics of glutaminase and glutamate decarboxylase producing lactic acid bacteria from fermented Thai foods

L-glutaminase and glutamic acid decarboxylase (GAD) catalyzes the hydrolysis of L-glutamine and glutamate, respectively. L-glutaminase widely used in cancer therapy along with a combination of other enzymes and most importantly these enzymes were used in food industries, as a major catalyst of bioconversion. The current investigation was aimed to screen and select L-glutaminase, and GAD producing lactic acid bacteria (LAB). A total of 338 LAB were isolated from fermented meat, fermented fish, fermented soya bean, fermented vegetables and fruits. Among 338 isolates, 22 and 237 LAB has been found to be positive for L-glutaminase and GAD, respectively. We found that 30 days of incubation at 35 ºC and pH 6.0 was the optimum condition for glutaminase activity by G507/1. G254/2 was found to be the best for GAD activity with the optimum condition of pH 6.5, temperature 40 ºC and ten days of incubation. These LAB strains, G507/1 and G254/2, were identified as close relative of Lactobacillus brevis ATCC 14869 and Lactobacillus fermentum NBRC 3956, respectively by 16S rRNA sequencing. Further, improvements in up-stream of the fermentation process with these LAB strains are currently under development.

Trust Embedded Open Innovation: Human-Centricity in the Financial

Globalization and interconnectedness in the worldwide sphere have changed the existing and prevailing modus operandi of organizations around the globe and have challenged existing practices along with the business as usual mindset. There are no rules in terms of creating a competitive advantage and positioning within an unstable, constantly changing and volatile globalized business environment. The financial industry, the locomotive or the flagship industry of global economy, especially, within the aftermath of the financial crisis, has reached a certain point trying to recover and redefine its strategic orientation and positioning within the global business arena. Innovation has always been a trend and a buzzword and by many has been considered as the ultimate answer to any kind of problem. The mantra Innovate or Die has been prevailing in any organizational entity in a, sometimes, ruthless endeavour to develop cutting-edge products and services and capture a landmark position in the market. The emerging shift from a closed to an open innovation paradigm has been considered as new operational mechanism within the management and leadership of the company of the future. To that respect, open innovation has been experiencing a tremendous growth research trajectory by putting forward a new way of exchanging and using surplus knowledge in order to sustain innovation within organizations and in the level of industry. In the abovementioned reality, there seems to be something missing: the human element. This research, by going beyond the traditional narratives for open innovation, aims at making an innovative theoretical and managerial contribution developed and grounded on the on-going discussion regarding the individual and organizational barriers to open innovation within the financial industry. By functioning across disciplines and researching out to primary data, it debunks the myth that open innovation is solely a knowledge inflow and outflow mechanism and sheds light to the understanding on the why and the how organizational open innovation works by enlightening the broader dynamics and underlying principles of this fascinating paradigm. Little attention has been given to the role of the human element, the foundational pre-requisite of trust encapsulated within the precise and fundamental nature of organizing for open innovation, the organizational capabilities, the individual profiles of open innovation leaders, the definition of open innovation in the realms of the financial industry, the strategic intent of the financial industry and the need for nurturing a societal impact for human development. To that respect, this research introduces the trust-embedded approach to open innovation as a new insightful way of organizing for open innovation. It unveils the peculiarities of the corporate and individual spheres that act as a catalyst towards the creation of productive open innovation activities. The incentive of this research captures the fundamental question revolving around the need for financial institutions to recognise the importance for organizing for open innovation. The overarching question is why and how to create a corporate culture of openness in the financial industry, an organizational environment that can help open innovation excel. This research shares novel and cutting edge outcomes and propositions both under the prism of theory and practice. The trust-embedded open innovation paradigm captures the norms and narratives around the way of leading open innovation within the 21st century by cultivating a human-centricity mindset that leads to the creation of human organizations, leaving behind the dehumanization mindset currently prevailing within the financial industry.

Qualidade sanitária de sementes de aveia-preta (Avena strigosa Schreb.) produzidas no estado do Rio Grande do Sul, safra 1999/2000

Este trabalho teve como objetivo avaliar a qualidade sanitária de sementes de aveia-preta (Avena strigosa Schreb.) produzidas no Estado do Rio Grande do Sul. Foram avaliados 81 lotes de sementes oriundos de 16 municípios de diferentes regiões fisiográficas. Utilizou-se o método do substrato papel, com 400 sementes por lote. Foram detectados os fungos Alternaria sp., Chaetomium sp.,Cladosporium sp., Colletotrichum sp., Curvularia sp., Epicoccum sp., Nigrospora sp., Colletotrichum sp., Fusarium sp. e os fungos de armazenamento Aspergillus sp.e Penicillium sp.A maior incidência média foi dos fungos Phoma sp.e Bipolaris spp., com 18,4 e 22,4% respectivamente. Pode-se concluir que deve haver um melhor manejo da cultura da aveia-preta, visando diminuir a contaminação das sementes por fungos, principalmente, nas regiões típicas produtoras de cereais de inverno.

Perfluorattuja yhdisteitä sisältävien jätevesien puhdistus- ja analyysimenetelmät

Perfluoratut alkyyliyhdisteet eli PFAS-yhdisteet ovat synteettisiä orgaanisia yhdisteitä, joissa on fluorattu hiiliketju. Hiilen ja fluorin väliset vahvat sidokset ovat muodostuneet ongelmaksi jätevedenpuhdistamoilla, sillä yhdisteet eivät hajoa puhdistamoilla käytössä olevilla vedenpuhdistusmenetelmillä. Yhdisteitä kertyy luontoon jätevesien mukana. Kandidaatintyössä on vertailtu yhdisteitä sisältävien vesien käsittelymenetelmiä parhaiten soveltuvan menetelmän löytämiseksi. Menetelmien kustannuksia tai soveltuvuutta vedenpuhdistamomittakaavan prosessiksi ei ole arvioitu. Lisäksi työssä on koottu yhdisteitä sisältävien jätevesien analysointiin sopivia analyysimenetelmiä. Soveltuvat puhdistus- ja analyysimenetelmät on esitelty uusien tieteellisten artikkelien pohjalta. Mahdollisia erotusmenetelmiä ovat membraanierotus ja sorptio. Membraaneista soveltuvimpia ovat nanosuodatus- ja käänteisosmoosimembraanit, joilla erottuvat jopa 0,0001 μm:n kokoiset partikkelit. PFAS-yhdisteet voidaan erottaa sorptiolla muun muassa aktiivihiileen. Yhdisteiden rakenne hajoaa nykyaikaisilla hapetusmenetelmillä ja polttamalla lietteen mukana. Hapettaminen permanganaatin avulla ei tuottanut hyvää tulosta, mutta fotokemiallisella hapetuksella ja alhaisen lämpötilan plasmatekniikalla (NTP) yhdisteiden rakenne hajosi lähes kokonaan. Fotokemiallinen hapetus onnistui erityisesti perfluorokarboksyylihapoilla, joiden rakenne hajosi jopa kolmessa tunnissa. Yleisimmin käytetty analyysimenetelmä on nestekromatografin ja massaspektrometrin yhdistelmä (LC-MS/MS) ja matriisivaikutus minimoidaan tyypillisesti kiinteäfaasiuutolla (SPE). Työssä esitellyistä käsittelymenetelmistä parhaiten soveltuva on NTP-menetelmä, koska sillä saatiin tutkimusten mukaan hajotettua yhdisteiden rakenne muita menetelmiä lyhyemmässä ajassa ja se soveltuu parhaiten kaikille PFAS-yhdisteille. NTP-menetelmässä ei tarvita katalyyttiä tai lisäkemikaaleja. Voimakkaana hapettimena toimivat epästabiilit hydroksyyliradikaalit, jotka syntyvät koronapurkauksen kautta. Koronapurkauksessa muodostuu myös otsonia ja lisäksi vapaa happi voi tehostaa hapettumista. Menetelmässä muodostuvien hajoamistuotteiden hallinta vaatii lisätutkimusta. Mahdollinen hallintakeino voisi olla esimerkiksi hapettumisessa vapautuvien fluoridi-ionien saostaminen. Muodostuvien hajoamistuotteiden toksisuutta voitaisiin tarkkailla biosensorilla.

Neopentyyliglykolin ja propionihapon välisen esteröintireaktion kinetiikka

Glykolien esterit ovat haluttuja pintareaktiivisia aineita. Niitä voidaan valmistaa esteröintireaktiolla karboksyylihappojen kanssa katalyytin läsnä ollessa, jolloin toivottu reaktiotuote on yleensä muodostuva monoesteri. Monoesterin saannon lisäämiseksi reaktiossa muodostuvaa vettä voidaan poistaa jatkuvasti reaktiosta. Reaktion tasapainotilan tutkiminen on kuitenkin tärkeää, jotta reaktion kinetiikka tunnettaisiin mahdollisimman hyvin. Tällöin reaktiotuotteita ei poisteta reaktioseoksesta reaktion aikana. Glykolit esteröityvät happojen kanssa kahdessa vaiheessa. Ensimmäisessä vaiheessa muodostuu monoesteriä ja vettä ja toisessa vaiheessa diesteriä ja vettä. Kokeiden perusteella ensimmäinen vaihe on selvästi toista vaihetta nopeampi reaktio. Kirjallisuudessa on esitetty myös kaksi sivureaktiota, transesteröityminen ja disproportionaatio. Reaktion kinetiikka voidaan kuvata ilman näitä pieniä sivureaktiota, mutta täydellisen kuvaamisen vuoksi on ne myös otettava huomioon. Reaktion kinetiikan tutkimiseksi suoritettiin viisi laboratoriokoetta eri lämpötiloissa neopentyyliglykolilla ja propionihapolla homogeenisen para-tolueenisulfonihapon toimiessa katalyyttina. Lähtöaineiden ja tuotteiden konsentraatioita seurattiin ajan funktiona ja saatujen tulosten perusteella sovitettiin reaktiomekanismin differentiaaliyhtälöiden reaktionopeusvakiot. Nopeusvakioiden lämpötilariippuvuutta tutkittiin Arrheniuksen yhtälön avulla. Lisäksi määritettiin tasapainovakiot kullekin osareaktiolle.

A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

Green diesel synthesis by hydrodeoxygenation of lipids extracted from Chlorella algae in supercritical hexane

Lipids were extracted from Chlorella algae with supercritical hexane. The high lipids yield of approximately 10% was obtained at optimum conditions of 300 rpm stirring speed and 2 h duration compared to the total contents of lipids being 12%. Furthermore, an easiness of hexane recovery may be considered as economically and ecologically attractive. For the first time, in the current work catalytic hydrodeoxygenation (HDO) of Chlorella algal lipids was studied over 5 wt% Ni/H-Y-80 and 5 wt% Ni/SiO2 at 300 C and under 30 bar total pressure in H2. A comparative HDO of stearic acid was carried out under similar conditions. The conversion of lipids was about 35% over 5 wt% Ni/H-Y-80 after 6h, whereas, 5 wt% Ni/SiO2 was totally deactivated after 60 min. The selectivity to hydrocarbons (C15-C18) is 6%. As a comparison, complete conversion of stearic acid over 5 wt% Ni/H-Y-80 was achieved in 6 h. The transformation of lipids proceeded mostly via hydrogenation and hydrolysis with formation of free fatty acid (FFA). The lower activity might be attributed to deactivation of catalysts caused by chlorophylls and carotenoids. Even though the conversion is low, future studies in HDO of lipids extracted from other algae species having higher lipid content could be proposed. Coke resistant catalyst might be considered to improve catalytic activity.

Perceived learning needs in staff development of some care providers in five long-term care settings in Southern Ontario /

This exploratory descriptive study described what 20 care providers in 5 long-term care facilities perceived to aid or hinder their learning in a work-sponsored learning experience. A Critical Incident Technique (Woolsey, 1986) was the catalyst for the interviews with the culturally and professionally diverse participants. Through data analysis, as described by Moustakas (1994), I found that (a) humour, (b) the learning environment, (c) specific characteristics of the presenter such as moderate pacing, speaking slowly and with simple words, (d) decision-making authority, (e) relevance to practice, and (f) practical applications best met the study participants' learning needs. Conversely, other factors could hinder learning based on the participants' perceptions. These were: (a) other presenter characteristics such as a program that was delivered quickly or spoken at a level above the participants' comprehension, (b) no perceived relevance to practice, (c), other environmental situations, and (d) the timing of the learning session. One of my intentions was to identify the emic view among cultural groups and professional/vocational affiliations. A surprising finding of this study was that neither impacted noticeably on the perceived learning needs of the participants. Further research with a revised research design to facilitate inclusion of more diverse participants will aid in determining if the lack of a difference was unique to this sample or more generalizable on a case-to-case transfer basis to the study population.

Exploring the personal and professional lives of teachers in the search for authenticity /

"We teach who we are" (Palmer, 1998, p. 2). This simple, yet profound, statement was the catalyst that began my thesis journey. Using a combination of self-study and participant narratives, Palmer's idea was explored as search for authenticity. The self-study component of this narrative was enhanced by the stories of two other teachers, both women. I chose to use narrative methodology to uncover and discover the relationship between the personal and professional lives of being a teacher. Do teachers express themselves daily in their classrooms? Do any lessons from the classroom translate into teachers' personal lives? The themes of reflection, authenticity, truth, and professional development thread themselves throughout this narrative study. In order to be true to myself as a teacher/researcher, arts-based interpretations accompany my own and each participant's profile. Our conversations about our pasts, our growth as teachers and journeys as individuals were captured in poetry and photographic mosaics. Through rich and detailed stories we explored who we are as teachers and how we became this way. The symbiotic relationship between our personal and professional lives was illustrated by tales of bravery, self-discovery, and reflection. The revelations uncovered illustrate the powerful role our past plays in shaping the present and potentially the friture. It may seem indulgent to spend time exploring who we are as teachers in a time that is increasingly focused on improving student test scores. Yet, the truth remains that, "Knowing myself is as crucial to good teaching as knowing my students and my subject" (Palmer, 1998, p. 2).

Kinetic studies of the effect of organic sulphides on the oxidation of other sulphides /

The rates of oxidation of three Organic sulphides viz. methyl phenyl sulphide, (P), p -me thoxyphenyl methyl sulphide (M) and methyl p-nitrophenyl sulphide (N). have been obtained in ethanol using MoO-(acac)- as catalyst and Bu OOH as the oxidizing agent. A Hammett plot gave a rho value of -2.1 and the activation energies for the oxidation of P, M and N were estimated to be 63.60, 40.12 and 197.46 Kj mol respectively. The effect of organic sulphide on the oxidation of another sulphide was also ascertained. Positive and negative deviations were observed from the expected slope.

A narrative journey of teacher reflexivity and authenticity in technological environments /

This qualitative narrative inquiry was driven by my desire to further explore my personal discovery that my utilization of educational technologies in teaching and learning environments seemed to heighten a sense of creativity, which in turn increased reflective practice and authenticity in my teaching. A narrative inquiry approach was used as it offered the opportunity to uncover the deeper meanings of authenticity and reflection as participants' personal experiences were coconstructed and reconstructed in relationship with me and in relationship to a social milieu. To gain further insight into this potential phenomenon, I engaged in 2 conversational interviews with 2 other teachers from an Ontario College in a large urban centre who have utilized educational technologies in their teaching and learning communities and I maintained a research journal, constructed during the interview process, to record my own emerging narrative accounts, reflections, insights and further questions. The field texts consisted of transcriptions of the interviews and my reflective journal. Research texts were developed as field texts were listened to multiple times and texts were examined for meanings and themes. The educational technologies that both women focused on in the interview were digital video of children as they play, learn and develop and the use of an audible teacher voice in online courses. The invitation given to students to explore and discover meaning in videos of children as they watched them with the teacher seemed to be a catalyst for authenticity and a sense of synergy in the classroom. The power of the audible teacher voice came through as an essential component in online learning environments to offer students a sense of humanness and connection with the teacher. Relationships in both online and face to face classrooms emerged as a necessary and central component to all teaching and learning communities. The theme of paradox also emerged as participants recognized that educational technologies can be used in ways that enhance creativity, authenticity, reflection and relationships or in ways that hinder these qualities in the teaching and learning community. Knowledge of the common experiences of college educators who utilize educational technologies, specifically digital video of children to educate early childhood educators, might give meaning and insight to inform the practice of other teachers who seek authentic, reflexive practice in the classroom and in on line environments.

Intramolecular carbenoid insertion : reactions of [alpha] -diazoketones derived from benzothienyl, pyrolyl and indolyl alkanoic acids with rhodium (II) acetate

Recent studies have shown that the rhodium (II) acetate decomposition chemistry observed for a-diazoketones tethered to thienyl, furanyl, and benzofuranyl moieties is dependent not only on the nature of the heteroatom but also on the length of the aliphatic tether linking the diazoketone moiety with the aromatic fragment. The present thesis expands on these results and focuses on a-diazoketones tethered to benzothiophenes, pyrroles and indoles by a methylene linker. In the case of benzothiophenes, it was shown that the rhodium catalyst decomposition of I-diazo-4-(3-benzothienyl)-2-butanone (146) and 1-diazo-4-(3benzothienyl)- 2-butanone (152) allow for the isolation of 1,2,3a,3b-tetrahydro-3Hbenzo[ b]cyclopenta[1,3]cyclopropa- [1 ,2-d]thiophen-3-one (147) and 1,2,3a,3btetrahydro- 3H-benzo[b]cyclopenta[1,3]cyclopropa[1,2-d]thiophen-3-one (153). However treatment of 1-diazo-3-(3-Benzothienyl)-2-Propanone (165) with Rh(II) acetate results in the formation of 2,3-Dihydro-1H-benzo[b]cyclopenta[d]thiophen-2-one (159), while 1diazo- 3-(2-Benzothienyl)-2-Propanone with the same condition gives 5,5-bis( 1benzothiophen- 2-ylmethyl)-2(5H)-furanone (166) along with the tricycle 159. The chemistry of the pyrrolyl and the indolyl moieties linked to terminal adiazoketone systems was also investigated. The decomposition of I-diazo-(2-pyrrolyl)-2propanone (173) results in the formation of two products; the N-H insertion product IHpyrrolizin- 2(3H)-one (176) and the alkylation product 4,6-dihydrocyclopenta[b]pyrrol5( 1 H)-one (180). When 1-Diazo-3-(3-indoly)-3-propanone (194) is treated with catalytic amount of Rh (II) 3,4-dihydrocyclopenta[b]indol-2(1H)-one (193) is isolated quantitatively. The later reaction when monitored using IH NMR the intermediate 200 can be seen whose structure was confirmed by the comparison to series of model compounds. The mechanisms underlying these reactions as well as their synthetic utility is discussed.

Kinetic and mechanistic studies for the molybdenum- catalyzed oxidation of organic sulfides and olefins by t- DuO2H

This research was focussed on the effects of light, solvent and substituents in the molybdenum-catalyzed oxidation of phenylmethyl sulfides with t-Bu02H and on the effect of light in the molybdenum-catalyzed epoxidation of l-octene with t-Bu02H. It was shown that the Mo(CO)6-catalyzed oxidation of phenylmethyl sulfide with t-Bu02H~ at 35°C, proceeds 278 times faster underUV light than under laboratory lighting, whereas the Mo02(acac)2-catalyzed oxidation proceeds only 1.7 times faster under UV light than under normal laboratory lighting. The difference between the activities of both catalysts was explained by the formation of the catalytically active species, Mo(VI). The formation of the Mo(VI) species, from Mo(CO)6 was observed from the IR spectrum of Mo(CO)6 in the carbonyl region. The Mo(CO)6-catalyzed epoxidation of l-octene with t-Bu02H showed that the reaction proceeded 4.6 times faster under UV light than in the dark or under normal laboratory lighting; the rates of epoxidations were found to be the same in the dark and under normal laboratory lighting. The kinetics of the epoxidations of l-octene with t-Bu02H, catalyzed by Mo02(acac)2 were found to be complicated; after fast initial rates, the epoxidation rates decreased with time. The effect of phenylmethyl sulfide on the Mo(CO)6-catalyzed epoxidation of l-octene waS studied. It was shown that instead of phenylmethyl sulfide, phenylmethyl sulfone, which formed rapidly at 85°C, lowered the reaction rate. The epoxidation of l-octene was found to be 2.5 times faster in benzene than in ethanol. The substituent effect on the Mo02(acac)2-catalyzed oxidations of p-OH, p-CHgO, P-CH3' p-H, p-Cl, p-Br, p-CHgCO, p-HCO and P-N02 substituted phenylmethyl sulfides were studied. The oxidations followed second order kinetics for each case; first order dependency on catalyst concentration was also observed in the oxidation of p-CHgOPhSMeand PhSMe. It was found that electron-donating groups on the para position of phenylmethyl sulfide increased the rate of reaction, while electronwithdrawing groups caused the reaction rate to decrease. The reaction constants 0 were determined by using 0, 0- and 0* constants. The rate effects were paralleled by the activation energies for oxidation. The decomposition of t-Bu02H in the presence of M.o (CO)6, Mo02 (acac)2 and VO(acac)2 was studied. The rates of decomposition were found to be very small compared to the oxidation rates at high concentration of catalysis. The relative rates of the Mo02(acac)2-catalyzed oxidation of p-N02PhSMe by t-Bu02H in the presence of either p-CH30PhSMe or PhSMe clearly show that PhSMe and p-CHgOPhSMe act as co-catalysts in the oxidation of p-N02PhSMe. Benzene, mesity1ene and cyclohexane were used to determine the effect of solvent in the Mo02 (acac)2 and Mo(CO)6-catalyzed oxidation of phenylmethyl sulfide. The results showed that in the absence of hydroxylic solvent, a second molecule of t-Bu02H was involved in the transition state. The complexation of the solvent with the catalyst could not be explained.The oxidations of diphenyl sulfoxide catalyzed by VO(acac)2, Mo(CO)6 and Mo02(acac)2 showed that VO(acac)2 catalyzed the oxidation faster than Mo(CO)6 and Mo02 (acac)2_ Moreover, the Mo(CO)6-catalyzed oxidation of diphenyl sulfoxide proceeded under UV light at 35°C.