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.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Grantham Township Records Collection

Item one is a minute book for Grantham Township, Ontario. It records the proceedings of meetings from 1818-1854 and the names of parish and town officers from 1818 to 1842. Names include: Chisholm, Ball, Steele, TenBroeck, Shipman, Laraway, McKerney, Adams, Pawling, Merritt, Rolls, Robertson, Lampman, Phelps, Darling. Also notes the laws agreed upon for the period - mainly dealing with livestock. Item two is a report and evidence of boundary line disputes in the Township of Grantham. Includes affidavits from witnesses to the boundary dispute and a report to the Honourable the Commissioner of Crown Lands Quebec. The affadavits were recorded in 1844, and transcribed into the folio in 1852. Lewis A. Ball was the commissioner before whom the affadavits were sworn and duly recorded. Includes field notes by Frederic F. Passmore, Provincial land surveyor. The boundary lines in dispute were 1. between the 2nd and 3rd Concessions, from Lot no. 1 to Lot no. 5, 2. between the 4th and 5th concessions, from lot no. 4 to lot no. 5 and 3. between lots 14 in the 9th and 10th concession of the Township of Grantham.

Elucidation of odour-potent compounds and sensory profiles of Vidal blanc and Riesling icewines from the Niagara Peninsula : effect of harvest date and crop level

I t was hypothesized that the freeze/thaw cycles endured by icewine grapes would change their chemical composition, resulting in unique chemical fingerprint and sensory properties, and would be affected by harvest date (HD) and crop level (CL). The objectives were: 1) to identify odour-active compounds using gas chromatographic and sensory analysis; 2) to determine the effect of CL and HD on these compounds; 3) to determine the icewine sensory profiles; 4) to correlate analytical and sensory results for an overall icewine profile. CharmAnalysis™ determined the Top 15 odour-potent compounds in Vidal and Riesling icewine and table wines; 24 and 23 compounds, respectively. The majority of the compounds had the highest concentrations in the icewines compared to table wines. These compounds were used as the foundation for assessing differences in icewine chemical profiles from different HD and CL. Vidal and Riesling icewine were made from grapes picked at different HD; HI : 19 December; H2: 29 December; H3: 18 January; H4: 11 February (Vidal only). HI wines differed from H3 and H4 wines in both Vidal and Riesling for aroma compounds and sensory profiles. - Three·CL [control (fully cropped), cluster thin at fruit set to one basal cluster/shoot (TFS), and cluster thin at veraison to one basal cluster/shoot (TV)] were evaluated for Riesling and Vidal cultivars over two seasons. Vidal icewines had the highest concentration of aroma compounds in the control and TV icewines in 2003 and in TFS icewines in 2004. In Riesling, most aroma compounds had the highest concentration in the TV icewines and the lowest concentration in the TFS wine for both years. The thinned treatments were associated with almost all of the sensory attributes in both cultivars, both years. HD and CL affected the chemical variables, aroma compounds and sensory properties of Vidal and Riesling icewines and freeze/thaw events changed their sensory profile. The most odour-potent compounds were p-damascenone, cis-rose oxide, 1- octen-3-ol, 4-vinylguaiacol, ethyl octanoate, and ethyl hexanoate. The role of Pdamascenone as a marker compound for icewine requires further investigation. This research provides a strong foundation for the understanding the odour-active volatiles and sensory profiles important to icewine.

Second Welland Canal - Book 3, Survey Map 18 - Through Humberstone

Survey map of the Second Welland Canal created by the Welland Canal Company showing the area through Humberstone Township. Identified structures associated with the Canal are the north and south back ditches, Towing Path and spoil banks. Surveyor measurements and notes can be seen in red and black ink and pencil. Local area landmarks include Tram Way to Peat Beds. Roads running parallel to Canal are the Road to Port Colborn and the northern Road Allowance. Roads running parallel to Canal are Road Allowance between the 2nd and 3rd Concession, Road Allowance between the 3rd and 4th Concession. Properties and property owners are noted as follows: J. Thompson, J. Sullivan, J. Leady, John Neff and Peter Neff. Other properties include: Lot No. 27, 3rd Concession, Lot No. 26, 3rd Concession and Lot No. 25, 3rd Concession."Humberstone" - Scale 4 Chs. per Inch

Second Welland Canal - Book 3, Survey Map 19 - Petersburgh and Humberstone

Survey map of the Second Welland Canal created by the Welland Canal Company showing the areas in and around Petersburg and Humberstone. Identified structures associated with the Canal include North and South Back Ditches, Bridge Tender's Building, Towing Path, Old Back Ditch, and Covered Drain. Features of the First Welland Canal are noted in red ink. Surveyor measurements and notes can be seen in red and black ink and pencil. Local area landmarks include bridge, barns, ruins of Stone Mill (burnt), Wesbern (Wabern) Hotel and spoil banks. Roads labelled running parallel to Canal is the south Road Allowance. Roads perpendicular to Canal include Road Allowance between 1st and 2nd Concession, Road to Waterloo Ferry, Road Allowance between 2nd and 3rd Concessions. Properties and property owners/renters are identified as follows: A. Augustine, Captain Duffil, O. Farres, I. Schooley, George Augustine, E. Schooley (Schooly), R. and J. Kilmer (Killmer), J. Urich, J. Thompson (Tompson), M. Reeb, G. Wilson, J. Klee, John Steel, E. Augustine, Furry, J. Jackson, Robert House, R. White, J. Crame, D. Saff, J. Kinnard, J. Schooley, Dickson, C. Erhoff, and G. Rother."Village of Petersburgh" - Scale 2 Chs. per Inch "Humberstone" - Scale 4 Chs. per Inch,

Welland Canal Survey of Lands Jacob Tenbroeck, 1828

Survey map and description of Jacob TenBrock's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; tow path, 12 mile creek, property line between Peter May and Jacob Tenbroeck. The land includes part of lot no.22 in the 2nd and 3rd concession of Grantham. The land is a total of 26 acres and contains 1 road. Surveyor notes are seen in pencil on the map.

Elucidation of the Retinoid Signalling Pathway Involved in Axon Guidance in Lymnaea stagnalis and Xenopus laevis

The vitamin A metabolite, retinoic acid (RA), is known to play a crucial role in several developmental processes including axial patterning and differentiation. More recently, RA has been implicated in the regenerative process acting through its classical signaling pathway, the nuclear receptors, retinoic acid receptor (RAR) and retinoid X receptor (RXR), to mediate gene transcription. Moreover, RA has been shown to act as a guidance molecule for growth cones of regenerating motorneurons of the pond snail, Lymnaea stagnalis. Our lab has recently shown that RA can induce this morphological response independent of nuclear transcription, however, the role of the retinoid receptors in RA-induced chemoattraction is still unknown. Here, I show that the retinoid receptors, RXR and RAR, may mediate the growth cones response to the metabolically active retinoic acid isomers, all-trans and 9-cis RA, in Lymnaea stagnalis. Data presented here show that both an RXR and RAR antagonist can block growth cone turning in response to application of both isomers. Because no prior investigations have shown growth cone turning of individual vertebrate neurons, I aimed to show that both retinoic acid isomers were capable of inducing growth cone turning of embryonic spinal cord neurons in the frog, Xenopus laevis. For the first time in Xenopus, I showed that both all-trans and 9-cis RA were able to induce significantly more neurite outgrowth from cultured embryonic spinal cord neurons and induce positive growth cone turning of individual growth cones. In addition, I showed that the presence of the RXR antagonist, HX531, blocked 9-cis RA-induced growth cone turning and the RARβ antagonist, LE135, blocked all-trans RA-induced growth cone turning in this species. Evidence provided here shows for the first time, conservation of retinoic acid-induced growth cone turning in a vertebrate model system. In addition, these data show that the receptors involved in this morphological response may be the same in vertebrates and invertebrates.

Globalization and Its Impact on Assessment: Moving Toward a New Story

Globalization has resulted in large-scale international and local assessments closely tied to notions of accountability and competitiveness in a globalized economy. Although policy makers seek to ensure citizens meet the demands of a global knowledge-based economy, such assessments may also impede the development of requisite 21st century skills. While standardization currently is viewed as the most effective measurement of student achievement, several Canadian and international jurisdictions are moving toward assessment for learning (AfL). This conceptual study sought to identify whether AfL or standardized assessment most effectively meets 21st century learning goals in the wake of rapid global change. It applies a Story Model theoretical framework to understand the current, the new emerging, and the future ideal story of education from a personal, cultural, and global lens. The study examines the main critiques and/or challenges of standardized testing, the benefits of AfL for student learning, and new teaching and assessment approaches to the development of 21st century learning goals. The study applies the Story Model’s inside-outside/past-future approach to determine the future direction of assessment. Results show that the new story of assessment will most likely entail a model that integrates both standardized testing and in-class assessments in the form of AfL and PBL.

Port Weller Dry Docks collection, 1959-1967

Port Weller Dry Docks Limited was officially established on April 25, 1946, near Lock 1 of the Welland Canal. Charles A. Ansell was the company’s first President and General Manager. Initially, the company focused on repairing ships, but in June, 1951, built their first ship, the Scott Misener. In 1956, the Upper Lakes and St. Lawrence Transportation Co. purchased all of the shares of Port Weller Dry Docks Limited. In the mid-eighties, ULS (Upper Lakes Shipping) International (which owned the Port Weller dry docks), and Canada Steamship Lines, merged their operations. As a result, the Port Weller Dry Docks became a division of this newly formed company, known as Canadian Shipbuilding and Engineering Limited. In 2007, Seaway Marine & Industrial Inc. took over ownership of the Port Weller Dry Docks, but declared bankruptcy in July 2013.

Physical Activity and the Entanglement of Meaning Making for Females

This research takes a phenomenological approach through narratives to investigate the meanings females attribute to their experiences with physical activity. Nine females across the age ranges of 10-80 were asked to share three meaningful physical activity stories. These experiences could be positive or negative in nature as long as they were reflective of a meaningful experience for the participant. The aim of the research was to explore the types of physical activity experiences that females find meaningful. The results indicate that participants perceived the following to be meaningful within their experience: social support, benefits to personal health and well-being, recognition and acknowledgment, empowerment, body control, early positive experience and identity formation. Participants’ stories offered an enlightened understanding of the meanings active females associate with physical activity across their lifespans that perhaps can assist in formulating and developing strategies to encourage and promote involvement in physical activity.

Raising Creativity: Exploring How Creativity Can be Nurtured in Educational Contexts

The question of how we can encourage creative capacities in young people has never been more relevant than it is today (Pink, 2006; Robinson as cited in TEDtalksDirector, 2007; Eisner as cited in VanderbiltUniversity, 2009). While the world is rapidly evolving, education has the great challenge of adapting to keep up. Scholars say that to meet the needs of 21st century learners, pedagogy must focus on fostering creative skills to enable students to manage in a future we cannot yet envision (Robinson as cited in TEDtalksDirector, 2007). Further, research demonstrates that creativity thrives with autonomy, support, and without judgment (Amabile, 1996; Codack [Zak], 2010; Harrington, Block, & Block, 1987; Holt, 1989; Kohn, 1993). So how well are schools doing in this regard? How do alternative models of education nurture or neglect creativity, and how can this inform teaching practice all around? In other words, ultimately, how can we nurture creativity in education? This documentary explores these questions from a scholarly art-based perspective. Artist/researcher/teacher Rebecca Zak builds on her experience in the art studio, academia, and the art classroom to investigate the various philosophies and strategies that diverse educational models implement to illuminate the possibilities for educational and paradigmatic transformation. The Raising Creativity documentary project consists of multiple parts across multiple platforms. There are five videos in the series that answer the why, who, how, what, and now what about creativity in education respectively (i.e., why is this topic important, who has spoken/written on this topic already, how will this issue be investigated this time, what was observed during the inquiry, and now what will this mean going forward?). There is also a self-reflexive blog that addresses certain aspects of the topic in greater depth (located here, on this website) and in the context of Rebecca's lived experience to complement the video format. Together, all video and blog artifacts housed on this website function as a polyptych, wherein the pieces can stand alone individually yet are intended to work together and fulfill the dissertation requirements for Rebecca's doctorate degree in education in reimagined ways.

Electron Transfer Involving the Phylloquinone (A1) Cofactor of Photosystem I Examined with Time Resolved Absorbance and Electron Paramagnetic Resonance Spectroscopy

The dependence of the electron transfer (ET) rate on the Photosystem I (PSI) cofactor phylloquinone (A1) is studied by time-resolved absorbance and electron paramagnetic resonance (EPR) spectroscopy. Two active branches (A and B) of electron transfer converge to the FX cofactor from the A1A and A1B quinone. The work described in Chapter 5 investigates the single hydrogen bond from the amino acid residue PsaA-L722 backbone nitrogen to A1A for its effect on the electron transfer rate to FX. Room temperature transient EPR measurements show an increase in the rate for the A1A- to FX for the PsaA-L722T mutant and an increased hyperfine coupling to the 2-methyl group of A1A when compared to wild type. The Arrhenius plot of the A1A- to FX ET in the PsaA-L722T mutant suggests that the increased rate is probably the result of a slight change in the electronic coupling between A1A- and FX. The reasons for the non-Arrhenius behavior are discussed. The work discussed in Chapter 6 investigates the directionality of ET at low temperature by blocking ET to the iron-sulfur clusters FX, FA and FB in the menB deletion mutant strain of Synechocyctis sp. PCC 6803, which is unable to synthesize phylloquinone, by incorporating the high midpoint potential (49 mV vs SHE) 2,3-dichloro-1,4-naphthoquinone (Cl2NQ) into the A1A and A1B binding sites. Various EPR spectroscopic techniques were implemented to differentiate between the spectral features created from A and B- branch electron transfer. The implications of this result for the directionality of electron transfer in PS I are discussed. The work discussed in Chapter 7 was done to study the dependence of the heterogeneous ET at low temperature on A1 midpoint potential. The menB PSI mutant contains plastiquinone-9 in the A1 binding site. The solution midpoint potential of the quinone measures 100 mV more positive then wild-type phylloquinone. The irreversible ET to the terminal acceptors FA and FB at low temperature is not controlled by the forward step from A1 to FX as expected due to the thermodynamic differences of the A1 cofactor in the two active branches A and B. Alternatives for the ET heterogeneity are discussed.

List of Trust Deeds signed by S.D. Woodruff, 1899

List of trust deeds (one page handwritten) and request to the sons of Samuel D. Woodruff to grant and allow on 2nd and 3rd trusts the amounts as allowed to Mr. Woodruff and his wife Jane. This is signed by S.D. Woodruff, June 20, 1899.

Indenture (vellum) between the Honourable William Dickson of Niagara and Robert Dickson of Niagara

Indenture (vellum) between the Honourable William Dickson of Niagara and Robert Dickson of Niagara for 970 acres in the 1st and 2nd Concessions of Dumphries. Some of the details on the outside of the document are faded and illegible. All text on the inside is legible, Jan. 9, 1841.