A G. C./M. S. study of the reaction and decomposition products of pentafluorophenyl-grignard and lithium reagents

Decomposition and side reactions of, and the synthetic use of, pentafluorophenylmagnesium bromide and pentafluorophenyllithium have been investigated using G,C9/M.S, techniques• Their reactions with reagents such as CgF^X (X - H, F, CI, Br, 1), C6F4X2 (X - H, CI)f C6F3C13, C6H6. (CgX5)3P (X = H, F), (C6X5)3P=0 (X = H, F), (CgX5)Si (CH3)3 (X = H, F) and (CH0K SiCl , n = 1,2, in ether or ether/n-hexane were studied• In addition to the principal reaction of synthetic use, namely the replacement of a halogen by a pentafluorophenyl group, two types of side reactions were observed* These were (i) intermolecular loss of LiF via a nucleophilic substitution, and (ii) intramolecular loss of LiF, followed by the addition of either inorganic salts such as lithium or magnesium halides, or organometal compounds such as organolithium or organo-Grigaard* G.C«/M.S. techniques were routinely employed to study complicated reaction mixtures. Although mass spectrometry alone has disadvantages for the identification of isomers, deduction of the most probable pathway often helps overcome this problem.

Reactions of steroidal epoxides with strong organic bases and an investigation into the syntheses of some labelled pregnane derivatives

Reactions of 5,6- and 4,5-epoxycholestane derivatives with strong bases were investigated. Epoxidation of 3a-acetoxycholest-5-ene also gave a new compound along with the anticipated epoxides. Interconversions of the latter were observed. Some possible mechanisms of its formation and rearrangements have been pIioposed. No reaction was observed with any of the 5,6- and 4,5-steroidal epoxides employed in the present study, using potassium tertiary butoxide under refluxing conditions. n-Butyllithium reacted only with 5,6-epoxycholestanes bearing a ketal moiety at the C3 carbon. Opening of the ketal group was observed with n-butyllithium in the case of a ~-epoxide. The reaction was also investigated in the absence of epoxide functionality. A possible mechanism for the opening of ketal group has been proposed. Lithium diethylamide (LDEA) was found effective in rearranging 5,6- and 4,5-epoxides to their ~orresponding allylic alcohols. These rearrangements presumably proceed via syn-eliminations, however the possibility of a corresponding anti-elimination has not been eliminated. A substituent effect of various functional groups (R = H, OH, OCH2CH20) at C3 has-been observed on product distribution in the LDEApromoted rearrangements of the corresponding epoxides. No reaction of these epoxides was observed with lithium diisopropylamide (LDA) • In the second part of the project, several attempts were made towards the sYRthesis of deoxycorticoste~one~17,2l,2l~d3' a compound desirable for the 2l-dehydroxylation studies of deoxycorticosterone. Several routes were investigated, and some deuterium labelled pregnane derivatives were prepared in this regard. Microbial 21-hydroxylation of progesteronel7,21,21,2l- d4 by ~ niger led to loss of deuterium from C21 of the product. An effort was made to hydroxylate progesterone microbially under neutral condtions.

Reactions of various aromatic nitro-compounds and anthraquinones with selected bases and nucleophiles

The Introducti on deals mainly with hi storical studies on aryne chemi stry and ring closure via arynes , hydride replacement from aromatic rings by nucleophi les, c l eavage of anthr aquinones in basic medium and the Leuckart reaction . This work can be divided into two main s ect i ons. Section I is concerned with the investigation of t he reaction of some aromatic ni t ro-compounds with potassamide in l iquid ammonia. 3-Amino-4- nitrobenzophenone was obtained from the reacti on of 4-nitrobenzophenone with t his reagent, toge t her with benzoic acid formed in a competing Haller-Bauer reaction. Nitrobenzene under these conditions gave a complex mixture from which 2-phenylphenol was isolated; a reaction i nvolving benzyne may be i nvo l ved. 4-Nitrodiphenyl sulfone gave 4-aminodiphenyl sulfone and 4-nitroani l ine. 4-Ethoxydiphenyl sulfone and 4-ethoxynitrobenzene were isolated when ethanol was used as a co-solvent in the reaction. Oxidative coupling reactions were observed with nitrotoluenes. 4-Nitrotoluene gave 4,4t-dinitrobibenzyl which i n a pro longed reaction gave 4,4t-dinitros t ilbene . 2-Nitrotoluene gave 2 , 2 t-dinitrobibenzyl, but not the corresponding stilbene derivative even after a longer time . A rather i nteresting result was obtained with 1-nitro-2,4,6- trimethylbenzene which gave a stilbene derivative only. Also the corresponding stilbene was obtained from bis-(4-nitrophenyl)-methane in a rather slow r eaction with this reagent . Section II deals wi th (i) the preparation of 5-chloro- 1-N-methyl aminoanthraquinone and a new synthesis of N-methyl acridones and (ii) treatment of chloro-anthraquinones with fo rmamide and a new synthesis of chloro-anthracenes . 5-Chloro-1 -N-methylaminoanthraqui none was synthesised f rom 1,5-dichloroanthraquinone by treatment with N-methylformamide. Treatment of 5-chloro-1-N-methylaminoanthraquinone with potassamide in liquid ammonia or with potassium t-butoxide i n t-butylbenzene gave N-methylacridone-1-carboxylic acid. This pleasing result, t he outcome of r i ng opening and alter native ring closure, is being extended to related ring systems.

An examination of NHL fans' reactions to the cancelled 2004-2005 season

AN EXAMINATION OF NHL FANS' REACTIONS TO THE CANCELLED 2004- 2005 SEASON Chad Asselstine Faculty of Applied Health Sciences, Brock University Gary Bettman, the Commissioner of the National Hockey League (NHL) stepped in front of the worldwide media on February 16, 2005 to announce that there would be no NHL games played during the 2004-2005 season. Two sides were prominent during the labour dispute; the NHL owners and the NHLP A, however a third side that became the forgotten party was the fans (NHLF A, 2005). The fans are the consumers of the NHL and all the brands associated with its franchises, they are the people who provide the revenues that allow owners to pay the players' salaries. The present study is situated within the sport marketing framework, particularly within the fan loyalty literature to provide an understanding of the impact of the 2004- 2005 lockout on the forgotten party, NHL fans. This study examines 16 fans' experiences in four stages: becoming a fan of the NHL, being a fan prior to the lockout, being a fan during the lockout including their anticipated reaction to the return of the NHL, and their actual reaction to the return of the NHL. Data was collected using face-to-face interviews with each ofthe participants, resulting in 16 fans' stories of how the lockout impacted them specifically. Through analysis of the data themes began to emerge including the fans' understanding that there was a need to restructure game play, the business operations of the NHL, a desire for service recovery strategies which would exceed fans' expectations, 4 and the desire for alternative forms of consumption including alternative hockey leagues as well as the growing popularity of poker playing. The study summarizes the effects that the NHL lockout had on the relationship between 16 individual fan~ and their favourite teams, and concludes with Suggestions for Future Research and Implications for Sport Marketers that emerged from this unique case in the history of North American professional sport.

Stock market reactions to changes in the FTSE SmallCap and S&P/TSX SmallCap indices

Stocks added to (deleted from) the Russell 2000 and the S&P 600 indexes experience positive (negative) abnormal returns following the announcement. However, researchers disagree on whether these abnormal returns are permanent or temporary and offer competing explanations. I address this controversy by examining market reactions for firms that are added to or deleted from the FTSE Small Cap index (the main testing sample) and the S&P/TSX SmallCap index (the comparison sample). For the main testing sample, all stocks except pure additions, experience a permanent price change that is accompanied by a permanent change in liquidity. However, for the comparison sample, abnormal returns over the announcement period fully reverted within 30 days. In further examination of stock liquidity for the main testing sample, sample stocks experience permanent change in liquidity. Taken together, the observed results support the price pressure and liquidity hypotheses.

Michael Hogue fonds

Michael H. [Henry] Hogue (1878-1963) was the son of Lemuel and Frances Hogue of Wainfleet Township, Welland County. In 1901 Michael Hogue was married to Margaret Case and they had five sons, William, Lemuel, Harry, Ross and Frank. In the 1911 Census of Canada he is residing in Welland and working as a blacksmith for Howard H. Lymburner. At Lymburner’s retirement, Hogue purchased the business and moved it from 15 Niagara Street, Welland to 12 Frazer Street, Welland. Mr. Hogue’s blacksmith activities included work with various industries in Welland including the expansion of blacksmithing work into the automobile industry. Mr. Hogue also worked for subcontractors Canadian Dredge & Dock and G.L. Campbell. These jobs included work related to the Welland Ship Canal in 1923. The business ceased operation in 1956.

Welland Canal Survey of Lands Michael and Jacob Silverthorn, 1834

Survey map and description of Michael and Jacob Silverthorn'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; line between Burger and Silverthorn's land, reservoir, wood land, road leading to Quaker settlement, line between Jacob and Michael Silverthorn's land. The deeds for both lands are dated September 25, 1834. Surveyor notes are seen in pencil on the map.

Market reactions to changes in the Nasdaq-100 Index membership

We examine stock market reactions around the Nasdaq-100 Index reconstitutions. We find a symmetric and transitory price response accompanied by a significant increase in trading volume on the effective date. Firms added to the Nasdaq-100 Index experience significant increases in institutional ownership, the number of market makers, and the number of shareholders. In contrast, firms removed from the index show significant decreases in the number of institutional shareholders. Additions to the Nasdaq-100 Index also show significant increases in four liquidity measures, whereas deletions demonstrate significant decreases in two liquidity measures. These changes in liquidity are related to the abnormal return on the announcement day. Taken together, the results suggest support for the price pressure, liquidity, and investor awareness hypotheses.

Michael Hornyansky Fonds,

Michael Sands Hornyansky was the son of well-known artist, Nicholas Hornyansky and a cellist. He attended Oakwood Collegiate, Toronto; University College in Toronto and Merton College, Oxford where he was a Rhodes scholar. He won the Newdigate prize for poetry in 1951. Dr. Hornyansky taught English Language and Literature at Carleton University, Ottawa for 10 years before moving to Niagara in 1964. He was the founding chairman of the English Department of Brock University where he remained until his retirement in 1993. Some of his achievements include:The Golden Phoenix, a retelling of French Canadian folk tales and the publishing of papers on children’s literature and the discriminating use of the English language. He also reviewed poetry for the University of Toronto Quarterly. Michael Hornyansky died on May 14th, 2008 in Alberta at the age of 81. The annual Michael Hornyansky prize for creative writing was established at Brock University.

Role Differences in the Perception of Injustice

The current dissertation examined role differences in the perception of injustice; specifically, differences in how victims and offenders respond to a situation that they both agree is unfair. Past research has demonstrated that role affects reactions to transgressions and injustice, including recall of transgressions, and attributions of blame and responsibility (e.g., Baumeister, Stillwell, & Wotman, 1990; Mikula, Athenstaedt, Heschgl, & Heimgartner, 1998). However, to date, little work has examined role differences in perceptions of why an event is perceived as unfair (i.e., how an injustice is framed) or how justice should be restored. These were the perceptions I focused on in the present thesis. I also examined potential concerns that may motivate victims' and offenders' justice reactions, as well as the potential interaction between role and relationship quality in predicting justice reactions. In Studies 1 and 2, several of the predicted role differences in concerns were found; however, these did not lead to the expected differences in framing and restoration. In Study 1, using a vignette methodology, I found differences primarily in how victims and offenders believed justice should be restored. Overall, the significant role effects showed an accommodating response pattern (e.g., offenders proposed punishment more than did victims and neutral observers, whereas victims recommended minimal compensation more than did offenders and neutral observers), inconsistent with previous research and my hypotheses. Study 2, which employed a sample of romantic couples, substantiated the accommodating pattern found in Study 1. Study 3, which sampled a broader range of relationships, also showed i \ examples of accommodating reactions. In addition, Study 3 provided some support for the hypothesized interaction between role and relationship quality, such that responses were more accommodating as relationship quality increased. For example, offenders more strongly endorsed methods of restoration such as offender apology and recognition of the relationship with increasing relationship quality. Overall, the results from this dissertation support the general notion that victims and offenders respond to injustice differently, and, in-line with previous research on other justice-related responses (e.g., Mikula et at, 1998), suggest that victims and offenders show an other-serving, accommodating tendency in justice reactions when relationship quality is high.

Compensatory Arm Reactions in Individuals with Parkinson’s Disease

This study examined how perturbation-evoked compensatory arm reactions in individuals with Parkinson’s disease (PD) are influenced by explicit verbal instruction. Ten individuals with PD and 15 older adults without PD responded to surface translations with or without specific instruction to reach for and grasp the handrail. Electromyographic (EMG) and kinematic recordings were taken from the reaching arm. Results showed that individuals with and without PD benefitted similarly from explicit instruction. Explicit instruction resulted in earlier (p=0.005) and larger (p<0.001) medial deltoid EMG responses in comparison to no specific instructions. Compensatory arm reactions also occurred with a higher peak medio-lateral wrist velocity (p<0.001) and higher peak shoulder abduction angular velocity (p<0.001) with explicit instruction. Explicit instruction positively influenced compensatory arm reactions in individuals with and without PD. Future research is needed to determine whether the benefits of instruction persist over time and translate to a loss of balance in real life.

Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Photograph - Mr. & Mrs. Michael Henry (nee Almedie Mann)

A photograph of Mr. & Mrs. Michael Henry (nee. Almedie Mann) taken by G.F. Maitland, photographer, St. Paul Street, St. Catharines.

Letter- Michael H. Wilson to Donald Ziraldo, 1993

A letter from Michael H. Wilson, Minister of Industry, Science and Technology and Minister of International Trade, dated 7 May, 1993. He discusses the achievements of Inniskillin in the "Vinitaly" wine exhibition. Wilson also remarks on the great accomplishments of Mr. Ziraldo as chairman of the Ontario Vintners Quality Alliance (VQA).

Letter - Michael D. Harris to Donald Ziraldo, 2000

A letter from Premier Mike Harris to Donald Ziraldo 15 June, 2000. The correspondence discusses the possibility of agricultural preserve in Niagara.