An investigation into the oxidation of organic sulphides, organic selenides and simple hydrocarbons by Mortierella isabellina NRRL 1757

The work presented in this thesis is divided into three separate sections 4!> Each' 'section is involved wi th a different problem, however all three are involved with a microbial oxidation of a substrate~ A series of 'aryl substituted phenyl a.nd be,nzyl methyl sulphides were oxidized to the corre~pondi~g sulphoxides by 'Mo:rtierellai's'a'b'e'llina NRR.L17'S7 @ For this enzymic Qxidation, based on 180 labeled experiments, the oxygen atom is derived fr'orn the atmosphere and not from water. By way of an u~.traviolet analysis, the rates of oxidation, in terms of sulphox~ de appearance, were obtained and correlated with the Hatnmett p s~grna constants for the phenyl methyl sulphide series. A value of -0.67 was obtained and, is interpreted in terms of a mechanism of oxidation that involves an electrophilic attack on the sulphide sulphur by an enzymic ironoxygen activated complex and the conversion of the resulti!lg sulphur cation to sulphoxide. A series of alkyl phenyl selen~des have been incubated with the fu~gi, Aspergillus niger ATCC9l42, Aspergillus fO'etidus NRRL 337, MIIJisabellina NF.RLl757 and'He'lminth'osparium sp'ecies NRRL 4671 @l These fu?gi have been reported to be capable of carrying out the efficient oxidation of sulphide to sulphoxide, but in no case was there any evidence to supp'ort the occurrence of a microbialox,idation. A more extensive inves·t~gation was carried out with'M,e 'i's'a'b'e'l'l'i'na, this fu~gus was capable of oxidizing the correspondi~g sulphides to sulphoxi.de·s·$ Usi:ng a 1abel.edsubstra.te, [Methyl-l4c]-methyl phenyl selenide, the fate of this compound was invest~gated followi!lg an i'ncubation wi th Me isabellina .. BeSUldes th. e l4C-ana1YS1Q S-,'. a quant"ltta"lve selen'lum ana1Y"S1S was carried out with phenyl methyl selenide. These techniques indicate that thesel'enium was capable of enteri!1g thefu!1gal cell ef'ficiently but that s'ome metabolic cleav~ge of the seleni'um-carbon bond' may take plac'e Ie The l3c NMR shifts were assigned to the synthesized alkyl phenyl sulphides and selenides@ The final section involved the incubation ofethylben~ zene and p-e:rtr.hyltoluene wi th'M ~ 'isab'e'llina NRRL 17574b Followi~ g this incubation an hydroxylated product was isolated from the medium. The lH NMR and mass spectral data identify the products as I-phenylethanol and p-methyl-l-phenylethanol. Employi!lg a ch'iral shift re~gent,tri~ (3-heptafluorobutyl-dcamphorato)'- europium III, the enantiomeric puri ty of these products was invest~gated. An optical rotation measurement of I-phenylethanol was in ~greement with the results obtained with the chiral shift re~gen,te 'M.isabe'l'lina is capable of carryi~g out an hydroxylation of ethylbenzene and p-ethyltoluene at the ~ position.

Biotransformation of polycylic aromatic compounds by fungi and an investigation into the oxidation of alkylbenzenes by Mortierella isabellina NRRL 1757

Incubations of several polycyclic heteroaromatic compounds and two polycyclic aromatic hydrocarbons with a series of common fungi have been performed. The fungi Cunninghamella elegans ATCC 26269, Rhizopus arrhizus ATCC 11145, and Mortierella isabellina NRRL 1757 were studied in this regard. Of the aza heteroaromatics, only dibenzopyrrole gave a ring hydroxylated product following the incubation with C. elegans. From the thio heteroaromatics studied, dibenzothiophene was metabolized by all the three fungi and thioxanthone by C. elegans and M. isabellina giving sulfones and sulphoxides. Thiochromanone was metabolized stereoselectively to the corresponding sulphoxide by C. elegans. Methyl substituted thioxanthones on incubation with C. elegans produced oxidative products, arising from S -oxidation and hydroxylation at the methyl group. Of the cyclic ketones studied, only fluorenone was reduced to hydroxyfluorene and this metabolism is compared with that reported with cytochrome P-450 monooxygenases of hepatic microsomes. A series of para-substituted ethylbenzenes has been transformed stereoselectively to the 1-phenylethanols by incubation with M. isabellina. Comparisons of the enantiomeric purities obtained from products with their respective para substituent of the same steric size but different electronic properties indicate that the stereoselectivity of hydroxylation at benzylic carbon may be susceptible to electron donating or withdrawing factors in some cases, but that observation is not va lid in all the comparisons. The stereochemistry of the reaction is discussed in terms of three possible steps, ethylbenzene ---) 1-phenylethanol ---) acetophenone ---) 1-phenylethanol. This metabolic pathway could account for the inconsistencies observed in the comparisons of optical purities and electronic character of para substituents. Furthermore, formation of 2-phenylethanol (in some cases), l-(p-acetylphenyl)ethanol from p-diethylbenzene, and N-acetylation of p-ethylaniline was observed. n-Propylbenzene was also converted to optically active 1-phenylpropanol. Acetophenone, p-ethylacetophenone, and o(,~,~-trifluoroacetophenone were transformed to 1-phenylethanol, l-(p-ethylphenyl)ethanol, and 1-phenyl-2,2,2-trifluoroethanol, respectively, with high chemical and excellent optical yields. The 13 C NMR spectra of several substrates and metabolic products have been reported and assigned for the first time.

NMR studies of mixed tetrahaloborates and some related boron trihalide complexes /|nGary John Schrobilgen. -- 260 St. Catharines, Ont. : [s. n.],

Nuclear magnetic resonance spectroscopy has been used to study donor-acceptor complexes of boron trifluoride with several ureas, tetramethylthiourea, tetramethylselenourea, and tetramethylquanidine as well as adducts of tetramethyl- -urea with BF2Cl, BFC1 2 , and BC1 3 - A large number of mixed tetrahaloborate ions, including some of the ternary ones such as BF2CIBr-,have been obtained by ligand exchange reactions and studied by NMR techniques. The bonding in these ions is of the same inherent interest as the bonding in the isoelectronic tetrahalomethanes which have been the subject of many detailed studies and have been involved in a controversy concerning the existence of and the nature of "fluorine hyperconjugation" or C-F P1T- Pn bonding_ Ligand exchange reactions also gave rise to the difluoroboron cation, (TMU)20BF2+o The difluoroboron cation has been observed in solutions of TMU-BF3 , and has been proposed as a possible intermediate for fluorine exchange reactions in BF3 adducts.

Reactions of some non-enolisable chloroketones with amide ion and a new synthesis of acridones /|nGuo-shyoung John Chen. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed mainly towards the investigation of the reacti.ons of· substituted chlorobenziophenones under strongly basi,c conditions. The work 'can be divided into two main sections. The Introduction deals mainly with historical studies on aryne chemistry and the Haller-Bauer reaction. Secti.on I i.s concerned with syntheses of 2-benzamido-2'chlorobenzophenone and 2-benzamido~3'-chlorobenzophenone,and with thei,r respective reactions wi.th potassium amide in ammonia. o-Chlorophenylacetic acid was converted to the acid chloride and then by Friedel-Craftsreaction with benzene to w-(o-chlorophenyl)acetophenone. Reaction wi.th phenylhydrazine and Fischer cyclization gave 3- (0chlorophenyl)- 2-phenylindole, which was ozonized to 2-benzamido-2'chlorobenzophenone. The isomeric 3' -chlor,..o ke: tone was similarly synthesised from m-chlorophenylacetic acid. Both the 2'- and 3' -ch.loroketones gave N-benzoylacridone on treatment with potassium amide in ammonia; an aryne mechanism is involved for the 3'-chloroketone but aryne and nucleophilic substitution mechanisms are possible for the 2'-chloroketone. Hydrolysis of the 2'- and 3'-chloroketones gave 2-amino-2'chlorobenzophenone and 2-amino-3'-chlorobenzophenone respectively. A second new acridone synthesis is given in the Appendix involving reactions of these two ketones with potassium t-butoxide in t-butylbenzene. i Section 2 deals with the investigation of the reaction of some tricyclic ch1orobenzophenones with potassium amide in liquid ammonia. These were 1-ch1orof1uorenone; which was pr~pared in several steps from f1uoranthene, and 1- and 2-ch1oroanthraquinones. 1-Ch1orof1uorenone gave 1-aminof1uorenone ; 1-ch1oroanthraquinone gave 1- and 2-aminoanthraquinones; 2-ch1oroanthraquinone was largely recovered from the attempted reaction.

From absolutes to aesthetics : John Dewey and the art of experience /

In this thesis I sought to capture something of the integrity of John Dewey's larger vision. While recognizing this to be a difficult challenge, I needed to clear some of the debris of an overly narrow reading of Dewey's works by students of education. The tendency of reducing Dewey's larger philosophical vision down to neat theoretical snap shots in order to prop up their particular social scientific research, was in my estimation slowly damaging the larger integrity of Dewey's vast body of work. It was, in short, killing off the desire to read big works, because doing so was not necessary to satisfying the specialized interests of social scientific research. In this thesis then I made a plea for returning the Humanities to the center of higher education. It is there that students learn how to read and to think—skills required to take on someone of Dewey's stature. I set out in this thesis to do just that. I took Dewey's notion of experience as the main thread connecting all of his philosophy, and focused on two large areas of inquiry, science and its relation to philosophy, and aesthetic experience. By exploring in depth Dewey's understanding of human experience as it pertains to day-to-day living, my call was for a heightened mode of artful conduct within our living contexts. By calling on the necessity of appreciating the more qualitative dimensions of lived experience, I was hoping that students engaged in the Social Sciences might begin to bolster their research interests with more breadth and depth of reading and critical insight. I expressed this as being important to the survival and intelligent flourishing of democratic conduct.

Pen and sunlight sketches of scenery reached by the Grand Trunk Railway system and connections with summer routes and fares to principal points : including Niagara Falls, Thousand Islands, Rapids of the St. Lawrence, Montreal, Quebec, Parry Sound, Georgian Bay, Muskoka Lakes, Adirondacks, Lake St. John, Mackinac Island, Midland District Lakes, the White Mountains, the Suquenay River, Rangeley Lakes and the sea-shore.--

At head of title: "Great tourist route of America".

John Burtniak Postcard Collection

326 images (b&w and col.) mounted on 54 poster boards ; 64 x 36 cm or smaller. 4 compact disc

City of the Falls clippings, 1833, n.d.

The clippings describe the City of the Falls and its attempts by its shareholders to sell lots to this newly developing city. The venture by shareholders W. Allan, James Buchanan, Thomas Clark, J.H. Dunn, Thomas Dixon, General Murray, James Robinson, Samuel Street and William Witla intended to favourably position their city as a destination for “affording an easy approach for the annual assemblage of the Fashionable, the Learned and the Great”. The venture failed due to the building of the Buffalo and Niagara Falls railway.

Custom House Niagara forms, 1833

In 1833 William Clarke, the collector of customs at Niagara, completed and signed four forms for the movement of goods between Niagara and York, and Niagara and Brantford. The forms were issued to the firm of Lewis & Gray, James Armstrong, J.A. Wilks, and William Blackely. The goods being transported included scythes, corn brooms, hide whips, sacks, snuff, shovels, spades and two apple trees.

Gainsborough [Presbyterian] Church records, 1833-1836, 1841-1846, 1855-1857, 1860-1864, 1866 [photocopy]

The Gainsborough Presbyterian Church was organized prior to 1833, but no records were kept until this date. In 1809, the church was lead by Rev. Daniel Ward Eastman. In 1833 the church became part of the Niagara Presbytery of the American Presbyterian Church. The records include transfer of membership, records of marriages, lists of subscribers and session minutes. Photocopies from originals were made in 1977 by E. Phelps, University of Western Ontario, prior to their deposit with the United Church of Canada Archives, Toronto, Ont.

John Smith, M.P fonds, 1930, 1949-1950, 1954, 1957-1962, n.d.

John Smith (1894-1977), son of Daniel Smith and Annie Douglas was a native of Scotland, immigrating to Canada in 1913. He first worked as a coach builder, then as a carpenter, finally developing his own contracting business. During WWI he served overseas with the 10th Battery, RCA as a sergeant. In 1924 Smith married Jean Wood, and together they had a daughter Irene (Hugh Langley). Smith first entered politics in 1940 serving as an alderman for the next 11 years. In 1954 he was elected mayor of the city of St. Catharines, and was twice returned to office by acclamation, serving until 1957 when he successfully ran as the Progressive Conservative candidate representing Lincoln County in the federal election. He won the election by a 10 000 vote majority. He served his constituents in Ottawa until he was defeated in the 1962 election. After leaving politics Mr. Smith was active in his community. He spearheaded the establishment of the St. Catharines Museum, and then was appointed its first director in 1966, serving in that capacity until 1972. He was an active member of the board of governors of the St. Catharines General Hospital and a life member and former president of the Lincoln County Humane Society. In 1971 he was voted Citizen of the Year for the city of St. Catharines. John Smith died on February 8, 1977 and was buried at Victoria Lawn Cemetery. Source: The St. Catharines Standard, February 9, 1977, page 1