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.

Welland Canal Survey of Lands Abraham Augustine, 1837

Survey map and description of Jacob Augustine's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. The land surveyed is lot #26 in Humberstone.Noteable features include; canal, concession, line between Abraham and Jacob Augustine's land. The land totals 7 1/4 acres. Surveyor notes are seen in pencil on the map.

Welland Canal Survey of Lands Jacob Augustine, 1837

Survey map and description of Jacob Augustine's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. The land surveyed is lot #27 in Humberstone. Noteable features include; canal, concession, line between Neff and J. Augustine's land. The land totals 8 acres. Surveyor notes are seen in pencil on the map.

Letter to Mr. Henry H. Collier, 1837

Henry Haight Collier, was born in Howard, Steuben County, N. Y., November 28, 1818. His father, Richard Collier, was from Green County, in the same State. His grandfather, Isaac Collier, and his great-grandfather were originally from England. His mother, Mary Haight, was of Dutch origin. In 1835, Henry went to St. Catharines, where his elder brother, Richard Collier, resided. He spent two years at Grantham Academy, and then returned to Steuben County, to read law in Bath, with Edward Howell, and subsequently with Hammond and Campbell. Mr. Collier never opened a law office. He studied law for two years and in 1839 he went to Texas where he was connected with the State and Treasury Departments. In 1845 Mr. Collier returned to St. Catharines and opened a general store called St. Catharines Agricultural Works with his brother. The store remained open until May, 1877. He added the manufacturing of lumber in 1850, and manufacturing of agricultural implements in 1869. He built one of the first saw mills on the canal, on Lock No. 5, in St. Catharines. In July, 1877, he was appointed Collector of Customs. He became a Village Councilor for St. Paul’s Ward in 1859, and held that office from fifteen to twenty years. He was Deputy Reeve and member of the County Council for two terms. He was the Mayor of St. Catharines in 1872 and 1873. He was also Chairman of the Board of Water Commissioners of the city, during the time that the works were being built. He was a Justice of the Peace for twenty years or more. Mr. Collier was affiliated with the Reform Party and he was a Knight Templar in the Masonic fraternity and an Odd Fellow. He was also active in the Methodist Church. On June 1, 1858, he married Cornelia, daughter of Moses Cook, of "Westchester Place," St. Catharines, and had a daughter and son. Mary J. (married name: Mrs. Frank Camp) was a graduate of the Female Seminary at Hamilton, and Henry Herbert was a student in the University of Toronto. Henry H. Collier died on July 15, 1895 and is buried in Victoria Lawn Cemetery, St. Catharines, Ontario. Sources: www.accessgeneology.com "Historical Profiles from Victoria Lawn Cemetery" by Paul E. Lewis "Sincerely Lamented St. Catharines Obituaries 1817-1918" by Paul Hutchison

Letters to the Honourable John H. Dunn, 1837-1838

The recipient of the letters is John Henry Dunn who was born on St. Helena (a British territory island of volcanic origin located in the South Atlantic Ocean) in 1792 to John Charles Dunn and Elizabeth Bazette. He was married to Charlotte Roberts on May 4th, 1820 and they had 6 sons and 2 daughters. He came to Canada in 1820 in which year he became the Receiver General for Canada. He held this position until 1841.Charlotte died in 1835. In 1822 he was named to the Province’s Legislative Council. He was president of the Welland Canal Company from 1825-1833. In 1836 he was named to the executive council of Upper Canada but resigned 3 weeks later with fellow counselors when lieutenant governor Sir Francis Bond refused the advice of the council. Dunn was made the Receiver General for the newly formed Province of Canada in 1841, and was elected to represent Toronto in the legislative assembly that year. He married his second wife on March 9th, 1842. Her name was Sophie-Louise Juchereau Duchsnay. They had a son and a daughter. In 1843 he resigned, and was not re-elected in 1844. He returned to England with his family and died in London on April 21, 1854. Dunn was a supporter of the Welland Canal, St. Lawrence Canals and other public improvements. Between the passage of the Canada Trade Act and the Act of the Union he had tried to insure that projects received funding despite financial constraints. He claimed that he has saved Upper Canada from bankruptcy. His son, Alexander Roberts Dunn received the Victoria Cross for his role in the Charge of the Light Brigade at Balaclava. Dunn Street in Niagara Falls is named after John Henry Dunn. The town and township of Dunnville were also named for him. Sources: http://biographi.ca/009004-119.01-e.php?id_nbr=3889 http://www.niagarafrontier.com/cityfalls.html

Dr. Stuart D. Scott Papers, 1837-2010 (non-inclusive)

Dr. Stuart D. Scott has written extensively in the fields of prehistory and history. As an archaeologist, he has traveled to some of the most significant sites in the world, including Pompeii, Stonehenge, the Valley of the Kings, Egypt’s pyramids and the Taj Mahal. He spent nine months excavating with the Tikal Project in Guatemala before returning to the University of Arizona where he received a Ph.D. in 1963. He excavated in New Zealand as a Fulbright scholar in 1963-1964. In the fall of 1964, Dr. Scott started a long career in the Anthropology Department of the State University of New York. He taught graduate and undergraduate archaeology courses and continued his archaeological and historical research. In 1979, Scott established the Old Fort Niagara Archaeology in Progress Project at Old Fort Niagara in Youngstown, New York. For many years, he became involved with historical archaeology in western New York. It was during this work that he became interested in the Upper Canada Rebellion of 1837-1838 and its aftermath. Dr. Scott and his wife, Patricia Kay Scott, would use Christmas breaks, summer vacations, and sabbatical years to travel. They were repeatedly lured back to the South Pacific, conducting research in New Zealand, Australia and many of the Micronesian and Polynesian islands. To tell the whole story of the Rebellion and the prison exiles, they traveled extensively in Canada, the United States, England and Tasmania to collect archival research and to experience the scenes of this remarkable narrative. In 2004, Dr. Scott published To the Outskirts of Habitable Creation: Americans and Canadians Transported to Tasmania in the 1840s, which told the story of the men captured, tried, convicted, and exiled as a result of the Rebellion, also called the Patriot War. Other contributions include: • A collaboration with Dr. Charles Cazeau on the book Exploring the Unknown, Great Mysteries Reexamined published by Plenum Press in 1979 • The Patriot Game: New Yorkers and the Canadian Rebellion of 1837-1838, which appeared in New York History, Vol. 68, No.3. 1987 • A Frontier Spirit: The Life of James Gemmell published in Australiasian Canadian Studies, Vol. 25, No. 2 2007 • To the Outskirts of Habitable Creation which appeared in the Friends of the National Archives, Vol. 20, No. 1 2009 • Numerous academic journal publications • Service on conference panels • Various research papers and proposals Before retiring in 1997 and while still a resident of Buffalo, N.Y., Dr. Scott spent considerable time with Brock University President Emeritus James A. Gibson and History Professor Colin Duquemin. The three shared a love of Rebellion history. It was largely because of this connection that Brock University was chosen as the recipient of Dr. Scott’s research materials.

Niagara Ship Canal [to accompany Bill H.R. no. 921], February 14, 1837 (1837)

Mr. Hard, from the Committee on Roads and Canals, made the following report.

Journal of the House of Assembly of Upper Canada (1836-1837) (1837)

The earlier Journals of the House of Assembly are to be found in: Ontario. Bureau of Archives. Report of the Bureau of Archives for the Province of Ontario (where they have been printed due to their non-existence in their original form.).

Photograph - Lorenzo Lamas, Laura Dickson, Donald Ziraldo

A photograph of Lorenzo Lamas, Laura Dickson and Donald Ziraldo at the Winetasting Inn on the Park November 1986.

Ann Eliza Hepburne Rooth fonds, 1837-1897

Ann Eliza Hepburne was born in Chippawa, Ontario, in 1821, to William Hepburne and Susan Shannon. In 1842, she married William Anthony Rooth in St. James Cathedral in Toronto. They continued to live in different parts of the Niagara region, including Drummondville, Welland and Port Colborne. William was the editor and proprietor of the Drummondville Reporter, as well as an accountant and insurance agent, and later worked for the Customs Service in Port Colborne. He died in 1878, and Eliza in 1899. Both are buried in Drummond Hill Cemetery in Niagara Falls, Ontario.

The Constitution, Toronto, Upper Canada, March 1, 1837

The Constitution, Toronto, Upper Canada, March 1, 1837.

The Constitution, Toronto, Upper Canada, April 12, 1837

The Constitution, Toronto, Upper Canada, April 12, 1837.

The Constitution, Toronto, Upper Canada (2 copies), September 6, 1837

The Constitution, Toronto, Upper Canada (2 copies), September 6, 1837.