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.

Copies of two dispatches upon the subject of the Welland Canal, 1827-1828

The material is a printed record of two dispatches sent by Sir Peregrine Maitland, Lieutenant Governor of Upper Canada to secretary of state for the colonies, the first in 1827 to Earl Bathurst, the second in 1828 to Right Hon. W. Huskisson. The dispatches concern funding for the canal as well as an introduction of William Hamilton Merritt as managing agent of the Welland Canal Company. It was the intention of the Welland Canal Company to send Mr. Merritt to England to gain further assistance from the government and private investors.

William Van Every fonds, 1784, 1804-1806, 1815-1816, 1828, 1832, n.d.

William Van Every, son of McGregory and Mary Wilcox (Jaycocks) Van Every, was born in New York state in 1765. During the Revolutionary War he joined Butler’s Rangers and served under Captain John McDonnell. He was granted three lots of land in the Township of Niagara, with additional lands granted at later dates. William married Elizabeth, daughter of George Young. Elizabeth was the widow of Col. Frederick Dochstader and mother of Catherine Dochstader, b. 1781. William Van Every died in 1832, his wife Elizabeth in 1851. Both are buried in the Warner Cemetery, in present day Niagara Falls. The children of William Van Every and Elizabeth Young were Mary, Elizabeth, Phoebe, John, Peter, William, Rebecca, Samuel and Joseph. Source: Mary Blackadar Piersol, The Records of the Van Every Family, Toronto : Best Printing, 1947. And, Patricia M. Orr, Historic Woodend, sponsored by Niagara Peninsula Conservation Authority, 1980?

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.

John R. Tenbroeck, 1828

Survey map and description of John R. Tenbroeck'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; the canal, bank of 12 mile creek. Surveyor notes are seen in pencil on the map. The land was surveyed by both Geo. Keefer and Wm. Rykert.

Welland Canal Survey of Lands Samuel Wood Esquire, 1828

Survey map and description of Samuel Wood's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. The same description of the land is also in a deed dated Septmeber 16, 1828 (see county registry 739). Noteable features include; the canal, the tow path, the tow path bridge. Surveyor notes are seen in pencil on the map. The original deed for the land is dated May 16, 1828.

Welland Canal Survey of Lands Job Northrup 1828

Survey map and description of Job Northrup'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; 12 mile creek, dry dock. The land was used by the Welland Canal Company for canal and hydraulic purposes. The total amount of land surveyed is 10 acres, 3 roads and 20 perches. The deed for the land is dated January 23rd 1828. Surveyor notes are seen in pencil on the map.The surveyor's notes on the map itself are as follows: "the plot in red lines, containing 2 roads and 10 perches, was laid off by Geo. Keefer on Aug. 2nd, 1834 as an additional quantity of land required by the Company for Lock house and other purposes". "The dry dock quantity is 1.2-32" "1 1/2 acres of the above survey for Dry Dock company. Survey July 18th 1833 by Geo. Keefer."

Welland Canal Survey of Lands Hannah Secord 1828

Survey map and description of Hannah Secord'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 Parnell and Secord's land, lock no.6, tow path, line between Clendenning and Secord's land. Surveyor notes are seen in pencil on the map. The deed for the land is dated February 28th, 1828. The land is located on part of lot 16 in the 6th concession of the township of Grantham. In total there are 12 acres, and 17 perches.

Letter to Mr. Walsh, Registrar Office, 1836

The man to whom the letter is addressed is Francis Leigh Walsh who was a land surveyor and registrar. Mr. Walsh was born on March 12, 1789 in Harford County, Maryland to Thomas Welsh, a United Empire Loyalist. In 1793, his family moved to Norfolk County and in 1810, Francis succeeded his father as registrar for Norfolk County. During the War of 1812 he served in the local militia and became a captain in 1824. He was the representative for Norfolk in the legislative assembly of Upper Canada from 1820 to 1828 and 1834 to 1836. He became justice of the peace in the London district in 1821 and 1838 in the Talbot district. He died in Simcoe on Oct. 14th, 1884. His son, Aquila Walsh served in the Legislative Assembly of the Province of Canada and in the Canadian House of Commons. Benjamin Hardison was born in Berwick in the Thirteen Colonies (British colonies on the Atlantic Coast of North America) on April 2, 1757 to Thomas Hardison and Mary Chadbourne. He was a farmer, miller and political figure. He was the representative for 4th Lincoln and Norfolk in the Legislative Assembly of Upper Canada from 1797-1800. On January 21, 1800 he married Jane Warren. He served with the American forces during the American Revolution at which time he was taken prisoner and sent to Canada. Later, he settled in Fort Erie where he was a captain in the militia and a justice of the peace for the Niagara district. He operated mills and a distillery in Fort Erie and died there on July 26, 1823. Source: http://en.vionto.com/show/me/Francis+Leigh+Walsh http://en.wikipedia.org/wiki/Benjamin_Hardison

Legal document involving John D M’Kay, Thomas Butler, and John Harris, February 5, 1828

Richard Leonard was a member of the 104th Regiment of the British Army. He fought during the War of 1812 at Sackett’s Harbour, Lundy’s Lane and Fort Erie. After the war he settled at Lundy’s Lane and was appointed lieutenant colonel of the 1st Lincoln Militia. He later became the Sheriff of Niagara. He died in 1833 and is buried in the Drummond Hill Cemetery.

The Niagara Herald May 22, 1828

The Niagara Herald was published from January 1828-1830 by James Gedd for James Crooks. This issue has Joseph Pell’s name written on the front page, May 22, 1828.

Farmers’ Journal, Welland Canal Intelligencer, St. Catharines, December 10, 1828

Farmers’ Journal, Welland Canal Intelligencer, St. Catharines, the names Gore Gasette and E.W. Banting are written on the front page, December 10, 1828.