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 Widow Griffith, 1824

Survey map and description of Widow Griffith'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 Chippewa river, canal, bridge, road. The deed is from Jonathan and Sarah Silverthorn and is dated August 15, 1824. The survey was completed by George Keefer. The land totals 1 acre and 38 perches. Surveyor notes are seen in pencil on the map.

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

Property Lost, Captured, or Destroyed by the Enemy 1812-14 (1824)

Government report in congress discussing property lost, captured, or destroyed by the British during the War of 1812.

Payment for Property - War of 1812-14 (1824)

Government report in congress discussing payment for property during the War of 1812.

St. Ursula's convent, or, the Nun of Canada: Containing scenes from real life. (1824)

"...the first novel ever written by a native-born Canadian"

Proposal for Construction of Brock’s Monument, Queenston, newspaper fragment, 1824

Brock’s Monument is owned by Parks Canada and maintained by the Niagara Parks Commission in collaboration with the Friends of Fort George and Niagara National Historic Sites. It is located in Queenston Heights Park atop the Niagara Escarpment. On March 14, 1815, Parliament passed an act to erect a monument to the memory of General Isaac Brock. A design by engineer Francis Hall was selected. He envisioned a 135 ft. tall Tuscan column, made out of stone with a winding staircase inside. By the spring of 1824, work had begun on the monument. In June of that year, the cornerstone was laid and William Lyon Mackenzie was in attendance at the ceremony. It was on October 13th, 1824 (the anniversary of Brock’s death) that 6000 people traveled to Queenston to inter the remains of Brock and Lieutenant-Colonel Macdonell. This was the second burial for both. After 3 years the tower had reached 135 feet, but there was no inscription at the base, the fence around the observation deck had not been installed and there was no statue of Brock. Hall submitted a plan to finish the statue, but he was turned down and a simple ornament was placed where the Brock statue should have been. A massive blast of gunpowder destroyed the monument in 1840. It is alleged that an American sympathizer with the Upper Canada Rebellion set off the blast. Brock and Macdonell’s bodies were reburied in the Hamilton Family Cemetery in Queenston. The present monument was rebuilt in 1853. William Thomas (designer of St. Michael’s Cathedral in Toronto) was the architect. Brock and Macdonell were once again laid to rest in separate vaults at the statue. In 1968, Brock’s Monument was declared a national historical site. In 2005, it was closed to the public due to safety concerns, but it reopened in 2010. Source: http://www.thecanadianencyclopedia.com/articles/brocks-monument-queenston-heights

Act of Parliament Preventing Private Distillation, Scotland, 1824

The Act begins: "An Act to continue, until the Tenth Day of November One thousand eight hundred and twenty-six, certain Parts of an Act of the Third Year of His present Majesty, among other Things for the preventing private Distillation in Scotland"