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.

Reflections upon the late correspondence between Mr. Secretary Smith, and Francis James Jackson, esq., Minister Plenipotentiary of His Britannic Majesty /

Originally published in the Federal Republican of Baltimore.

Hugh Alexander Papers, 1811-1816 [photocopy]

Hugh Alexander, b. 1780 arrived in Niagara shortly after his birth. He attended school and later apprenticed as a clerk. In 1797 he was granted 200 acres of land in Bertie township and became a merchant and trader in Fort Erie. He was the owner of a sailing vessel, the Chippawa, which he used to transport goods in the area. The ship was lost and/or confiscated as a result of War of 1812 skirmishes on Lake Erie. By 1812 Hugh Alexander was in business together with his brother Ephraim. The Alexander’s storehouse, store and house were burned by the British military when they abandoned Fort Erie ahead of the invading American military in late May 1813. At the time of the burning, Hugh Alexander was engaged as a Lieutenant with the 3rd Lincoln Militia. Prior to this Hugh Alexander had established a second mercantile in Stamford, opposite the green. Misfortune was to strike at this location as well when the British military abandoned the whole of the Niagara area to the invading American forces and the Stamford location was looted. After the end of the hostilities Alexander went on to rebuild his storehouse in Fort Erie and to re-establish his store in Stamford. Hugh Alexander died on November 2, 1817 and is buried in the Stamford Presbyterian Cemetery. Source: George A. Seibel, The Niagara Portage Road: 200 Years 1790-1990. Niagara Falls: City of Niagara Falls, 1990, p. 259-262.

Welland Canal Survey of Lands Christian May, 1831

Updated survey description of William May's land created by The Welland Canal Company. The land is now in the posession of Christian May as he was the heir for the property. The drawing for the property is the same drawing that goes with Peter May's land. It is marked as 'D' on that drawing. The land is described as 1 acre, with no roads on the property. Click on 'detail' for Peter May's property to see the map.

Welland Canal Survey of Lands Alexander Nickerson 1826

Survey map and description of Alexander Nickerson'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; locks no. 7, 8, 9, 10, line between Soper and Phelps land, concession line, Millard, sawmill, line between Phelps and Dittrick's land. Surveyor notes are seen in pencil on the map. The deed for the land is dated August 23, 1826. This land is owned by Alexander Nickerson, taken to be used by the Welland Canal Company and at the time of the survey was in the posession of Oliver Phelps. The land totals 15 acres, 2 roads, and 20 perches.

Welland Canal Survey of Lands George Marlatt 1826, 1831

Two survey maps and descriptions of George Marlatt's land created by The Welland Canal Company. The first is from 1826, as described in the deed of November 21, 1826. The second survey was done on August 29, 1831 by George Keefer. Included is a written description of the land along with a drawing of the land. Noteable features for the first survey (p.85) include; line between Kelly and Marlatt's land, lot division. Noteable features for the second survey (p.87) include; road to Beaverdams, reservoir, bridges, road allowance, lot divisions, line between Kelly and Marlatt's land. Surveyor notes are seen in pencil on the map.See also Page 90-91

Welland Canal Survey of Lands Andrew Wilson 1831

Survey map and description of Andrew Wilson'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 Marlatt and Wilson's land, canal. The land is a total of 23 acres, 1 road, and 33 perches. Surveyor notes are seen in pencil on the map. The land was surveyed by George Keefer in August 1831.Survey notes are on page 89, map is on page 91 and includes George Marlatt's land.

Welland Canal Survey of Lands John Watson, 1831

Survey map and description of John Watson'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 totals 2 acres, 1 road, and 21 perches. The land was surveyed on September 5th, 1831.

Welland Canal Survey of Lands St. Catharines Ditch, 1831

Survey map and description of the St. Catharines ditch land created by The Welland Canal Company. Included is a one and a half page written description of the land along with two drawings of the land. For the first drawing (p.156) noteable features include; line between Soper and O. Phelps land, road along the canal, Phelps mill, brewery, lock no. 5. For the second drawing (p.157) noteable features include; aquaduct, wood land, concessions, old distillery, line of company's land. Surveyor notes are seen in pencil on the map.See Pages 154-157

Reflections upon the late correspondence between Mr. Secretary Smith, and Francis James Jackson, esq., Minister Plenipotentiary of His Britannic Majesty

Originally published in the Federal Republican of Baltimore. Printed by Benjamin Edes

H.A.S. Dearborn letter, May 29, 1812

H.A.S. (Henry Alexander Scammell) Dearborn (1783-1851) was the son of Henry Dearborn, the American politician and veteran of the Revolutionary War and War of 1812. In the War of 1812, H.A.S Dearborn served as Brigadier General of the volunteer forces, responsible for the defence of Boston Harbour. From 1812-1829 he was collector of customs in Boston, from 1831-1833 he served as a representative from Massachusetts in the United States Congress, was adjutant general of Massachusetts from 1834-1843 and mayor of Roxbury from 1847-1851. Letter transcription: Dear Sir, My success in the line of recruiting has exceeded my most sanguine expectations. I have enlisted 24 1st Lt. 30—my 2nd Lt. 13, and my Ensign 9—Total 76. All very [ablebodied] men. In all probability my company will be full before the last day of June. I shall be in Boston on the 10th of June. I have not yet had the pleasure to hear of the arrival of your father at Boston. Please to offer my respects to your family, and to all my friends in the [office]. In haste, Yours, A.M. Clary.

A review of the case of Alexander McLeod: recently determined in the Supreme Court of Judicature of the state of New York (1841)

Alexander McLeod, a British subject, was tried for the murder of Amos Durfee and as an accomplice in the burning of the steamer Caroline, in the Niagara River, during the Canadian rebellion in 1837-1838.

Probate of Last Will and Testament of Alexander Simpson of Crowland Township

Probate of Last Will and Testament of Alexander Simpson of Crowland Township, January 29, 1872.

Indenture between Samuel DeVeaux Woodruff and Alexander Pettigrew

Indenture regarding articles of agreement between Samuel DeVeaux Woodruff of St. Catharines and Alexander Pettigrew of Merritton for parts of building lots 17, 18 and 19 of the Clifford Tract in Merritton (2 copies), Oct. 21, 1899.