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.

Letter Regarding Ensign Daniel Shannon's Military Pay from the Commissariat Office- 30 May 1817

A letter stating that Military Half Pay would from then on be paid from the Commissariat Office. As a result, they require a new letter of attorney. It also states the half pay amount of Daniel Shannon.

The Gleaner and Niagara Newspaper, December 18th, 1817

The Gleaner and Niagara Newspaper was a weekly paper in the town of Niagara-on-the-Lake that began publication December 4, 1817 and ceased in 1830. This bound volume has been divided by publication dates. Other dates included in the volume are: 25 December 1817 1818 January 1 1818 January 8 1818 January 15 1818 January 22 There is also a letter that was found inside the bound volume written by Andrew Heron on October 1 1817.

The Gleaner and Niagara Newspaper, December 25th, 1817

The Gleaner and Niagara Newspaper was a weekly paper in the town of Niagara-on-the-Lake that began publication December 4, 1817 and ceased in 1830. This bound volume has been divided by publication dates. Other dates included in the volume are: 1817 December 18 1818 January 1 1818 January 8 1818 January 15 1818 January 22 There is also a letter that was found inside the bound volume written by Andrew Heron on October 1 1817.

Naval Occurrences of the Late War Between Great Britain and the United States of America- 1817

Full title is "A Full and Correct Account of the Chief Naval Occurrences of the Late War Between Great Britain and the United States of America; preceded by a Cursory Examination of the American Accounts of their Naval Actions Fought Previous to that Period: to Which is Added an Appendix; with Plates" This is an expanded version of author William James' pamphlet "An Inquiry into the Merits of the Principal Naval Actions between Great Britain and the United States." (Halifax, Nova Scotia, 1816) In this work he discussed how American ships, during the War of 1812, were larger and more heavily armed and manned than those of the British. He therefore, stated that American victories were due only to their greater numerical force and not their superior seamanship. Naval Occurrences is a thorough documentation of the naval operations from the British perspective that addresses contradictions and inconsistencies within the American official documents as well as political and media accounts. This is perhaps his motivation for the words "Corrected Account" within the title. James' sentiments towards the US most likely sprouted from being held prisoner while visiting in 1812. (He was falsely accused of being a renegade seeking revenge on the US.) In 1813, he escaped to Halifax where he began writing on various naval topics. James became one of the leading authorities on British Naval History.

Report of the committee appointed to inquire what amendments are necessary to the Act granting bounties in land and extra pay to certain Canadian volunteers: January 11, 1817, read, and, together with the bill herewith reported, ordered to be printed. (1817)

Includes (p. 3-4) a letter from the Acting Secretary of War to the chairman of the committee dated Department of War, December 26th, 1816.

Report of a select committee to whom were referred the petition of Samuel Thompson and John Dailey: January 14, 1817, read, and ordered to lie upon the table (1817)

Concerning the request of the petitioners, former residents of Newark (present-day Niagara-on-the-Lake) in Upper Canada, for relief for the loss of their property when they were compelled to flee Canada after having aided the United States Army in the War of 1812.

The report of the Loyal and Patriotic Society of Upper Canada, with an appendix and a list of subscribers and benefactors (1817)

Minutes, accounts and other records, 1812-1816, of an association formed at York, to alleviate distress in Upper Canada resulting from war with United States.

Letter from Thomas Tudor Tucker, treasurer of the United States: transmitting his accounts for 1816, February 25, 1817

Bound with: Letter from the Secretary of the Treasury transmitting statements of the importations of goods, wares and merchandise... (60 p.).

Indenture Land Sold by Thomas Clark to Lewis Clement, 1817

Indenture regarding land sold by Thomas Clark of Stamford Township to Lewis Clement of Niagara Township. The land includes 50 acres in the northern half of Lot 58 in Niagara Township - instrument no. 5356, January 17, 1817.