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.

Breeding parameters of great cormorants (Phalacrocorax carbo carbo) at mixed species colonies on Prince Edward Island, Canada

Breeding parameters of Great Cormorants (PkaZac/iOCOfiCLX CCUibo dCUtbo) and Double-crested Cormorants (P. CLU/uXuA CMJhLtllb) were examined at two mixed species colonies at Cape Tryon and Durell Point, Prince Edward Island from 1976 to 1978. Differential access to nests at the two colony sites resulted in more complete demographic data for P. CCUibo than for P. CLUJiituA. In 1911j P. CCtfibo was present at both colonies by 21 March, whereas P. auAAJtuA did not return until 1 April and 16 April at Cape Tryon and Durell Point, respectively. Differences in the arrival chronology by individuals of each species and differences in the time of nest site occupation according to age, are suggested as factors influencing the nest site distribution of P. CXUtbo and P. aiVtituA at Cape Tryon. Forty-eight P. dOJtbo chicks banded at the Durell Point colony between 19 74 and 19 76 returned there to nest as two- to four-year olds in 19 77 and 19 78. Unmarked individuals with clutch-starts in April were likely greater than four years old as all marked two to four-year olds (with one possible exception) in 19 77 and 1978 had clutch-starts in May and June. Seasonal variation in the breeding success of P. dOJibo individuals was examined at Durell Point in 1977. Mean clutch-size, hatching success and fledging success exhibited a seasonal decline. Four- and 5-egg clutches represented the majority (75%) of all P. CCUibo clutches at Durell Point in 1977 and had the highest reproductive success (0.48 and 0.43 chicks fledged per egg laid respectively). Smaller clutches produced small broods with significantly higher chick mortality while larger clutches suffered high egg loss prior to clutch completion.

The crystal and molecular structure of thiamine hydroiodide /|nWilliam Edward Lee. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The x-ray crystal structure of thiamine hydroiodide,C1ZH18N40S12' has been determined. The unit cell parameters are a = 13.84 ± 0.03, o b = 7.44 ± 0.01, c = 20.24 ± 0.02 A, 8 = 120.52 ± 0.07°, space group P2/c, z = 4. A total of 1445 reflections having ,2 > 2o(F2), 26 < 40° were collected on a Picker four-circle diffractometer with MoKa radiation by the 26 scan technique. The structure was solved by the heavy atom method. The iodine and sulphur atoms were refined anisotropically; only the positional parameters were refined for the hydrogen atoms. Successive least squares cycles yielded an unweighted R factor of 0.054. The site of protonation of the pyrimidine ring is the nitrogen opposite the amino group. The overall structure conforms very closely to the structures of other related thiamine compounds. The bonding surrounding the iodine atoms is distorted tetrahedral. The iodine atoms make several contacts with surrounding atoms most of them at or near the van der Waal's distances A thiaminium tetrachlorocobaltate salt was produced whose molecular and crystal structure was j~dged to be isomorphous to thiaminium tetrachlorocadmate.

The pancreatic islet system of the rock bass /|nby Edward Francis Squires. -- 260 St. Catharines, Ont. : [s. n.],

The endocrine pancreas of the rock bass (Ambloplites rupestris) was examined by light and electron microscopy. Two cell types with staining properties similar to mammalian A and B cells, and a third, non-staining cell type were found in the spherical pancreatic islets that were surrounded by a connective tissue capsule and embedded in two small masses of exocrine tissue. From an analysis of the ultrastructure of the A and B cells, a secretory cycle for each of these cell types was proposed. The secretory cycle of the A cell consisted of three well defined stages: (1) A cell production stage: during which A granule formation occurred in the sacs of the Golgi apparatus and the cell was characterized by the presence of numerous secretory granules, some elements of lamellar endoplasmic reticulum, and a homogeneously granular nucleus. The cytoplasm contained few distended cisternae, variable numbers of free ribosomes, microtubules and small vesicles. (2) A cell release stage: during which the release of A granules occurred and the cell usually contained several large distended cisternae and variable numbers of secretory granules. Granule release mechanisms included exocytosis, by which individual granules were released into the extracellular space after their membranes fused with the plasmalemma, and emiocytosis, by which one or more granules were released into a large cisterna whose membrane fused with the plasmalemma and formed a pore through which the cisternal contents passed out of the cell. (3) A cell reorganization stage: during which the changeover from the release stage to the production stage occurred and the reorganization of organelles and membrane structures took place. The cell contained few secretory granules and numerous small endoplasmic reticular cisternae. The cytoplasm exhibited less electron density than either of the other two stages. The A granule after formation underwent a series of morphological changes which were described in four numerically identified phases. The secretory cycle of the B cell consisred of two stages: (1) B cell production stage: during which the B granule formation occurred in the sacs of the Go1gi apparatus. The cell was characterized by an irregular outline, the presence of numerous secretory granules, and an irregularly shaped nucleus which contained variable amounts of clumped chromatin. The cytoplasm contained moderate amounts of lamellar endoplasmic reticulum studded with ribosomes, several small vesicles, and an active Go1gi apparatus. (2) B cell release stage: during which the release of B granules occurred. The cell contained a rounded nucleus with dispersed chromatin, several distended endoplasmic reticular cisternae and a variable number of secretory granules. Granule release occu~ by emiocytosis and exocytosis similar to that found for the A cell.

Canada seventy years ago : or, Prince Edward's visit to Niagara /

Verse.

City of the Falls clippings, 1833, n.d.

The clippings describe the City of the Falls and its attempts by its shareholders to sell lots to this newly developing city. The venture by shareholders W. Allan, James Buchanan, Thomas Clark, J.H. Dunn, Thomas Dixon, General Murray, James Robinson, Samuel Street and William Witla intended to favourably position their city as a destination for “affording an easy approach for the annual assemblage of the Fashionable, the Learned and the Great”. The venture failed due to the building of the Buffalo and Niagara Falls railway.

Custom House Niagara forms, 1833

In 1833 William Clarke, the collector of customs at Niagara, completed and signed four forms for the movement of goods between Niagara and York, and Niagara and Brantford. The forms were issued to the firm of Lewis & Gray, James Armstrong, J.A. Wilks, and William Blackely. The goods being transported included scythes, corn brooms, hide whips, sacks, snuff, shovels, spades and two apple trees.

Edward Mirynech fonds, 1913-1914, 1946, 1952-1957, 1959-1960, 1965-1982, n.d.

Edward Mirynech joined the faculty at Brock University in 1964 as assistant professor of Geology. Edward Mirynech, the son of John and Katherine Mirynech, grew up in St. Catharines, attended Connaught Public School and received his formal education at the University of Toronto. Dr. Mirynech played several critical roles in the early development of the University. In addition to teaching, Dr. Mirynech was also the acting director of the athletics department, a coach for many of the early rowing, hockey and basketball teams and served the University as marshall for the sod turning ceremony for the new DeCew campus in 1965. Dr. Mirynech was instrumental in the founding of the physical education, geography and geological sciences programs. He served as acting chairman in 1968 when the department of geological sciences enrolled its first students. Part of the unique teaching program was the annual field trips to locations such as the Belleville area, extended summer teaching programs held in Trinidad-Tobago and the following year in Iceland. In 1972, the first graduation ceremony ever to be held in the Arctic, at Pond Inlet, NWT, made national news. Three geology students, on a study trip to the Arctic, received their degrees during a special ceremony. Dr. Mirynech was among the faculty team in Pond Inlet, NWT, representing Brock University. Dr. Mirynech retired from teaching in 1985, and passed away in 2004.

Gainsborough [Presbyterian] Church records, 1833-1836, 1841-1846, 1855-1857, 1860-1864, 1866 [photocopy]

The Gainsborough Presbyterian Church was organized prior to 1833, but no records were kept until this date. In 1809, the church was lead by Rev. Daniel Ward Eastman. In 1833 the church became part of the Niagara Presbytery of the American Presbyterian Church. The records include transfer of membership, records of marriages, lists of subscribers and session minutes. Photocopies from originals were made in 1977 by E. Phelps, University of Western Ontario, prior to their deposit with the United Church of Canada Archives, Toronto, Ont.

Niagara-Welland Power Company Limited fonds, 1833, 1852, 1904-1906, 1909, n.d.

The Welland Power and Supply Canal Company Limited, established in 1893 and incorporated in 1894 with a capital stock of $500,000. The aim of the company was to harness the natural water supply of the Niagara and Welland Rivers. In 1898 the Canadian Electrical News published a report by Henry Symons, QC outlining the main project of the company. This project involves the construction of a canal from the Welland River to the brow of the mountain at Thorold, a distance of 8 miles; the construction at Thorold of a power house, and from Thorold to Lake Ontario, a raceway by which to carry water into the lake. The estimate for the machinery to generate 100,000 horse power is £125,000; for transmission line to Toronto at a voltage of 10,000….The total estimate therefore amounts to £2,452,162, or roughly speaking, $12,000,000. Source: Canadian Electrical News, August 1898, p. 172. In 1899 the company officers petitioned the federal government desiring a name change to the Niagara-Welland Power Company Limited. Officers of the company were Harry Symons, President; Charles A. Hesson, Vice-President; and M.R. O’Loughlin, James B. Sheehan, James S. Haydon, Frederick K. Foster, directors; John S. Campbell, secretary-treasurer. The company’s head offices were located in St. Catharines, with a New York (City) office on Broad Street. In 1905 and 1909 the company petitioned the federal government for additional time to construct its works, which was granted. The company had until May 16, 1915 to complete construction. John S. Campbell (1860-1950) was a graduate of the University of Toronto and Osgoode Hall. During his university years John began his military career first in "K" Company, Queens Own rifles and then later as Commanding Officer of the 19th Lincoln Regiment, from 1906 to 1910. Upon his return to St. Catharines John Campbell served as secretary in the St. Catharines Garrison Club, a social club for military men begun in 1899. After being called to the Bar, he became a partner in the firm of Campbell and McCarron and was appointed to the bench in 1916, serving until retirement in 1934. Judge Campbell served as an alderman for several terms and was the mayor of St. Catharines in 1908 and 1909. He also served as the first chairman of the St. Catharines Public Utilities in 1914. John S. Campbell was married to Elizabeth Oille, daughter of Jerome B. and Charlotte (St. John) Oille. The family home "Cruachan" was located at 32 Church St.

Welland Canal Survey of Lands Village Lot in Allanburgh, 1833

Survey map and description of a village lot in Allanburgh. Created by The Welland Canal Company. Included is a written description of the land along with a drawing of the lot. Noteable features include; Holland road, grave land, Niagara street. The land totals 3/4 of an acre. Surveyor notes are seen in pencil on the map.

Welland Canal Survey of Lands Village of Allanburgh, 1833

Survey map and description of the Village of Allanburgh, created by The Welland Canal Company. Included is a drawing of the land. Noteable features include; lot divisions, Welland Canal, Niagara street, Holland road, lock 36 and 37, foundry, Canal street, mill, Canby street, Dover street, Rose street, Helen street, Water street, Falls street, Centre street, Welland street, Hall street, Clifton street, James street, Mary street, Catherine street, J.G. Stockley's land, reservoir, graveyard. Surveyor notes are seen in pencil on the map.

Plan of part of the lands of the Six Nations Indians, January 26, 1833

A plan of part of the lands of the Six Nations Indians, dated January 26, 1833. A note on the plan reads “Part of the lands of the Six Nations Indians as surveyed by order of their Superintendent, John Brant, Esq. Dated at the Mohawk Village, the 29th day of April, 1831. Part of which was returned to the office of the Honourable, the Commissior of Crown Lands, on the 31st Oct. 1831, and now rendered more complete by a continuation of the survey under the same order in 1832, and by information obtained from private practice not connected with my official instructions all of which is most respectfully submitted to the inspection and for the information of His Majesty’s Government by Lewis Burwell, Surveyor”. The map shows the early loyalist land holdings in the Brantford area.

Indenture between Captain Thomas Bushby and Sarah Bushby and Edward Clarke Campbell

Indenture of bargain and sale between Captain Thomas Bushby of the Island of Jersey and his wife Sarah Bushby to Edward Clarke Campbell of the town of Niagara regarding 100 acres in Sherbrooke Forest in the District of Niagara, also Lots 6 and 7 in the town plot of Sherbrooke. This document was registered in the Township of Sherbrooke on December 28, 1849 - instrument no. 503, March 17, 1849.