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.

Developing and nurturing professional learning communities: principles used by elementary administrators /

This study examined the strategies used by elementary school principals to facilitate and nurture the development of professional learning communities (PLC) within their school settings. Using a reputational sample of administrators whose schools were demonstrating observable characteristics of PLCs, this study documented and described the strategies and actions taken by the principals to move their schools forward. Data collection included the use of open-ended interviews as well as observations capturing the means by which the principals addressed the areas of culture, processes, and structures within their school setting. A grounded theory approach to data analysis uncovered 4 guiding principles used by the principals to facilitate the development of the PLCs within their school: (a) protecting the purpose; (b) attending to relationships; (c) sharing the responsibility; and (d) valuing the journey. The guiding principles were used by each administrator to anchor the decisions they made and develop responsive, contextspecific strategies to support the PLC at their school. The results highlighted the complex role of the principal and the supports required to tackle the difficult work of facilitating PLCs.

A qualitative analysis of reflection in undergraduate and graduate programs

The purpose ofthis study was to explore various types ofreflection and to explore reflection on action, reflection as a practice, and reflection as a process. In doing this, the intent was to discover the perceived benefits of reflection in the classroom and to provide guidelines for future use at the undergraduate and graduate level. The qualitative components in this study included the data collection strategy of semistructured interviews with 2 undergraduate students, 2 graduate students, 1 undergraduate studies professor, and 1 graduate studies professor. The data analysis strategies included a within-case analysis and a cross-case analysis. Through the interviews participants discussed their experiences with the use ofreflection in the classroom. Through the completion ofthis analysis the researcher expected to discover the benefits ofreflection at this level of education, as well as provide suggestions for future use. Both undergraduate and graduate students and professors were found to benefit from the use of reflection in the classroom. The use ofreflection in the undergraduate and graduate classroom was found to improve student/teacher and student/peer relationships, foster critical thinking, allow for connections between learned theory and life experience, and improve students' writing abilities. Based on the results ofthe study the implications ofreflection for the undergraduate and graduate classroom and for further research are provided.

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.

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

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