Synthesis of 4-hydroxycinnamic amides of di-, tri-, and tetraamines : potential insect toxins /

The monoconjugates of phenolic acids (i.e. coumaric acid) with polyamines such as spermidine and spermine are strikingly similar to some toxins from spiders and predatory wasps. Many plants contain phenolic acid polyamine conjugates and there is some reliable information supporting their roles as plant defense chemicals. Eleven monoacylated compounds of diamines, triamines, tetraamines and oxa-polyamine amines were prepared in three to seven steps: 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 and 32. The synthesis proceeds through stepwise construction of the polyamine backbone (as in 62 and 72), followed by protection and deprotection steps of the amino functions. Desymmetrization of readily available and prepared symmetrical polyamines is a key step in the synthesis. The protecting groups employed were tert-butoxycarbonyl (BOC) and trifluoroacetyl (TFA) group which were removed under different conditions: acid and base respectively. Deprotection and refunctionalization of the polyamine reagent demonstrated the versatility of these systems for N-acylation.

Ethical space in a secondary school: a case study /

Discourse in the provincial education system that includes Aboriginal peoples is a convoluted one-sided affair. This has contributed to the limited academic success for Aboriginal secondary students in the provincial school system. The Office of the Auditor General (2004) announced a 27-28 year gap in Academic success compared to non- Aboriginal students (p. I). Both Aboriginal and non-Aboriginal stakeholders are fiiistrated and confused with the lack of support for long-term solutions to address academic success for Aboriginal students. The boundaries in education that exist between the dominant society of Canada and Aboriginal peoples in education are hindering the development of ethical space in which to negotiate and apply "concrete arguments and concepts" (Ermine, 2000, p. 140) for 'best' solutions across the cultural divide. Recent literature suggests a gap in knowledge to address this cultural divide. This study reveals racism is still prevalent and the problem lies in the fallacy of Euro-Western pedagogical beliefs. There is a need to design ethical space that will assist transformation of cross-relations in education for inclusion of Aboriginal voices and content. I submit that ethical space involves physical and abstract space. This report is a qualitative, exploratory, and single case study of one northern Ontario secondary school attended by First Nations and Metis peoples who comprise 35% of the school population. Twenty-six stakeholders volunteered to participate in six interviews. The volunteers in this study are Aboriginal and non-Aboriginal. Aboriginal peoples are firom two First Nations, and Metis peoples. It is an Aboriginal designed and delivered study that a) describes an Aboriginally-designed research method to gather data across cultural divides in a secondary school, b) reviews Tri-Council Policy Section 6 (TCPS) regarding 'good practices' in ethical research involving Aboriginal peoples, and c) summarizes stakeholder perspectives of the 'best educational environment' for one secondary school.

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.

Arsenic speciation by ion-exchange chromatography with on- line determination by hydride generation: electronic modification of the D.C. plasma by photon counting

A method using L-cysteine for the determination of arsenous acid (As(III)), arsenic acid (As(V)), monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) by hydride generation was demonstrated. The instrument used was a d.c. plasma atomic emission spectrometer (OCP-AES). Complete recovery was reported for As(III), As(V), and DMAA while 86% recovery was reported for MMAA. Detection limits were determined, as arsenic for the species listed previously, to be 1.2, 0.8, 1.1, and 1.0 ngemL-l, respectively. Precision values, at 50 ngemL-1 arsenic concentration, were f.80/0, 2.50/0, 2.6% and 2.6% relative standard deviation, respectively. The L-cysteine reagent was compared directly with the conventional hydride generation technique which uses a potassium iodide-hydrochloric acid medium. Recoveries using L-cysteine when compared with the conventional method provided the following results: similar recoveries were obtained for As(III), slightly better recoveries were obtained for As(V) and MMAA, and significantly better recoveries for DMAA. In addition, tall and sharp peak shapes were observed for all four species when using L-cysteine. The arsenic speciation method involved separation by ion exchange .. high perfonnance liquid chromatography (HPLC) with on-line hydride generation using the L.. cysteine reagent and measurement byOCP-AES. Total analysis time per sample was 12 min while the time between the start of subsequent runs was approximately 20 min. A binary . gradient elution program, which incorporated the following two eluents: 0.01 and 0.5 mM tri.. sodium citrate both containing 5% methanol (v/v) and both at a pH of approximately 9, was used during the separation by HPLC. Recoveries of the four species which were measured as peak area, and were normalized against As(III), were 880/0, 290/0, and 40% for DMAA, MMAA and As(V), respectively. Resolution factors between adjacent analyte peaks of As(III) and DMAA was 1.1; DMAA and MMAA was 1.3; and MMAA and As(V) was 8.6. During the arsenic speciation study, signals from the d.c. plasma optical system were measured using a new photon-signal integrating device. The_new photon integrator developed and built in this laboratory was based on a previously published design which was further modified to reflect current available hardware. This photon integrator was interfaced to a personal computer through an AID convertor. The .photon integrator has adjustable threshold settings and an adjustable post-gain device.

Studies of nucleophilic attack on tris (pentafluorophenyl) phosphine and its oxides

The reaction of tris(pentafluorophenyl)phosphine [5] with the nucleophiles dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPA), diethyl formamide (DEF), hexaethylphosphoric triamide (HEPA), hydrazine, N,N-dimethyl hydrazine (in presence and/or absence of KF), phenylhydrazine, ammonium hydroxide, formamide, aniline, sodium hydrogen sulfide, and hexaethylphosphorous triamide was investigated. The reaction of [5] with DMF and HMPA gave the same product, namely tris-[4-(N,N-dimethylamino)-2,3,5,6-tetrafluorophenyl]phosphine [12] but in higher yield in the case of HMPA. Compound (5] also reacted with DEF to give tris[4-(N,N-diethylamino)-2,3,5,6-tetrafluorophenyl] phosphine [14]. When [51 was treated with HEPA, it gave a mixture of bis(pentafluorophe~yl)-(N,N-diethylamino-tetrafluorophenyl)phosphine, pentafluorophenyl-bis-(N,N-diethylamino-tetrafluorophenyl)phosphine and tris (N,N-diethylamino-tetrafluorophenyl)phosphine. Treatment of [5] with aqueeus hydrazine solution in excess ethanol gave tris(4-hydrazo-2,3,4,6-tetrafluorophenyl)phosphine [1s1 in high yield while reaction with aqueous hydrazine led to C-P cleavage and production of tetrafluorophenyl hydrazine. With N,N-dimethyl hydrazine, [5] gave tris(4-N,N-dimethylhydrazine-2,3,5,6-tetrafluorophenyl) phosphine {20j. The latter could be obtained in higher yield and shorter reaction time, by the addition of KF. The reaction of compound {51 with phenylhydrazine in THF gave bis(pentafluorophe~yl)-4-S-phenylhydrazino- 2,3,5,6-tetrafluorophenyl phosphine [22] in low yield. Reaction of [5] with ammonium hydroxide in THF at high pressure in the presence of KF gave tris-~4-amino-2,3,5,6-tetrafluorophenyl)phosphine [25]. Similarly, formamide led to a mixture of (C6F4NHZ)3P, (C6F4NHZ)ZPC6FS, (C6F4NHZ)ZPC6F4NHCHO, and C6F4NHZP(C6Fs)(C6F4NHCHO). When [5] was treated with aniline, a mixture of mono-, di-, and tri-substituted products was obtained. Sodium hydrogen sulfide in ethylene glycol/ pyridine led to C-P cleavage and the isolation of pentafluorobenzene and tetrafluorothiophenol. Reaction of [5] and its oxide [35] with different alkoxides in the corresponding alcohols led mainly to C-P bond cleavage products, with the exception of one case where sodium methoxide was used in ether, and which led to tris-(4-methoxy-2,3,9,6-tetrafluorophenyl)phosphine [37]. On the basis of various spectroscopic data, it was concluded that the para position in compound [5] was generally the favoured site of attack.

Baltimore Patriot and Evening Advertiser Vol. 3 No. 89- April 15, 1814

This daily paper, except Sundays, began publication on August 17, 1813 and ceased April 30, 1817. It was also published tri-weekly for a "COUNTRY" edition. The paper later became the Baltimore Patriot. Topics of interest include: Page 1: announcement Capt. M. Simmones Burnbury is seeking men to form a company of Sea Fencibles; Page 2: U.S. Legislature authorizes bill to increase the Marine Corps; U.S. Legislature authorizes bill to purchase vessels captured on Lake Erie; U.S. Senate bill authorizes the appointment of officers for the flotilla service; President of United States authorized to accept service of volunteer corps for defence of United States; Letter from Capt. A. H. Holmes to Lieut. Col. Butler detailing an American victory over the British near Detroit; announcement of British forces building barges for the purpose of attacking Detroit; War sloop Erie returns to Baltimore unable to reach sea due to British forces in the Chesapeake; Page 3: Death notice of Mr. Ward Fairchild of the U.S. Army; Page 4: Commander of the U.S. Flotilla seeks men for the Chesapeake Flotilla.

National Intelligencer Vol. XIII, No. 1984- June 8, 1813

The Intelligencer was an American newspaper that was established, in 1800, in Washington by Samuel Harrison Smith, a young Jeffersonian- Republican from Philadelphia. The paper was a supporter of the Jefferson and Madison administrations until 1810 when it was sold to Joseph Gales Jr. from North Carolina. In 1812 William Seaton joined Gales as a publishing partner. This paper made significant contributions to the nation and wielded considerable influence in political circles during its publication. It has been praised for its "high standard of journalistic excellence and high intellectual level of its contents". (William E. Ames , National Intelligencer: Washington's Leading Political Newspaper) The Intelligencer was, until 1810, named the National Intelligencer, and Washington Advertiser. It was a tri-weekly paper and had a peak circulation of 6, 000. Publication was suspended in 1869.

National Intelligencer Vol. XIII, No. __91- June 24, 1813

The Intelligencer was an American newspaper that was established, in 1800, in Washington by Samuel Harrison Smith, a young Jeffersonian- Republican from Philadelphia. The paper was a supporter of the Jefferson and Madison administrations until 1810 when it was sold to Joseph Gales Jr. from North Carolina. In 1812 William Seaton joined Gales as a publishing partner. This paper made significant contributions to the nation and wielded considerable influence in political circles during its publication. It has been praised for its "high standard of journalistic excellence and high intellectual level of its contents". (William E. Ames , National Intelligencer: Washington's Leading Political Newspaper) The Intelligencer was, until 1810, named the National Intelligencer, and Washington Advertiser. It was a tri-weekly paper and had a peak circulation of 6, 000. Publication was suspended in 1869.

National Intelligencer Vol. XIII, No. 1993- June 29, 1813

The Intelligencer was an American newspaper that was established, in 1800, in Washington by Samuel Harrison Smith, a young Jeffersonian- Republican from Philadelphia. The paper was a supporter of the Jefferson and Madison administrations until 1810 when it was sold to Joseph Gales Jr. from North Carolina. In 1812 William Seaton joined Gales as a publishing partner. This paper made significant contributions to the nation and wielded considerable influence in political circles during its publication. It has been praised for its "high standard of journalistic excellence and high intellectual level of its contents". (William E. Ames , National Intelligencer: Washington's Leading Political Newspaper) The Intelligencer was, until 1810, named the National Intelligencer, and Washington Advertiser. It was a tri-weekly paper and had a peak circulation of 6, 000. Publication was suspended in 1869.

National Intelligencer Vol. XVI, No. 2193- October 15, 1814

The Intelligencer was an American newspaper that was established, in 1800, in Washington by Samuel Harrison Smith, a young Jeffersonian- Republican from Philadelphia. War of 1812 related content includes: Page 1: Major General Winfield Scott's arrival in Washington escorted by Colonel Laval's cavalry; report from Sackett's Harbour on the American and British navies; a debate on a bill to temporarily remove the seat of government from the City of Washington due to the war; the Military Committee wishing to have the President commission gold medals for distinguished service for Major Generals Brown and Scott and silver medals to Brigadier Generals Ripley, Miller and Porter for their efforts at Chippewa, Erie and Niagara as well as gold medals to Brigadier General Gaines for efforts at Erie and Brigadier General Macomb for efforts at Plattsburg; resolutions of the House on the victory of Commodore Thomas Macdonough at the Battle on Lake Champlain; Page 2: more detail on the proposed removal of the seat of government from Washington; Page 3: a letter from Major General Andrew Jackson to the Secretary of War on repelling the British at Fort Bowyer on the Point of Mobile and naval battle reports on the vessels Hermes, Sophie, and Carron; a letter from Major William Lawrence to Andrew Jackson on the battle at Fort Bowyer; military promotions of Alexander Macomb, Roger Jones, J. Hindman; more on the removal of the seat of government; citizens of Washington offering to volunteer in defense of the city; banks willing to loan the government funds to re-build destroyed government buildings; assignments of Major General Scott, General Winder and Major General Gaines; report of 300 British prisoners from Fort Erie passed through Washington; Montreal newspaper report condemning Provost for his actions at the Battle of Lake Champlain; trouble with stage coaches traveling between New Haven and Bridgeport due to cannon fire; report of a British naval squadron appearing off New Port and by Long Island and New Bedford; report of enemy naval movements from Norfolk; announcement of a book entitled "A Narrative of the Battle of Bladensburg" by and officer of General Smith; Page 4: report on the amassing navy at Kingston under Drummond and the defenses at Sackett's Harbor; report of American and British naval news from Nova Scotia and the east coast; actions of the American sloop of war, The Peacock, in international waters; an enlistment announcement by Captain Perrin Willis of the 2nd Regiment Infantry; listing of American officers and privates released from parole on October 13; Other notices report on stray horses, properties for sale, runaway slaves, imprisonments, missing livestock, medical lectures at the University of Maryland, stage lines, auctions, etc. The paper was a supporter of the Jefferson and Madison administrations until 1810 when it was sold to Joseph Gales Jr. from North Carolina. In 1812 William Seaton joined Gales as a publishing partner. This paper made significant contributions to the nation and wielded considerable influence in political circles during its publication. It has been praised for its "high standard of journalistic excellence and high intellectual level of its contents". (William E. Ames , National Intelligencer: Washington's Leading Political Newspaper) The Intelligencer was, until 1810, named the National Intelligencer, and Washington Advertiser. It was a tri-weekly paper and had a peak circulation of 6, 000. Publication was suspended in 1869.

ORGANOSILICON BIOTECHNOLOGY: A BIO-INSPIRED APPROACH TO THE HYDROLYSIS OF ALKOXYSILANES and THE LIPASE-CATALYZED SYNTHESIS OF SILOXANE-CONTAINING POLYESTERS AND POLYAMIDES

The first part of this thesis studied the capacity of amino acids and enzymes to catalyze the hydrolysis and condensation of tetraethoxysilane and phenyltrimethoxysilane. Selected amino acids were shown to accelerate the hydrolysis and condensation of tetraethoxysilane under ambient temperature, pressure and at neutral pH (pH 7±0.02). The nature of the side chain of the amino acid was important in promoting hydrolysis and condensation. Several proteases were shown to have a capacity to hydrolyze tri- and tet-ra- alkoxysilanes under the same mild reaction conditions. The second part of this thesis employed an immobilized Candida antarctica lipase B (Novozym-435, N435) to produce siloxane-containing polyesters, polyamides, and polyester amides under solvent-free conditions. Enzymatic activity was shown to be temperature dependent, increasing until enzyme denaturation became the dominant pro-cess, which typically occurred between 120-130ᵒC. The residual activity of N435 was, on average, greater than 90%, when used in the synthesis of disiloxane-containing polyesters, regardless of the polymerization temperature except at the very highest temperatures, 140-150ᵒC. A study of the thermal tolerance of N435 determined that, over ten reaction cycles, there was a decrease in the initial rate of polymerization with each consecutive use of the catalyst. No change in the degree of monomer conversion after a 24 hour reaction cycle was found.

Canada’s new Open Access Policy: what does it mean for Brock researchers?

Presentation at Brock Library Spring Symposium 2015: What's really going on?