New Building Blocks for Dual-Property Molecule-Based Magnets

Two classes of compounds have been prepared and characterized as building blocks for chiral magnets and ferromagnetic conductors. In the fIrst project, the organic framework of a pentadentate, (N302) macro cycle has been synthetically modifIed to introduce phenyl substituents into its organic framework and the synthesis of four new [Fe(In(N302)(CN)2] complexes (I) - (IV) is presented. [Molecular diagram availble in pdf] This work represents the fIrst structural and magnetic studies of a family of spin crossover macrocycles that comprise of both structural and stereo-isomers. Magnetic susceptibility and Mossbauer data for the R,R-complex (I) is consistent with both a thermal and a light induced spin crossover transition. The X-ray data supports a change in geometry accompanying the thermal spin transition, from a high spin (HS) 7 -coordinate complex at room temperature to a low spin (LS) 5-coordinate complex at 100 K. The crystal structure ofthe racemic complex (III) reveals a HS, 7-coordinate complex at 200 K that undergoes no signifIcant structural changes on cooling. In contrast, the magnetic - susceptibility and Mossbauer data collected on a powder sample of the racemic complex are consistent with a LS complex. Finally, the meso complex (IV) was prepared and its structure and magnetic properties are consistent with a 5-coordinate LS complex that remains low spin, but undergoes conformational changes on cooling in solution. The chiral [Fe(H)(N302)(CN)2] macro cycle (I), together with its Mn(H) and Fe(H) derivatives have also been exploited as building blocks for the self-assembly of chiral magnets. In the second project, a synthetic route for the preparation of tetrathiafulvalene (TTF) donors covalently attached to a diisopropyl verdazyl radical via a cross conjugated pyridyl linker IS presented. Following this strategy, four new TTF-py- (diisopropyl)verdazyl radicals have been prepared and characterized (V) - (VIII) . [Molecular diagram available in pdf] The first (2:1) charge transfer complex ofa TTF-py-(diisopropyl)verdazyl radical donor and a TCNQ acceptor has been prepared and structurally characterized. The crystal packing shows that the donor and acceptor molecules are organized in a mixed stacking arrangement consistent with its insulating behaviour. EPR and magnetic susceptibility data support intramolecular ferromagnetic interactions between the TTF and the verdazyl radicals and antiferromagnetic interactions between TTF donors within a stack. In an attempt to increase the intramolecular exchange interaction between the two radicals, a TTF-x-(diisopropyl)verdazyl radical (IX) was prepared, where the two radicals are connected ia a conjugated divinylene linker. The neutral radical donors stack in a more favourable head-to-head arrangement but the bulky isopropyl groups prevent the donor radicals from stacking close enough together to facilitate good orbital overlap. [Molecular diagram available in pdf].

The neoliberalization of street vending policy in Lima, Peru: the politics of citizenship. property and public space in the production of a new urban marginality

Neoliberalism is having a significant and global impact on political, social and economic life across spaces. This work illustrates how neoliberalism is attempting to change the ways in which the urban poor - particularly those that participate in street vending - use urban spaces in Lima, Peru. Using municipal policies, newspaper articles and local academic texts I argue that there is a changing marginality in Lima that is being experienced by street vendors, and currently in los canas of Lima. In particular, I discuss formalization, a neoliberal strategy in street vending policy, which is used with eradication and social assistance strategies in attempts to re-regulate street vendors.

Cellular Mechanisms of Resveratrol's Interaction with Mitochondrial Reactive Oxygen Species Metabolism

Resveratrol, a polyphenol found naturally in red wines, has attracted great interest in both the scientific community and the general public for its reported ability to protect against many of the diseases facing Western society today. While the purported health effects of resveratrol are well characterized, details of the cellular mechanisms that give rise to these observations are unclear. Here, the mitochondrial antioxidant enzyme Mn superoxide dismutase (MnSOD) was identified as a proximal target of resveratrol in vitro and in vivo. MnSOD protein and activity levels increase significantly in cultured cells treated with resveratrol, and in the brain tissue of mice given resveratrol in a high fat diet. Preventing the increase in MnSOD levels eliminates two of resveratrol’s more interesting effects in the context of human health: inhibition of proliferative cell growth and cytoprotection. Thus, the induction of MnSOD is a critical step in the molecular mechanism of resveratrol. Mitochondrial morphology is a malleable property that is capable of impeding cell cycle progression and conferring resistance against stress induced cell death. Using confocal microscopy and a novel ‘cell free’ fusion assay it was determined that concurrent with changes in MnSOD protein levels, resveratrol treatment leads to a more fused mitochondrial reticulum. This observation may be important to resveratrol’s ability to slow proliferative cell growth and confer cytoprotection. Resveratrol's biological activities, including the ability to increase MnSOD levels, are strikingly similar to what is observed with estrogen treatment. Resveratrol fails to increase MnSOD levels, slow proliferative cell growth and confer cytoprotection in the presence of an estrogen receptor antagonist. Resveratrol's effects can be replicated with the specific estrogen receptor beta agonist diarylpropionitrile, and are absent in myoblasts lacking estrogen receptor beta. Four compounds that are structurally similar to resveratrol and seven phytoestrogens predicted to bind to estrogen receptor beta were screened for their effects on MnSOD, proliferative growth rates and stress resistance in cultured mammalian cells. Several of these compounds were able to mimic the effects of resveratrol on MnSOD levels, proliferative cell growth and stress resistance in vitro. Thus, I hypothesize that resveratrol interacts with estrogen receptor beta to induce the upregulation of MnSOD, which in turn affects cell cycle progression and stress resistance. These results have important implications for the understanding of RES’s biological activities and potential applications to human health.

Property Tax Assessment - Niagara Township No. 179

A tax assessment of property no. 179 for Mr. Theodore Field or Mr. George Field. The total reads 546 and is dated October 25, 1886. Handwritten is "paid" with signature of J.Y.E. Cairns (collector).

Property Lost, Captured, or Destroyed by the Enemy 1812-14 (1824)

Government report in congress discussing property lost, captured, or destroyed by the British during the War of 1812.

Payment for Property - War of 1812-14 (1824)

Government report in congress discussing payment for property during the War of 1812.

Message from the President of the United States transmitting documents relative to the execution of the first article of the late treaty between the United States and Great Britain.

"February 7, 1817, ordered to be printed for the use of the Senate." Message addressed to the Senate and dated February 7th, 1817. Consists of the covering letter from the President and a report from the Secretary of State, dated Department of State, February 5th, 1817; which itself consists largely of diplomatic correspondence between the United States and Great Britain Relates to the restitution of captured slaves by the British during the War of 1812-1814.

Message from the President of the United States, Recommending an Immediate Declaration of War Against Great Britain (1812)

"June 1st, 1812. Referred to the Committee on Foreign Relations. June 3d, 1812. Bill reported, declaring war ..."

Draft News Release - Great Lakes Water Quality Agreement

A News Release draft to be sent to "100 newspapers, radio and television stations (virtually all those with offices within 20 miles of the Lakes), make them available to the Press Gallery, special interest groups, trade publication and Mayors etc. of Great Lake-side communities". The release discusses the need for an upgrade to "the 1972 Canada-U.S. Great Lakes Water Quality agreement". Within the document, O'Sullivan is quoted that the agreement "should be upgraded to become a treaty with the United States, so that after all the effort which has already been put into tyring to clean up the Great Lakes we the provision which provides for cancellation by either party giving twelve months (notice) to do so". The total report is 61 pages in length.

Press Release - Great Lakes and St. Lawrence Seaway Assignment, 25 October 1973

A press release assigning Sean O'Sullivan to study the future of the Great Lakes and St. Lawrence Seaway.

Description of Mr. Samuel DeVeaux Woodruff's property on Ontario Street

Handwritten description of Mr. Samuel DeVeaux Woodruff’s property on Ontario Street which was sent by E. Gardiner to the Railway Company. This is a 1 page handwritten document. The land consisted of parts of Lots 20 and 21 in the 5th Concession of Grantham, June 26, 1901.

Calculations Regarding S.D. Woodruff's Property on Ontario Street

Calculations regarding S.D. Woodruff’s property on Ontario Street. 1 page of rough penciled calculations, n.d.

Presentation from the Office of Macdonald and Rykert regarding the Case of O'Connor vs. the Great Western Railway Co.

Presentation from the Office of Macdonald and Rykert regarding the Case of O’Connor vs. the Great Western Railway Co. This is a handwritten, 9 ½ page double sided document). Some of the witnesses for the plaintiff included: Robert Johnson, John Ryder, Edward Duffy, Gilbert Gregory, John Cutter, James Patterson, Samuel Rush and Francis Bigger, among others. They claimed that the Great Western Railway Co. was destroying their land. Jacob Dittrick claimed that the culverts were not large enough to carry off water. Mr. Jackson noticed injury to his flats. Wild grass was destroying the bottom grass, May 6, 1836.