Towards sustainable peace : peace-building and human security

Failed and fragile states that result from intrastate war pose severe threats to the security of both the international system and individual states alike. In the post-Cold War era, the international community has come to recognize the reality of these threats and the difficulty involved in ending violence and building sustainable peace in failed and fragile states. This work focuses upon the development of a comprehensive strategy for sustainable peace-building by incorporating the tenets of the human security doctrine into the peace-building process. Through the use of case studies of The Former Yugoslav Republic of Macedonia and East Timor, the development and refinement of the doctrine of human security will occur, as well as, an understanding of how and where human security fits into the sustainable peace-building equation. The end result of the analysis is the development of a hierarchical pyramid formation that brings together human security and peace-building into one framework that ultimately creates the foundation and structure of sustainable peace-building. With the development of a sustainable peace-building structure based upon the human security doctrine, the role of Canada in the support of sustainable peace-building is analyzed in relation to the form and level of involvement that Canada undertakes and contributes to in the implementation and support of sustainable peace-building initiatives. Following from this, recommendations are provided regarding what role(s) Canada should undertake in the sustainable peace-building process that take into consideration the present and likely future capabilities of Canada to be involved in various aspects of the peace-building process. ii This paper outlines the need for a peace-building strategy that is designed to be sustainable in order that failed and fragile states resulting from intrastate conflict do not regress or collapse back into a condition of civil war, and subsequently designs such a strategy. The linking of peace-building and human security creates the required framework from which sustainable peace-building is derived. Creating sustainable peace is necessary in order to increase the likelihood that both present and future generations existing in failed and fragile states will be spared from the scourge of intrastate war.

To see and to touch : God, honour, and irony in Shakespeare's English histories /

Failed and fragile states that result from intrastate war pose severe threats to the security of both the international system and individual states alike. In the post-Cold War era, the international community has come to recognize the reality of these threats and the difficulty involved in ending violence and building sustainable peace in failed and fragile states. This work focuses upon the development of a comprehensive strategy for sustainable peace-building by incorporating the tenets of the human security doctrine into the peace-building process. Through the use of case studies of The Former Yugoslav Republic of Macedonia and East Timor, the development and refinement of the doctrine of human security will occur, as well as, an understanding of how and where human security fits into the sustainable peace-building equation. The end result of the analysis is the development of a hierarchical pyramid formation that brings together human security and peace-building into one framework that ultimately creates the foundation and structure of sustainable peace-building. With the development of a sustainable peace-building structure based upon the human security doctrine, the role of Canada in the support of sustainable peace-building is analyzed in relation to the form and level of involvement that Canada undertakes and contributes to in the implementation and support of sustainable peace-building initiatives. Following from this, recommendations are provided regarding what role(s) Canada should undertake in the sustainable peace-building process that take into consideration the present and likely future capabilities of Canada to be involved in various aspects of the peace-building process. ii This paper outlines the need for a peace-building strategy that is designed to be sustainable in order that failed and fragile states resulting from intrastate conflict do not regress or collapse back into a condition of civil war, and subsequently designs such a strategy. The linking of peace-building and human security creates the required framework from which sustainable peace-building is derived. Creating sustainable peace is necessary in order to increase the likelihood that both present and future generations existing in failed and fragile states will be spared from the scourge of intrastate war.

Investigation of the role of the nucleus accumbens in amphetamine-induced 50 kHz ultrasonic vocalizations in the rat

There is extensive evidence that the mesolimbic dopamine system underlies the production of 50 kHz ultrasonic vocalizations in rats. In particular, the shell of the nucleus accumbens is associated with generation of frequency modulated 50 kHz calls (a specific type of 50 kHz call which can be subdivided into various subtypes). There is also evidence that amphetamine administered systemically preferentially increases the proportion of trill and step calls compared to other frequency modulated 50 kHz subtypes. The purpose of this study was to investigate the effect of drug administration route and the role of the nucleus accumbens shell in amphetamine-induced 50 kHz call profile in the rat. Three experiments investigated this by using subcutaneous and intra-accumbens microinjections of amphetamine, as well as procaine (a local anesthetic) blockade of the nucleus accumbens. Ultrasonic vocalizations were recorded digitally from 24 rats and were analysed for sonographic structure based on general call parameters. The results of the three experiments were partially supportive of the hypotheses. Systemic amphetamine was found to induce greater bandwidth in 50 kHz calling compared to spontaneous calls in a vehicle condition. Systemic amphetamine was also found to preferentially increase the proportion of trill and step subtypes compared to vehicle. Moreover, there was no difference in the proportions of 50 kHz subtypes resulting from intracerebral or systemic application of amphetamine. There was, however, a significant difference for bandwidth, with systemic amphetamine inducing greater bandwidth over intraaccumbens application. Procaine blockade of the nucleus accumbens shell paired with subcutaneous amphetamine produced no difference in bandwidth of calls compared with those after a vehicle pre-treatment similarly paired. There was no reduction in the proportions of trill and step 50 kHz subtypes as well, with the procaine condition showing significantly greater proportion of step calls. The results of the study support a role for the iii nucleus accumbens shell in the amphetamine-induced changes on 50 kHz call profile. They also indicate there are more regions and pathways involved in generating 50 kHz calls than the projections from the ventral tegmental area to the nucleus accumbens. The implications of this work are that frequency modulated 50 kHz subtypes may be generated by distinct neurophysiological mechanisms and may represent a profitable avenue for investigating different circuits of 50 kHz call categories in the rat.

Molecular Magnetism: The Design, Synthesis, and Characterization of New Building Blocks for Molecule-based Magnetic Materials

Two classes of building blocks have been prepared and characterized and their coordination chemistry explored working towards the preparation of new molecule-based magnetic materials. In the first project, the amine functionality of 3,3'-diamino-2,2'- bipyridine was exploited for the preparation of a new family of ligands (H2L 1)-(H2L 4). The molecular structures of three ligands have been fully characterized by X-ray crystallography. [molecular structure diagram will not copy here, but is available in full pdf.] The coordination chemistry of these ligands with divalent first row transition metal ions was investigated. For ligand (H2L1), the molecular structures of four coordination complexes with stoichiometries [Zn2(Ll)(OAc)(MeO)]2 (I), [Cu2(L1)(OAc)2 (II), [Li(L1)]3 (III), and [Ni(L1)]3 (IV) were determined by X-ray crystallography. For ligand (H2L2), a Cu(II) complex of stoichiometry [Cu3(L2)(OAc)3MeO] (V) was determined by X-ray crystallography. The magnetic properties of complexes (II), (III), and (V) have been fully elucidated. In project two, synthetic strategies for the preparation of porphyrin molecules bearing triol substituents is presented. Following this approach, three new porphyrin derivatives have been prepared and characterized [Zn(HPTPP-CH2C(CH20H)3)] (VI), [P(TPP)(OCH2C(CH2)H)3)2]+CL- (VII), and [P(OEP)(C6H5)(OCH2C(CH2OH)3)]+Cl- (VIII). Attempts to exchange the labile methoxide bridges of a tetraironIIl single molecule magnet of stoichiometry [Fe4(OMe)6(dpm)6] (Hdpm = dipivaloylmethane) with the triol appended porphyrins will be discussed. [molecular structure diagram will not copy here, but is available in full pdf.]

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Polyglutamine monomer structure and its implications for molecular self-assembly

Polyglutamine is a naturally occurring peptide found within several proteins in neuronal cells of the brain, and its aggregation has been implicated in several neurodegenerative diseases, including Huntington's disease. The resulting aggregates have been demonstrated to possess ~-sheet structure, and aggregation has been shown to start with a single misfolded peptide. The current project sought to computationally examine the structural tendencies of three mutant poly glutamine peptides that were studied experimentally, and found to aggregate with varying efficiencies. Low-energy structures were generated for each peptide by simulated annealing, and were analyzed quantitatively by various geometry- and energy-based methods. According to the results, the experimentally-observed inhibition of aggregation appears to be due to localized conformational restraint placed on the peptide backbone by inserted prolines, which in tum confines the peptide to native coil structure, discouraging transition towards the ~sheet structure required for aggregation. Such knowledge could prove quite useful to the design of future treatments for Huntington's and other related diseases.

Automatic Structure Generation using Genetic Programming and Fractal Geometry

Three dimensional model design is a well-known and studied field, with numerous real-world applications. However, the manual construction of these models can often be time-consuming to the average user, despite the advantages o ffered through computational advances. This thesis presents an approach to the design of 3D structures using evolutionary computation and L-systems, which involves the automated production of such designs using a strict set of fitness functions. These functions focus on the geometric properties of the models produced, as well as their quantifiable aesthetic value - a topic which has not been widely investigated with respect to 3D models. New extensions to existing aesthetic measures are discussed and implemented in the presented system in order to produce designs which are visually pleasing. The system itself facilitates the construction of models requiring minimal user initialization and no user-based feedback throughout the evolutionary cycle. The genetic programming evolved models are shown to satisfy multiple criteria, conveying a relationship between their assigned aesthetic value and their perceived aesthetic value. Exploration into the applicability and e ffectiveness of a multi-objective approach to the problem is also presented, with a focus on both performance and visual results. Although subjective, these results o er insight into future applications and study in the fi eld of computational aesthetics and automated structure design.

Ligand design for molecule-based magnetic and/or conducting materials

Work in the area of molecule-based magnetic and/or conducting materials is presented in two projects. The first project describes the use of 4,4’-bipyridine as a scaffold for the preparation of a new family of tetracarboxamide ligands. Four new ligands I-III have been prepared and characterized and the coordination chemistry of these ligands is presented. This project was then extended to exploit 4,4’-bipyridine as a covalent linker between two N3O2 macrocyles. In this respect, three dimeric macrocycles have been prepared IV-VI. Substitution of the labile axial ligands of the Co(II) complex IV by [Fe(CN)6]4- afforded the self-assembly of the 1-D polymeric chain {[Co(N3O2)H2O]2Fe(CN)6}n•3H2O that has been structurally and magnetically characterized. Magnetic studies on the Fe(II) complexes V and VI indicate that they undergo incomplete spin crossover transitions in the solid state. Strategies for the preparation of chiral spin crossover N3O2 macrocycles are discussed and the synthesis of the novel chiral Fe(II) macrocyclic complex VII is reported. Magnetic susceptibility and Mössbauer studies reveal that this complex undergoes a gradual spin crossover in the solid state with no thermal hysteresis. Variable temperature X-ray diffraction studies on single crystals of VII reveal interesting structural changes in the coordination geometry of the macrocycle accompanying its SCO transition. The second project reports the synthesis and characterization of a new family of tetrathiafulvalene derivatives VIII – XII, where a heterocyclic chelating ligand is appended to a TTF donor via an imine linker. The coordination chemistries of these ligands with M(hfac)2.H2O (M( = Co, Ni, Mn, Cu) have been explored and the structural and magnetic properties of these complexes are described.

Informing the structure of subjective well-being through examining changes in life satisfaction, positive affect, and negative affect

Subjective well-being (SWB) refers to how individuals evaluate and experience their lives in positive ways, and encompasses global judgments of life satisfaction (LS), as well as the frequency of positive and negative affect (PA and NA, respectively) in one’s life. To inform the current ambiguity concerning the structure of SWB, the aim of this Masters thesis was to evaluate the structure of SWB based on whether the three components of SWB change together or independently naturally, over time and following experimental manipulation. In Study 1, associations among changes in LS, PA, and NA were evaluated using a longitudinal approach tracking natural changes in the components over periods of three months and three years. Results indicated that change in one component was related to change in the other two components. In Study 2, an experimental design was used to manipulate each SWB component individually, and evaluate changes in all three components following each manipulation. Manipulation materials designed to target LS only were effective (i.e., led to heightened focus on LS, and not PA or NA) and created an increase in both LS and PA. Manipulation materials designed to target PA and NA only were not effective (i.e., led to heightened focus on the target component, as well as on LS). Furthermore, in both studies the strength of an individual’s SWB (assessed in terms of structural consistency and structural ambivalence in Study 1 and Study 2, along with subjective ambivalence in Study 2) did not consistently moderate the degree to which changes in the components were associated with one another. Together, these findings indicate that the structure of SWB may be complex and dynamic, rather than static. Alternatively, the components of SWB may not be easily manipulated in isolation of one another. Implications for existing structural models of SWB are discussed.