Fast atom bombardment mass spectrometry studies of ruthenium (II) polypyridy coordination complexes and of group V Triptycenes and related complexes

In order to investigate the use of Fast Atom Bombardment Mass Spectrometry (FAB-MS) as a tool for structural characterization, two groups of complexes are analyzed. The first group is a set of ruthenium(II) coordination complexes containing bidentate polypyridyl ligands. The positive and negative ion FAB-MS spectra are found to be sufficient to allow for an almost complete characterization of the central metal atom, the ligands and the counter anions contained in the intact complex. An unusual observation of mUltiply charged ions in the positive ion FAB-MS spectra (i.e. [RUL 3 ]2+) is explained to be as a result of the oxidative quenching of the excited state of the doubly charged ion by the matrix, 3-nitrobenzyl alcohol. An analysis of a mixture shows that the technique is a good one for identifying components therein. A group of triptycene and related complexes containing Group V elements is also analyzed by FAB-MS and the results. in terms of relative abundances of fragment ions, are found to be consistent with known metal-carbon bond strengths.

Mass spectral studies of some pentafluorophenyl derivatives of group V /|nby Andrew Tanner Rake. -- 260 St. Catharines, Ont. : [s. n.],

The mass spectra of compounds of t he series (C6F5 )3-n MP~ (n = 1,2,3, M = P and As ), (C6F5>3Sb, Ph) Sb and (C6F5 )2SbPh have been studied in detail and the important modes of fragmentation were e1ucidated, a ided by metastable ions. Various trends attributed to the central atom and or the . substituent groups have been noted and, where applicable, compared to recent studies on related phenyl and pentafluorophenyl compounds of groups IV and V. The mass spectra of fluorine containing organometallic compounds exhibit characteristic migrations of fluorine to t he central atom, giving an increasing abundance of MF+, MF2+' and RMF+ (R = Ph or C6F5) ions on descending the group_ The mass spectra of pentafluorophenyl , antimony, and arsenic compounds show a greater fragmentation of the aromatic ring than those of phosphorus. The mixed phenyl pentafluorophenyl derivatives show a characteristic pattern depending on the number of phenyl grm.lps present but show t he general characteristics of both the tris(phenyl) and tris(pentafluorophenyl) compounds. The diphenyl pentafluorophenyl der ivatives show the loss of biphenyl ion as the most import ant step, the los s of phenyl t o give the i on PhMC6F5 + being of secondary importance. The ,bis(pentafluorophenyl) phenyl derivatives fragment primarily by loss of PhC6F5 to give C6F5M+ ions, the abundance of t hese increasing r apidly from phosphorus to arsenic. This species then, exhibits a characteristic fragmentation observed in the tris(penta- fluorophenyl ) compounds. However, the abundance of (C6F5)2M+ species in these compounds i s small. I ons of the type C6H4MC6F4 + and tetrafluorobiphenylene ions C6H4C6F4 + also are observed on substitution of a phenyl group for a penta- fluorophenyl group. The fully fluorinated species (C6F4)2M+ is not observed, although octafluorobiphenylene ions , (C6F4)2+' are evident in several spectra . The appearance potentials of the major ions were obtatned from the ionisation efficiency curves. Attempts were made to correlate these to the effect of the central atom in substituent groups, but the large errors involved prevented the reaching of quantitative conclusions, although it would appear that the electron is removed from the ligand in the ionisation of t he parent molecule .

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3carbonyl I.R. stretch, Drago (22) et al have proposed that the angular di~tortion of the X-B-X bonds from sp2 (12 ) to sp3 (10 hybridization is proportional to the amount of charge transferred, i.e. to the nature of the base, and they have rejected the earlier concept of reorganization energy in explaining the formation of the adduct bond (19).

Paragenetic history of the Ordovician Trenton Group carbonates, Southwestern Ontario

Geochemical examination of the rock matrix and cements from core material extracted from four oil wells within southwestern Ontario suggest various stages of diagenetic alteration and preservation of the Trenton Group carbonates. The geochemical compositions of Middle Ordovician (LMC) brachiopods reflect the physicochemical water conditions of the ambient depositional environment. The sediments appear to have been altered in the presence of mixed waters during burial in a relatively open diagenetic microenvironment. Conodont CAl determination suggests that the maturation levels of the Trenton Group carbonates are low and proceeded at temperatures of about 30 - 50°C within the shallow burial environment. The Trenton Group carbonates are characterized by two distinct stages of dolomitization which proceeded at elevated temperatures. Preexisting fracture patterns, and block faulting controlled the initial dolomitization of the precursor carbonate matrix. Dolomitization progressed In the presence of warm fluids (60 75°C) with physicochemical conditions characteristic of a progressively depleted basinal water. The matrix is mostly Idiotopic-S and Idiotopic-E dolomite, with Xenotopic-A dolomite dominating the matrix where fractures occur. The second stage of dolomitization involved hydrothermal basinal fluid(s) with temperatures of about 60 - 70°C. These are the postulated source for the saddle dolomite and blocky calcite cements occurring in pore space and fractures. Rock porosity was partly occluded by Idiotopic-E type dolomite. Late stage saddle dolomite, calcite, anhydrite, pyrite, marcasite and minor sphalerite and celestite cements effectively fill any remaining porosity within specific horizons. Based on cathode luminescence, precipitation of the different diagenetic phases probably proceeded in open diagenetic systems from chemically homogeneous fluids. Ultraviolet fluorescence of 11 the matrix and cements demonstrated that hydrocarbons were present during the earliest formation of saddle dolomite. Oxygen isotope values of -7.6 to -8.5 %0 (PDB), and carbon isotope values of - 0.5 and -3.0 %0 (PDB) from the latest stage dog-tooth calcite cement suggest that meteoric water was introduced into the system during their formation. This is estimated to have occurred at temperatures of about 25 - 40°C. Specific facies associations within the Trenton Group carbonates exhibit good hydrocarbon generating potential based on organic carbon preservation (1-3.5%). Thermal maturation and Lopatin burial-history evaluations suggest that hydrocarbons were generated within the Trenton Group carbonates some time after 300 Ma . Progressively depleted vanadium trends measured from hydrocarbon samples within southwestern Ontario suggests its potential use as a hydrocarbon migration indicator on local (within an oilfield) and on regional scales.

Chapman family group on porch, New Year's Day, 1929-1930

Chapman family group on porch, New Year's Day, 1929-1930. Written on back: "Father, Mother, Sister, with Jim, his wife and daughter."

Group portrait with Charles Clarke Chapman, Samuel James, and George Arthur Chapman Sr., circa 1900.

Copy of a damaged group portrait with Charles Clarke Chapman on the left, Samuel James on the right, and young man in front with hat and tie is George Arthur Chapman Sr., circa 1900.

Orientation of Non-Native 2-Monosubstituted and 2,3-Disubstituted 1,4-Naphthoquinones in the A1 binding site of PSI and the effect on the rate of electron transfer : an electron paramagnetic resonance spectroscopy study

The proce-ss ofoxygenic photosynthesis is vital to life on Earth. the central event in photosynthesis is light induced electron transfer that converts light into energy for growth. Ofparticular significance is the membrane bound multisubunit protein known as Photosystem I (PSI). PSI is a reaction centre that is responsible for the transfer of electrons across the membrane to reduce NADP+ to NADPH. The recent publication ofa high resolution X-ray structure of PSI has shown new information about the structure, in particular the electron transfer cofactors, which allows us to study it in more detail. In PSI, the secondary acceptor is crucial for forward electron transfer. In this thesis, the effect of removing the native acceptor phylloquinone and replacing it with a series of structurally related quinones was investigated via transient electron paramagnetic resonance (EPR) experiments. The orientation of non native quinones in the binding site and their ability to function in the electron transfer process was determined. It was found that PSI will readily accept alkyl naphthoquinones and anthraquinone. Q band EPR experiments revealed that the non-native quinones are incorporated into the binding site with the same orientation of the headgroup as in the native system. X band EPR spectra and deuteration experiments indicate that monosubstituted naphthoquinones are bound to the Al site with their side group in the position occupied by the methyl group in native PSI (meta to the hydrogen bonded carbonyl oxygen). X band EPR experiments show that 2, 3- disubstituted methyl naphthoquinones are also incorporated into the Al site in the same orientation as phylloquinone, even with the presence of a halogen- or sulfur-containing side chain in the position normally occupied by the phytyl tail ofphylloquinone. The exception to this is 2-bromo-3-methyl --.- _. -. - -- - - 4 _._ _ _ - _ _ naphthoquinone which has a poorly resolved spectrum, making determination of the orientation difficuh. All of the non-native quinones studied act as efficient electron acceptors. However, forward electron transfer past the quinone could only be demonstrated for anthraquinone, which has a more negative midpoint potential than phylloquinone. In the case of anthraquinone, an increased rate of forward electron transfer compared to native PSI was found. From these results we can conclude that the rate ofelectron transfer from Al to Fx in native PSI lies in the normal region ofthe Marcus Curve.

Occupational therapist and client experiences of a mental health group

The purpose of this qualitative study was to understand the client and occupational therapist experiences of a mental health group. A secondary aim was to explore the extent to which this group seemed to have reflected a client-centred approach. The topic emerged from personal and professional issues related to the therapist as teacher and to inconsistencies in practice with the profession's client-centred philosophy. This philosophy, the study's frame of reference, was established in terms of themes related to the client-therapist relationship and to client values. Typical practice was illustrated through an extensive literature review. Structured didacticexperiential methods aiming toward skill development were predominant. The interpretive sciences and, to a lesser extent, the critical sciences directed the methodology. An ongoing support group at a community mental health clinic was selected as the focus of the study; the occupational therapist leader and three members became the key participants. A series of conversational interviews, the . core method of data collection, was supplemented by observation, document review, further interviews, and fieldnotes. Transcriptions of conversations were returned to participants for verification and for further reflection. Analysis primarily consisted of coding and organizing data according to emerging themes. The participants' experiences of group, presented as narrative stories within a group session vignette, were also returned to participants. There was a common understanding of the group's structure and the importance of having "air time" within the group; however, differences in perceptions of such things as the importance of the group in members' lives were noted. All members valued the therapeutic aspects of group, the role of group as weekly activity and, to a lesser extent, the learning that came from group. The researcher's perspective provided a critique of the group experience from a client-centred perspective. Some areas of consistency with client-centred practice were noted (e.g., therapist attitudes); however the group seemed to function far from a client-centred ideal. Members held little authority in a relationship dominated by the leaders, and leader agendas rather than member values controlled the session. Possible reasons for this discrepancy ranging from past health care encounters through to co-leader discord emerged. The actual and potential significance of this study was discussed according to many areas of implications: to OT practice, especially client-centred group practice, to theory development, to further areas of research and methodology considerations, to people involved in the group and to my personal growth and development.

Predictors of prejudice perceptions and the role of group identification in international students

The purpose of the present study was first to determine what influences international students' perceptions of prejudice, and secondly to examine how perceptions of prejudice would affect international students' group identification. Variables such as stigma vulnerability and contact which have been previously linked with perceptions of prejudice and intergroup relations were re-examined (Berryman-Fink, 2006; Gilbert, 1998; Nesdale & Todd, 2000), while variables classically linked to prejudicial attitudes such as right-wing authoritarianism and openness to experience were explored in relation to perceptions of prejudice. Furthermore, the study examined how perceptions of prejudice might affect the students' identification choices, by testing two opposing models. The first model was based on the motivational nature of social identity theory (Tajfel & Turner, 1986) while the second model was based on the cognitive nature of self-categorization theory/ rejection-identification model (Turner, Hogg, Oakes, Reicher, & Wetherell, 1987; Schmitt, Spears, & Branscombe,2003). It was hypothesized that stigma vulnerability, right-wing authoritarianism, openness to experience and contact would predict both personal and group perceptions of prejudice. It was also hypothesized that perceptions of prejudice would predict group identification. If the self-categorizationlrejection-identification model was supported, international students would identify with the international students. If the social mobility strategy was supported, international students would identify with the university students group. Participants were 98 international students who filled out questionnaires on the Brock University Psychology Department Website. The first hypothesis was supported. The combination of stigma vulnerability, right-wing authoritarianism, openness to experience and contact predicted both personal and group prejudice perceptions of international students. Furthermore, the analyses supported the self-categorizationlrejectionidentification model. International identification was predicted by the combination of personal and group prejudice perceptions of international students.

Vitamin D status and latent tuberculosis infection : a preliminary study in a group of healthy Mexican agricultural workers

Vitamin D metabolites are important in the regulation of bone and calcium homeostasis, but also have a more ubiquitous role in the regulation of cell differentiation and immune function. Severely low circulating 25-dihydroxyvitamin D [25(OH)D] concentrations have been associated with the onset of active tuberculosis (TB) in immigrant populations, although the association with latent TB infection (LTBI) has not received much attention. A previous study identified the prevalence of LTBI among a sample of Mexican migrant workers enrolled in Canada's Seasonal Agricultural Workers Program (SA WP) in the Niagara Region of Ontario. The aim of the present study was to determine the vitamin D status of the same sample, and identify if a relationship existed with LTBI. Studies of vitamin D deficiency and active TB are most commonly carried out among immigrant populations to non-endemic regions, in which reactivation of LTBI has occurred. Currently, there is limited knowledge of the association between vitamin D deficiency and LTBI. Entry into Canada ensured that these individuals did not have active TB, and L TBI status was established previously by an interferon-gamma release assay (IGRA) (QuantiFERON-TB Gold In-Tube®, Cellestis Ltd., Australia). Awareness of vitamin D status may enable individuals at risk of deficiency to improve their nutritional health, and those with LTBI to be aware of this risk factor for disease. Prevalence of vitamin D insufficiency among the Mexican migrant workers was determined from serum samples collected in the summer of 2007 as part of the cross sectional LTBI study. Samples were measured for concentrations of the main circulating vitamin D metabolite, 25(OH)D, with a widely used 1251 250HD RIA (DiaSorin Inc.®, Stillwater, MN), and were categorized as deficient «37.5 nmoI/L), insufficient (>37.5 nmollL, < 80 nmol/L) or sufficient (2::80 nmoI/L). Fisher's exact tests and t tests were used to determine if vitamin D status (sufficiency or insufficiency) or 25(OH)D concentrations significantly differed by sex or age categories. Predictors of vitamin D insufficiency and 25(OH)D concentrations were taken from questionnaires carried out during the previous study, and analyzed in the present study using multiple regression prediction models. Fisher's exact test and t test was used to determine if vitamin D status or 25(OH)D concentration differed by LTBI status. Strength of the relationship between interferongamma (IFN-y) concentration (released by peripheral T cells in response to TB antigens) and 25(OH)D concentration was analyzed using a Spearman correlation. Out of 87 participants included in the study (78% male; mean age 38 years), 14 were identified as LTBI positive but none had any signs or symptoms of TB reactivation. Only 30% of the participants were vitamin D sufficient, whereas 68% were insufficient and 2% were deficient. Significant independent predictors of lower 25(OH)D concentrations were sex, number of years enrolled in the SA WP and length of stay in Canada. No significant differences were found between 25(OH)D concentrations and LTBI status. There was a significant moderate correlation between IFN-y and 25(OH)D concentrations ofLTBI-positive individuals. The majority of participants presented with Vitamin D insufficiency but none were severely deficient, indicating that 25(OH)D concentrations do not decrease dramatically in populations who temporarily reside in Canada but go back to their countries of origin during the Canadian winter. This study did not find a statistical relationship between low levels of vitamin D and LTBI which suggests that in the presence of overall good health, lower than ideal levels of 2S(OH)D, may still be exerting a protective immunological effect against LTBI reactivation. The challenge remains to determine a critical 2S(OH)D concentration at which reactivation is more likely to occur.

Hydrosilylation and hydroboration catalyzed by imido-hydride complexes of molybdenum (IV)

This thesis describes the synthesis, structural studies, stoichiometric and catalytic reactivity of novel Mo(IV) imido hydride complexes (Cp)(ArN)Mo(H)(PMe3) (1) and (Tp )(ArN)Mo(H)(PMe3) (2). Both 1 and 2 catalyze hydrosilylation of a variety of carbonyls. Detailed kinetic and DFT studies found that 1 reacts by an unexpected associative mechanism, which does not involve Si-H addition either to the imido group or the metal. Despite 1 being a d2 complex, its reaction with PhSiH3 proceeds via a a-bond metathesis mechanism giving the silyl derivative (Cp )(ArN)Mo(SiH2Ph)(PMe3). In the presence of BPh3 reaction of 1 with PhSiH3 results in formation of (Cp)(ArN)Mo(SiH2Ph)(H)2 and (Cp)(ArN)Mo(SiH2Ph)2(H), the first examples ofMo(VI) silyl hydrides. AI: 1 : 1 reaction between 2, PhSiD3 and carbonyl substrate established that hydrosilylation is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional mechanism based on carbonyl insertion carbonyl. As 2 is nomeactive to both the silane and ketone, the only mechanistic alternative we are left with is that the metal center activates the carbonyl as a Lewis acid. The analogous nonhydride mechanism was observed for the catalysis by (ArN)Mo(H)(CI)(PMe3), (Ph3P)2(I)(O)Re(H)(OSiMe2Ph) and (PPh3CuH)6. Complex 2 also catalyzes hydroboration of carbonyls and nitriles. We report the first case of metal-catalyzed hydroboration of nitriles as well as hydroboration of carbonyls at very mild conditions. Conversion of carbonyl functions can be performed with high selectivities in the presence of nitrile groups. This thesis also reports the first case of the HlH exchange between H2 and Si-H of silanes mediated by Lewis acids such as Mo(IV) , Re(V) , Cu(I) , Zn(II) complexes, B(C6Fs)3 and BPh3.

I Believe in me, not OCB: Evaluation of Group Function-Based CBT as a Treatment for Obsessive Compulsive Behaviour in Four Children with HFA

Researchers have conceptualized repetitive behaviours in individuals with Autism Spectrum Disorder (ASD) on a continuum oflower-Ievel, motoric, repetitive behaviours and higher-order, repetitive behaviours that include symptoms ofOCD (Hollander, Wang, Braun, & Marsh, 2009). Although obsessional, ritualistic, and stereotyped behaviours are a core feature of ASD, individuals with ASD frequently experience obsessions and compulsions that meet DSM-IV-TR (American Psychiatric Association, 2000) criteria for Obsessive-Compulsive Disorder (OCD). Given the acknowledged difficulty in differentiating between OCD and Autism-related obsessive-compulsive phenomena, the present study uses the term Obsessive Compulsive Behaviour (OCB) to represent both phenomena. This study used a multiple baseline design across behaviours and ABC designs (Cooper, Heron, & Heward, 2007) to investigate if a 9-week Group Function-Based Cognitive Behavioural Therapy (CBT) decreased OCB in four children (ages 7 - 11 years) with High Functioning Autism (HFA). Key treatment components included traditional CBT components (awareness training, cognitive-behavioural skills training, exposure and response prevention) as well as function-based assessment and intervention. Time series data indicated significant decreases in OCBs. Standardized assessments showed decreases in symptom severity, and increases in quality of life for the participants and their families. Issues regarding symptom presentation, assessment, and treatment of a dually diagnosed child are discussed.

Investigating Changes in Parent Knowledge about Obsessive Compulsive Behaviour Following Group Function-Based Cognitive Behavioural Therapy for Children with High Functioning Autism

This study investigated improvements in parent knowledge of effective intervention strategies following participation in a group function-based CBT treatment (GFbCBT) package for children with comorbid OCD and ASD. Nineteen parents of children ages 7-12 years with High Functioning Autism (HFA) participated in the 9-week treatment program. Key components of treatment included psychoeducation and mapping, cognitive-behavioural skills training, function-based interventions and exposure and response prevention (ERP). Treatment sessions also included direct parent education, which followed a behavioural skills training model (Miltenberger, 2008). Parent knowledge (N = 19) was measured pre and post treatment using a vignette about a child demonstrating obsessive-compulsive behaviour. Results of a one-tailed pairwise t-test indicated statistically significant changes (p=.036) in overall parent knowledge following participation in treatment. Statistically significant changes were also found in parents’ ability to generate ERP and function-based intervention strategies. These results provide preliminary evidence that parents benefit from active involvement in the GFbCBT treatment package.

Rings, Group Rings, and Their Graphs

We associate some graphs to a ring R and we investigate the interplay between the ring-theoretic properties of R and the graph-theoretic properties of the graphs associated to R. Let Z(R) be the set of zero-divisors of R. We define an undirected graph ᴦ(R) with nonzero zero-divisors as vertices and distinct vertices x and y are adjacent if xy=0 or yx=0. We investigate the Isomorphism Problem for zero-divisor graphs of group rings RG. Let Sk denote the sphere with k handles, where k is a non-negative integer, that is, Sk is an oriented surface of genus k. The genus of a graph is the minimal integer n such that the graph can be embedded in Sn. The annihilating-ideal graph of R is defined as the graph AG(R) with the set of ideals with nonzero annihilators as vertex such that two distinct vertices I and J are adjacent if IJ=(0). We characterize Artinian rings whose annihilating-ideal graphs have finite genus. Finally, we extend the definition of the annihilating-ideal graph to non-commutative rings.