Legitimacy in question : elite-mass relations, constitutional reform and Canadian democracy /

During the 1980s and 1990s, Canadian political authority orientations underwent a significant transformation. Canadians are no longer deferential towards their political elites. Instead, they are autonomous, challenging, and increasingly participatory, and this continuing trend has brought the procedural legitimacy of the Canadian political process into question. The following study of elite-mass relations within Canadian democracy attempts to provide insight into the meaning of this change and how it should be addressed. An attitudinalbehavioural analysis ofthe electorate presents evidence that popular cynicism and alienation is rooted more deeply in a dissatisfaction with political institutions and traditions than with politicians. A structural analysis of the elected political elite reveals the failure of consociational traditions to provide effective representation as well as the minimal impact which the aforementioned orientation shift has had upon this elite. An event-decisional analysis, or case study, ofelite-mass relations in the arena of constitutional politics augments these complementary profiles and illustrates how the transformed electorate has significantly restricted the elected political elite's role in constitutional reform. The study concludes that the lack ofresponsiveness, representativeness, and inclusiveness ofCanada's elected political elite, political institutions, and political traditions has substantially eroded the procedural legitimacy of Canadian democracy during the 1980s and 1990s. Remedying these three deficiencies in the political system, which are the objects of increasing public demand, may restore legitimacy, but the likelihood that such reforms will be adopted is presently uncertain in the face of formidable difficulties and obstacles.

Determinants of left ventricular mass as measured by Doppler echocardiography in pre-adolescents

This study examined factors contributing to the differences in left ventricular mass as measured by Doppler echocardiography in children. Fourteen boys (10.3 ± 0.3 years of age) and 1 1 girls (10.5 ± 0.4 years of age) participated in the study. Height and weight were measured, and relative body fat was determined from the measurement of skinfold thickness according to Slaughter et al. (1988). Lean Body Mass was then calculated by subtracting the fat mass from the total body mass. Sexual maturation was self-assessed using the stages of sexual maturation by Tanner (1962). Both pubic hair development and genital (penis or breast for boys and girls respectively) development were used to determine sexual maturation. Carotid Pulse pressure was assessed by applanation tomometry in the left carotid artery. Cardiac mass was measured by Doppler Echocardiography. Images of cardiac structures were taken using B-Mode and were then translated to M- Mode. The dimensions at the end diastole were obtained at the onset of the QRS complex of the electrocardiogram in a plane through a standard position. Measurements included: (a) the diameter of the left ventricle at the end diastole was measured from the septum edge to the endocardium mean border, (b) the posterior wall was measured as the distance from to anterior wall to the epicardium surface, and (c) the interventricular septum was quantified as the distance from the surface of the left ventricle border to the right ventricle septum surface. Systolic time measurements were taken at the peak of the T-wave of the electrocardiogram. Each measurement was taken three to five times before averaging. Average values were used to calculate cardiac mass using the following equation (Deveraux et al. 1986). Weekly physical activity metabolic equivalent was calculated using a standardize activity questionnaire (Godin and Shepard, 1985) and peakV02 was measured on a cycloergometer. There were no significant differences in cardiovascular mesurements between boys and girls. Left ventricular mass was correlated (p<0.05) with size, maturation, peakV02 and physical activity metabolic equivalent. In boys, lean body mass alone explained 36% of the variance in left ventricular mass while weight was the single strongest predictor of left ventricular mass (R =0.80) in girls. Lean body mass, genital developemnt and physical activity metabolic equivalent together explained 46% and 81% in boys and girls, respectively. However, the combination of lean body mass, genital development and peakV02 (ml kgLBM^ min"') explained up to 84% of the variance in left ventricular mass in girls, but added nothing in boys. It is concluded that left ventricular mass was not statistically different between pre-adolescent boys and girls suggesting that hormonal, and therefore, body size changes in adolescence have a main effect on cardiac development and its final outcome. Although body size parameters were the strongest correlates of left ventricular mass in this pre-adolescent group of children, to our knowledge, this is the first study to report that sexual maturation, as well as physical activity and fitness, are also strong associated with left ventricular mass in pre-adolescents, especially young females. Arterial variables, such as systolic blood pressure and carotid pulse pressure, are not strong determinants of left ventricular mass in this pre-adolescent group. In general, these data suggest that although there is no gender differences in the absolute values of left ventricular mass, as children grow, the factors that determine cardiac mass differ between the genders, even in the same pre-adolescent age.

A fast atom bombardment mass spectrometry study of tris (3, 6-dioxaheptyl) amine-alkali metal halide complexes and hydrogen bonded complexes

The objective of this thesis was to demonstrate the potential of fast atom bombardment mass spectrometry (FABMS) as a probe of condensed phase systems and its possible uses for the study of hydrogen bonding. FABMS was used to study three different systems. The first study was aimed at investigating the selectivity of the ligand tris(3,6-dioxaheptyl) amine (tdoha) for the alkali metal cations. FABMS results correlated well with infrared and nmr data. Systems where a crown ether competed with tdoha for a given alkali metal cation were also investigated by fast atom bombardment. The results were found to correlate with the cation affinity of tdoha and the ability of the crown ether to bind the cation. In the second and third studies, H-bonded systems were investigated. The imidazole-electron donor complexes were investigated and FABMS results showed the expected H-bond strength of the respective complexes. The effects of concentration, liquid matrix, water content, deuterium exchange, and pre-ionization of the complex were also investigated. In the third system investigated, the abundance of the diphenyl sulfone-ammonium salt complexes (presumably H-bonded) in the FABMS spectrum were found to correlate with qualitative considerations such as steric hindrance and strength of ion pairs.

A mass spectrometric study of some pesticides /|nK. S. Subramanian. -- 260 St. Catharines, Ont. : [s. n.],

The fragmentation processes in the mass spectra of a series of organophosphorus, organochlorine, thio and dithiocarbamate as well as a number of miscellaneous pesticides have been studied i n detail by using the Bendix timeof- flight, MS-12 single-focussing and MS-30 double-focussing mass spectrometers. Interpretation of all the spectra have been presented; their mode s of dissociation elucidated, aided by metastable transitions wherever possible and the structures of the various f ragmentation species postulated wherever f easible. The fragmentation mechanisms are based on the concepts of inductive, resonance and steric ef~ects. Multiple bond cleavages accompanied by simultaneous bond formation and rearrangement reactions involving cycli c t r ansition states have clarified t he formation of various ions . Due emphasis has been placed on the effect of the functional groups or substituents in altering the mass spectral behaviour of the pesticides as they form the basis for the identifi cation of the otherwise identical pesticides. The organophosphorus pesticides which have been studied include i) the phosphates (eg: DDVP and Phosdrin ); ii) phosphorothionates (eg: Parathion, 0-2, 4 dichloro phenyl 0, O-diethyl thionophosphate); iii) phosphorothioites (eg: Tributyl phosphorotrithioite); i V) phosphorothioates (eg: Ethion) and v) phosphorodithioates (eg: Carbophenolthion). Cleavages and rearrangements of the ester moiety dominate the spectrum of phosdrin while that of DDVP is + dominated by t he fragmentation modes of the (OH30)2P=0 + moiety. Fragmentation §f the (CH30)2P=S characterises the spectrum of (OH30)2"P -Cl while cleavages of the + (C2H50 )2P=S species mark the spectra of parathion and 0-2, 4- di chlorophenyl O, O-diethyl thiophosphate. The 0(, cl eavages of the thioether f unction rather than + cleavages of the (C2H50)2P=S signify the spectrum of carbophenolthion. Tributyl phosphorotrithioite behaves more like an aliphatic hydrocarbon than like the corresponding phosphites. The isopropyl and butyl esters of 2, 4 dichlorophenoxy acetic acid show cleavage and rearrangement ions typical of an ester. In spite of its structural similari ty to pp' - DDT and pp' - DDD, Kalthane has a completely different mass spectral behaviour due to the influence of its hydroxyl function. The thiocarbamate pesticides studied include Eptam and Perbulate. Both are structurally similar but having different alkyl substituents on nitrogen and sulphur. This structurQlsimilarity leads to similar types of (N-C), (O-S) and (S-alkyl cleavages). However, perbulate differs from Eptam in showing a rearrangement ion at mle 161 and in forming an isocyanate ion as the base peak. In Eptam the base peak i s the alkyl ion. The dithiocarbamate, Vegadex, resembles the thiocarbamates in undergoing simple cleavages but it differs from them in having a weak parent ion; in the formation of its base peak and in undergoing a series of rearrangement reactions. The miscellaneous pesticides studied include 1-Naphthalene acetic aCid- methyl ester, Fiperonyl butoxide and Allethrin. The ester i s stable to electron impact and shows only fewer ions. Piper onyl butoxide, a polyether, shows characteristics of an et her, alcohol and aldehyde . Allethrin is regarded as an ester of the type R-C-O-R1 with n R being a substituted cyclopr opane moiety and o Rt, a substituted cyclopentenone mOiety. Accordingly it shows cleavage ions typical of an aliphatic ester and undergoes bond ruptures of the cyclic moieties to give unusual ions. Its base peak is an odd electron ion, quite contrary to expectations.

Comparative electron impact and fast atom bombardment mass spectrometric studies of some HMPA adducts of phenyltin and phenyllead halides and studies of strong hydrogen bonding by FAB-MS

The fragmentation patterns and mass spectra of some phenyl tin and -lead halide adducts with hexamethylphosphoramide are compared by subjecting them t~ electron impact and fast atom bombardment ionization in a mass spectrometer. This comparison is restricted to the metal-containing ions. Ligand-exchange mechanisms of some of the metal-containing species are explored by FAB-MS. Several moisturesensitive organo-metallics and H-bonded systems have been examined by FAB for attempted characterization, but without any success. Scavenging and trapping of water molecules by complex aggregates in solutions of quaternary ammonium fluorides and hydroxides are investigated by FAB to complement previous NMR-studies.

Fast atom bombardment and electron impact mass spectrometry studies of some aryltin compounds and ferrocenes

Both El MS and FAB MS behavior of two groups of compounds, aryltin and ferrocene compounds, have been studied. For the aryltin compounds, the effect of substituent group position, substituent group type and ligand type on the El spectra have been explored in the El MS studies. The fragmentation mechanism has been investigated under El with linked scans, such as fragment ion scans(BJE), parent ion scans(B2JE) and constant neutral radical loss scans(B2(1-E)JE2). In the FAB MS studies, matrix optimization experiments have been carried out. The positive ion FAB MS studies focused on the effect of substituent group position, substituent group type and ligand type on the spectra. The fragmentation mechanisms of all the samples under positive ion FAB have been studied by means of the linked scans. The CA positive ion FAB fragmentation studies were also carried out for a typical sample. Negative ion FAB experiments of all the compounds have been done. And finally, the comparison of the El MS and FAB MS has been made. For ferrocenes, the studies concentrated on the fragmentation mechanism of each compound under El with linked scan techniques in the first field-free region and the applicability of positive/negative ion FAB MS to this group of compounds. The fragmentation mechanisms under positive ion FAB of those ferrocenes which can give positive ion FAB MS spectra were studied with the linked scan techniques. The CA +ve F AB fragmentation studies were carried out for a typical sample. Comparison of the E1 MS and FAB MS has been made.

Fast atom bombardment mass spectrometry of the coordination complexes of the ligand 5, 5, 7, 12, 12, 14- hexamenthyl-1, 4, 8, 11-tetraazacycloteradecane

A number of metal complexes containing the ligand 5,5,7,12,12,14-hexamethyl-l,4,8,11-tetra-azatetradecane were synthesized and analyzed using electron impact (EI) and fast atom bombardment (FAB). The FAB mass spectra were obtained in positive and negative ion mode. FAB in the positive ion mode proved to be the most successful technique for the identification of these compounds. In the majority of cases the spectra obtained using positive ion FAB were structurally informative, although not all showed molecular (M+) or quasimolecular ([M+H]+) ions. The fragmentations observed were characteristic of the ligands, and were interpreted based on the chemistry of these compounds.