Problems of allometric scaling analysis: examples from mammalian reproductive biology.

Biological scaling analyses employing the widely used bivariate allometric model are beset by at least four interacting problems: (1) choice of an appropriate best-fit line with due attention to the influence of outliers; (2) objective recognition of divergent subsets in the data (allometric grades); (3) potential restrictions on statistical independence resulting from phylogenetic inertia; and (4) the need for extreme caution in inferring causation from correlation. A new non-parametric line-fitting technique has been developed that eliminates requirements for normality of distribution, greatly reduces the influence of outliers and permits objective recognition of grade shifts in substantial datasets. This technique is applied in scaling analyses of mammalian gestation periods and of neonatal body mass in primates. These analyses feed into a re-examination, conducted with partial correlation analysis, of the maternal energy hypothesis relating to mammalian brain evolution, which suggests links between body size and brain size in neonates and adults, gestation period and basal metabolic rate. Much has been made of the potential problem of phylogenetic inertia as a confounding factor in scaling analyses. However, this problem may be less severe than suspected earlier because nested analyses of variance conducted on residual variation (rather than on raw values) reveals that there is considerable variance at low taxonomic levels. In fact, limited divergence in body size between closely related species is one of the prime examples of phylogenetic inertia. One common approach to eliminating perceived problems of phylogenetic inertia in allometric analyses has been calculation of 'independent contrast values'. It is demonstrated that the reasoning behind this approach is flawed in several ways. Calculation of contrast values for closely related species of similar body size is, in fact, highly questionable, particularly when there are major deviations from the best-fit line for the scaling relationship under scrutiny.

Preoperative nutritional screening by the specialist instead of the nutritional risk score might prevent excess nutrition: a multivariate analysis of nutritional risk factors.

BACKGROUND: The aim of the current study was to assess whether widely used nutritional parameters are correlated with the nutritional risk score (NRS-2002) to identify postoperative morbidity and to evaluate the role of nutritionists in nutritional assessment. METHODS: A randomized trial on preoperative nutritional interventions (NCT00512213) provided the study cohort of 152 patients at nutritional risk (NRS-2002 ≥3) with a comprehensive phenotyping including diverse nutritional parameters (n=17), elaborated by nutritional specialists, and potential demographic and surgical (n=5) confounders. Risk factors for overall, severe (Dindo-Clavien 3-5) and infectious complications were identified by univariate analysis; parameters with P<0.20 were then entered in a multiple logistic regression model. RESULTS: Final analysis included 140 patients with complete datasets. Of these, 61 patients (43.6%) were overweight, and 72 patients (51.4%) experienced at least one complication of any degree of severity. Univariate analysis identified a correlation between few (≤3) active co-morbidities (OR=4.94; 95% CI: 1.47-16.56, p=0.01) and overall complications. Patients screened as being malnourished by nutritional specialists presented less overall complications compared to the not malnourished (OR=0.47; 95% CI: 0.22-0.97, p=0.043). Severe postoperative complications occurred more often in patients with low lean body mass (OR=1.06; 95% CI: 1-1.12, p=0.028). Few (≤3) active co-morbidities (OR=8.8; 95% CI: 1.12-68.99, p=0.008) were related with postoperative infections. Patients screened as being malnourished by nutritional specialists presented less infectious complications (OR=0.28; 95% CI: 0.1-0.78), p=0.014) as compared to the not malnourished. Multivariate analysis identified few co-morbidities (OR=6.33; 95% CI: 1.75-22.84, p=0.005), low weight loss (OR=1.08; 95% CI: 1.02-1.14, p=0.006) and low hemoglobin concentration (OR=2.84; 95% CI: 1.22-6.59, p=0.021) as independent risk factors for overall postoperative complications. Compliance with nutritional supplements (OR=0.37; 95% CI: 0.14-0.97, p=0.041) and supplementation of malnourished patients as assessed by nutritional specialists (OR=0.24; 95% CI: 0.08-0.69, p=0.009) were independently associated with decreased infectious complications. CONCLUSIONS: Nutritional support based upon NRS-2002 screening might result in overnutrition, with potentially deleterious clinical consequences. We emphasize the importance of detailed assessment of the nutritional status by a dedicated specialist before deciding on early nutritional intervention for patients with an initial NRS-2002 score of ≥3.

Ideal Body Size as a Mediator for the Gender-Specific Association Between Socioeconomic Status and Body Mass Index: Evidence From an Upper-Middle-Income Country in the African Region.

While obesity continues to rise globally, the associations between body size, gender, and socioeconomic status (SES) seem to vary in different populations, and little is known on the contribution of perceived ideal body size in the social disparity of obesity in African countries. We examined the gender and socioeconomic patterns of body mass index (BMI) and perceived ideal body size in the Seychelles, a middle-income small island state in the African region. We also assessed the potential role of perceived ideal body size as a mediator for the gender-specific association between SES and BMI. A population-based survey of 1,240 adults aged 25 to 64 years conducted in December 2013. Participants' BMI was calculated based on measured weight and height; ideal body size was assessed using a nine-silhouette instrument. Three SES indicators were considered: income, education, and occupation. BMI and perceived ideal body size were both higher among men of higher versus lower SES (p< .001) but lower among women of higher versus lower SES (p< .001), irrespective of the SES indicator used. Multivariate analysis showed a strong and direct association between perceived ideal body size and BMI in both men and women (p< .001) and was consistent with a potential mediating role of perceived ideal body size in the gender-specific associations between SES and BMI. Our study emphasizes the importance of gender and socioeconomic differences in BMI and ideal body size and suggests that public health interventions that promote perception of healthy weight could help mitigate SES-related disparities in BMI.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

From protest to powerlessness : a Marxist analysis of the Ontario NDP /

Using Marxist state theory as an analytical framework, this thesis explains the problems faced by the Ontario New Democratic Party government (1990-1995) in implementing a social democratic agenda. Not only was the government constrained in its ability to implement progressive policy, but it was also pushed to implement a Social Contract (involving legislated wage cuts to public sector employees) that alienated the party's base of support, making it more difficult for the party to organize in the future. Although this study relies predominantly on a reinterpretation of existing research on the topic, some primary research is used in the analysis, including interviews with members of the labour movement and former MPPs and analysis of the news media's treatment of the party/ government. Historical and class analytical perspectives are used to explain the evolution of the ONDP's structure and policies, as well as to assess the relative strength of the working class and its ability to support a social democratic political agenda. It was found that the ONDP' s unwillingness to develop a long term plan for social democracy, and its inability to act as a mass party or to build a strong working class movement, made it more difficult for the party to succeed when it formed the government. Moreover, the class nature of the capitalist state, along with pressure exerted by a well mobilized capitalist class, worked to limit the government' s options.

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.

Teaching media literacy skills about commercials: a comparative analysis of media literacy instruction /

In this study, methods of media literacy instruction including analytic activities, production activities, and a combination of analytic and production activities were compared to determine their influence on grade 8 students' knowledge, attitudes, and behaviours towards commercials. The findings showed that media literacy instruction does improve media literacy skills. Specifically, activities that included an analytic component or an analytic and production component were significantly better than activities that included a production component. Participants that completed analytic or analytic and production activities were able to discern media-related terms, target audience, selling techniques, social values, and stereotypes in commercials better than participants that completed only production activities. The research findings also showed obstacles when teaching media literacy. When engaged in analytic activities, the difficulties included locating suitable resources, addressing the competition from commercials, encouraging written reflection, recognizing social values, and discussing racial stereotypes. When engaged in production activities, the difficulties were positioning recording stations, managing group work, organizing ideas, filming the footage, computer issues, and scheduling time. Strategies to overcome these obstacles are described.

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.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.

Residues in soils : a gas chromatography - mass spectrometry study

Combined gas chromatography and mass spectrometry has been used to identify unknown residues in soils (especially pesticides). The effect of U.V. light on DDT and linuron and quantitative estimation of elemental sulfur in different soils has also been carried out.

"The whole earth as village" : a chronotopic analysis of Marshall McLuhan's "Global Village" and Patrick McGoohan's The Prisoner

Marshall McLuhan's "global village", and his theories on communications and technology, in conjunction with Patrick McGoohan's television series The Prisoner (ATV, 1967-1968) are explored in this thesis. The Prisoner, brainchild of McGoohan, is about the abduction and confinement of a British government agent imprisoned within the impenetrable boundaries of a benign but totalitarian city -state called "The Village". The purpose of his abduction and imprisonment is for the extraction of information regarding his resignation as a government spy. Marshall McLuhan originally popularized the phrase "the global village" in The Gutenberg Galaxy: The Making o/the Topographic Man (1962), asserting that, "The new electronic interdependence recreates the world in the image of a global village" (p. 31). This thesis argues that valid parallels exist between McGoohan's conception of "village", as manifested in The Prisoner, and McLuhan's global village. The comprehensive methodological stratagem for this thesis includes Marshall McLuhan's "mosaic" approach, Mikhail Bakhtin's concept ofthe "chronotope", as well as a Foucauldian genealogicallhistorical discourse analysis. In the process of deconstructing McLuhan's texts and The Prisoner as products of the 1960s, an historical "constellation" (to use Walter Benjamin's concept) of the same present has been executed. By employing this synthesized methodology, conjunctions have been made between McLuhan's theories and the series' main themes of bureaucracy as dictatorship, the perversion of science and technology, freedom as illusion, and the individual in opposition to the collective. A thorough investigation of the global village and The Prisoner will determine whether or not Marshall McLuhan and/or Patrick McGoohan visualize the village as an enslaving technological reality.

Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Systematic analysis of protein complexes involved in the human RNA polymerase II machinery

La transcription, la maturation d’ARN, et le remodelage de la chromatine sont tous des processus centraux dans l'interprétation de l'information contenue dans l’ADN. Bien que beaucoup de complexes de protéines formant la machinerie cellulaire de transcription aient été étudiés, plusieurs restent encore à identifier et caractériser. En utilisant une approche protéomique, notre laboratoire a purifié plusieurs composantes de la machinerie de transcription de l’ARNPII humaine par double chromatographie d’affinité "TAP". Cette procédure permet l'isolement de complexes protéiques comme ils existent vraisemblablement in vivo dans les cellules mammifères, et l'identification de partenaires d'interactions par spectrométrie de masse. Les interactions protéiques qui sont validées bioinformatiquement, sont choisies et utilisées pour cartographier un réseau connectant plusieurs composantes de la machinerie transcriptionnelle. En appliquant cette procédure, notre laboratoire a identifié, pour la première fois, un groupe de protéines, qui interagit physiquement et fonctionnellement avec l’ARNPII humaine. Les propriétés de ces protéines suggèrent un rôle dans l'assemblage de complexes à plusieurs sous-unités, comme les protéines d'échafaudage et chaperonnes. L'objectif de mon projet était de continuer la caractérisation du réseau de complexes protéiques impliquant les facteurs de transcription. Huit nouveaux partenaires de l’ARNPII (PIH1D1, GPN3, WDR92, PFDN2, KIAA0406, PDRG1, CCT4 et CCT5) ont été purifiés par la méthode TAP, et la spectrométrie de masse a permis d’identifier de nouvelles interactions. Au cours des années, l’analyse par notre laboratoire des mécanismes de la transcription a contribué à apporter de nouvelles connaissances et à mieux comprendre son fonctionnement. Cette connaissance est essentielle au développement de médicaments qui cibleront les mécanismes de la transcription.

Large scale identification of protein SUMOylation by mass spectrometry in HEK293 cells

Les fichiers qui accompagnent mon document sont des tableaux supplémentaires réalisés avec Excel (Microsoft Office), dans la version papier du mémoire ces fichiers sont sur un CD-ROM.