Asymmetric oxidation of sulfides

This review discusses synthesis of enantiopure sulfoxides through the asymmetric oxidation of prochiral sulfides. The use of metal complexes to promote asymmetric sulfoxidation is described in detail, with a particular emphasis on the synthesis of biologically active sulfoxides. The use of non-metal-based systems, such as oxaziridines, chiral hydroperoxides and peracids, as well as enzyme-catalyzed sulfoxidations is also examined.

Étude des mécanismes de surenroulement de l'ADN induit par la transcription chez Escherichia coli

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Pigments of sediment cores of the Northwest European Continental Margin

In the context of the European OMEX Programme this investigation focused on gradients in the biomass and activity of the small benthic size spectrum along a transect across the Goban Spur from the outer Celtic Sea into Porcupine Abyssal Plain. The effects of food pulses (seasonal, episodic) on this part of the benthic size spectrum were investigated. Sediments sampled during eight expeditions at different seasons covering a range from 200 m to 4800 m water depth were assayed with biochemical bulk measurements: determinations of chloroplastic pigment equivalents (CPE), the sum of chlorophyll a and its breakdown products, provide information concerning the input of phytodetrital matter to the seafloor; phospholipids were analyzed to estimate the total biomass of small benthic organisms (including bacteria, fungi, flagellata, protozoa and small metazoan meiofauna). A new term 'small size class biomass' (SSCB) is introduced for the biomass of the smallest size classes of sediment-inhabiting organisms; the reduction of fluorescein-di-acetate (FDA) was determined to evaluate the potential activity of ester-cleaving bacterial exoenzymes in the sediment samples. At all stations benthic biomass was predominantly composed of the small size spectrum (90% on the shelf; 97-98% in the bathyal and abyssal parts of the transect). Small size class biomass (integrated over a 10 cm sediment column) ranged from 8 g C/m**2 on the shelf to 2.1 g C/m**2 on the adjacent Porcupine Abyssal Plain, exponentially decreasing with increasing water depth. However, a correlation between water depth and SSCB, macrofauna biomass as well as metazoan meiofauna biomass exhibited a significantly flatter slope for the small size classes in comparison to the larger organisms. CPE values indicated a pronounced seasonal cycle on the shelf and upper slope with twin peaks of phytodetrital deposition in mid spring and late summer. The deeper stations seem to receive a single annual flux maximum in late summer. SSCB and heterotrophic activity are significantly correlated to the amount of sediment-bound pigments. Seasonality in pigment concentrations is clearly followed by SSCB and activity. In contrast to macro- and megafauna which integrate over larger periods (months/years), the small benthic size classes, namely bacteria and foraminifera, proved to be the most reactive potential of the benthic communities to any perturbations on short time scales (days/weeks). The small size classes, therefore, occupy a key role in early diagenetic processes.

Coagent Modified Polypropylene Prepared by Reactive Extrusion: A New Look Into the Structure-Property Relations of Injection Molded Parts

Peroxide-mediated reactive extrusion of linear isotactic polypropylene (L-PP) was conducted in the presence of trimethylolpropane trimethacrylate (TMPTMA) and triallyl trimesate (TAM) coagents, using a twin screw extruder. The resulting coagent-modified polypropylenes (CM-PP) had higher viscosities and elasticities, as well as increased crystallization temperature compared to PP reacted only with peroxide (DCP-PP). Additionally, deviations from terminal flow, and strain hardening were observed in PP modified with TAM, signifying the presence of long chain branching (LCB). The CM-PP formulations retained the modulus and tensile strength of the parent L-PP, in spite of their lower molar mass and viscosities, whereas their elongation at break and the impact strength were better. This was attributed to the finer spherulitic structure of these materials, and to the disappearance of the skin-core layer in the injection molded specimens.

EXAMINING HOW SAME-GENDER AND MIXED-GENDER COUPLES NAVIGATE SEXUAL ISSUES IN THEIR RELATIONSHIPS

Sexual scripts—the definitions and expectations that individuals hold for sexual interactions—are thought to play an important role in the maintenance of sexual well-being. Sexual scripts can be rigid or flexible, and they can be concordant or discordant between members of a couple. Sex therapists support sexual script flexibility for maintaining sexual and relationship satisfaction when couples are navigating sexual issues. However, empirical research examining the role of sexual script flexibility and the degree of script concordance/discordance in couples’ sexual well-being has been limited, due in part to the limited measures available. Furthermore, within the existing research, there has been an unfortunate tendency to exclude individuals in same-gender relationships – perpetuating the long-standing knowledge gap in the literature on positive sexuality in diverse relationships. To address these gaps in the literature, we conducted a series of online studies that recruited individuals in diverse relationships. A measure of individual sexual script flexibility in response to sexual issues was developed (Chapter 2); in addition, the structure of an existing measure assessing couple sexual scripts in response to a sexual issue was evaluated (Chapter 3). Chapter 4 examined how individuals in diverse relationships compared on measures of individual sexual script flexibility and on couple sexual scripts. Findings suggest that there are more similarities than differences across diverse couples. Chapter 5 explored how flexibility in an individual’s approach to sexual issues relates to sexual well-being, specifically by assessing sexual communication and partner responses as mediators. Results suggest that individual sexual script flexibility relates to sexual well-being through reciprocal partner processes. Collectively, this research program suggests that more similarities than differences exist between individuals in same- and mixed-gender relationships, and that partners are important to consider in the relationship between individual sexual script flexibility and sexual well-being. These findings have implications for sex and couple therapy; these results emphasize the importance of interventions that target both members of the couple, and further our understanding of sexuality in same- and mixed-gender relationships.

Predicting the Dispersal Potential of an Invasive Polychaete Pest along a Complex Coastal Biome

Boccardia proboscidea is a recently introduced polychaete in South Africa where it is a notorious pest of commercially reared abalone. Populations were originally restricted to abalone farms but a recent exodus into the wild at some localities has raised conservation concerns due to the species’ invasive status in other parts of the world. Here, we assessed the dispersal potential of B. proboscidea by using a population genetic and oceanographic modeling approach. Since the worm is in its incipient stages of a potential invasion, we used the closely related Polydora hoplura as a proxy due its similar reproductive strategy and its status as a pest of commercially reared oysters in the country. Populations of P. hoplura were sampled from seven different localities and a section of the mtDNA gene, Cyt b and the intron ATPSa was amplified. A high resolution model of the coastal waters around southern Africa was constructed using the Regional Ocean Modeling System. Larvae were represented by passive drifters that were deployed at specific points along the coast and dispersal was quantified after a 12-month integration period. Our results showed discordance between the genetic and modeling data. There was low genetic structure (Φ = 0.04 for both markers) and no geographic patterning of mtDNA and nDNA haplotypes. However, the dispersal model found limited connectivity around Cape Point—a major phylogeographic barrier on the southern African coast. This discordance was attributed to anthropogenic movement of larvae and adult worms due to vectors such as aquaculture and shipping. As such, we hypothesized that cryptic dispersal could be overestimating genetic connectivity. Though wild populations of B. proboscidea could become isolated due to the Cape Point barrier, anthropogenic movement may play the critical role in facilitating the dispersal and spread of this species on the southern African coast.

Predicting the Dispersal Potential of an Invasive Polychaete Pest along a Complex Coastal Biome

Boccardia proboscidea is a recently introduced polychaete in South Africa where it is a notorious pest of commercially reared abalone. Populations were originally restricted to abalone farms but a recent exodus into the wild at some localities has raised conservation concerns due to the species’ invasive status in other parts of the world. Here, we assessed the dispersal potential of B. proboscidea by using a population genetic and oceanographic modeling approach. Since the worm is in its incipient stages of a potential invasion, we used the closely related Polydora hoplura as a proxy due its similar reproductive strategy and its status as a pest of commercially reared oysters in the country. Populations of P. hoplura were sampled from seven different localities and a section of the mtDNA gene, Cyt b and the intron ATPSa was amplified. A high resolution model of the coastal waters around southern Africa was constructed using the Regional Ocean Modeling System. Larvae were represented by passive drifters that were deployed at specific points along the coast and dispersal was quantified after a 12-month integration period. Our results showed discordance between the genetic and modeling data. There was low genetic structure (Φ = 0.04 for both markers) and no geographic patterning of mtDNA and nDNA haplotypes. However, the dispersal model found limited connectivity around Cape Point—a major phylogeographic barrier on the southern African coast. This discordance was attributed to anthropogenic movement of larvae and adult worms due to vectors such as aquaculture and shipping. As such, we hypothesized that cryptic dispersal could be overestimating genetic connectivity. Though wild populations of B. proboscidea could become isolated due to the Cape Point barrier, anthropogenic movement may play the critical role in facilitating the dispersal and spread of this species on the southern African coast.

The puppet as a tool for working in Art Therapy

This article aims to investigate the possibilities of building puppets in art therapy workshop, for this it realizes a tour of the primitive use of the puppet as a magical twin and potential towards the study of authors who have used the puppets as a therapeutic tool from the first half of the twentieth century. It’s raised an own theoretical organization, which includes the consideration of the significance of the body in the construction and management of the puppet and the puppet transitional perspective, halfway of external reality and psychic reality as an object that makes fantasy and reality arises built.

The discrepancy between social isolation and loneliness as a clinically meaningful metric: findings from the Irish and English longitudinal studies of ageing (TILDA and ELSA)

Objective
Scant evidence is available on the discordance between loneliness and social isolation among older adults. We aimed to investigate this discordance and any health implications that it may have.

Method
Using nationally representative datasets from ageing cohorts in Ireland (TILDA) and England (ELSA), we created a metric of discordance between loneliness and social isolation, to which we refer as Social Asymmetry. This metric was the categorised difference between standardised scores on a scale of loneliness and a scale of social isolation, giving categories of: Concordantly Lonely and Isolated, Discordant: Robust to Loneliness, or Discordant: Susceptible to Loneliness. We used regression and multilevel modelling to identify potential relationships between Social Asymmetry and cognitive outcomes.

Results
Social Asymmetry predicted cognitive outcomes cross-sectionally and at a two-year follow-up, such that Discordant: Robust to Loneliness individuals were superior performers, but we failed to find evidence for Social Asymmetry as a predictor of cognitive trajectory over time.

Conclusions
We present a new metric and preliminary evidence of a relationship with clinical outcomes. Further research validating this metric in different populations, and evaluating its relationship with other outcomes, is warranted.

Optimization and Prediction of Mechanical and Thermal Properties of Graphene/LLDPE Nanocomposites by Using Artificial Neural Networks

The focus of this work is to develop the knowledge of prediction of the physical and chemical properties of processed linear low density polyethylene (LLDPE)/graphene nanoplatelets composites. Composites made from LLDPE reinforced with 1, 2, 4, 6, 8, and 10 wt% grade C graphene nanoplatelets (C-GNP) were processed in a twin screw extruder with three different screw speeds and feeder speeds (50, 100, and 150 rpm). These applied conditions are used to optimize the following properties: thermal conductivity, crystallization temperature, degradation temperature, and tensile strength while prediction of these properties was done through artificial neural network (ANN). The three first properties increased with increase in both screw speed and C-GNP content. The tensile strength reached a maximum value at 4 wt% C-GNP and a speed of 150 rpm as this represented the optimum condition for the stress transfer through the amorphous chains of the matrix to the C-GNP. ANN can be confidently used as a tool to predict the above material properties before investing in development programs and actual manufacturing, thus significantly saving money, time, and effort.

Prevalence and risk of Down syndrome in monozygotic and dizygotic multiple pregnancies in Europe: implications for prenatal screening

OBJECTIVE: To determine risk of Down syndrome (DS) in multiple relative to singleton pregnancies, and compare prenatal diagnosis rates and pregnancy outcome.

DESIGN: Population-based prevalence study based on EUROCAT congenital anomaly registries.

SETTING: Eight European countries.

POPULATION: 14.8 million births 1990-2009; 2.89% multiple births.

METHODS: DS cases included livebirths, fetal deaths from 20 weeks, and terminations of pregnancy for fetal anomaly (TOPFA). Zygosity is inferred from like/unlike sex for birth denominators, and from concordance for DS cases.

MAIN OUTCOME MEASURES: Relative risk (RR) of DS per fetus/baby from multiple versus singleton pregnancies and per pregnancy in monozygotic/dizygotic versus singleton pregnancies. Proportion of prenatally diagnosed and pregnancy outcome.

STATISTICAL ANALYSIS: Poisson and logistic regression stratified for maternal age, country and time.

RESULTS: Overall, the adjusted (adj) RR of DS for fetus/babies from multiple versus singleton pregnancies was 0.58 (95% CI 0.53-0.62), similar for all maternal ages except for mothers over 44, for whom it was considerably lower. In 8.7% of twin pairs affected by DS, both co-twins were diagnosed with the condition. The adjRR of DS for monozygotic versus singleton pregnancies was 0.34 (95% CI 0.25-0.44) and for dizygotic versus singleton pregnancies 1.34 (95% CI 1.23-1.46). DS fetuses from multiple births were less likely to be prenatally diagnosed than singletons (adjOR 0.62 [95% CI 0.50-0.78]) and following diagnosis less likely to be TOPFA (adjOR 0.40 [95% CI 0.27-0.59]).

CONCLUSIONS: The risk of DS per fetus/baby is lower in multiple than singleton pregnancies. These estimates can be used for genetic counselling and prenatal screening.