Psychosocial predictors of maternal emotional availability: Longitudinal analyses of the Mercy Pregnancy and Emotional Wellbeing Study (MPEWS) pregnancy cohort

Understanding the psychosocial predictors of the mother-infant relationship may provide important information to explain the variation in interaction quality observed between dyads. This research examined specific psychosocial predictors of maternal emotional availability (EA): maternal depression and trauma. In addition, the maternal psychosocial predictors of pacifier use during a mother-infant interaction were investigated. Data for the three empirical studies was drawn from 210 women recruited in early pregnancy until six-months postpartum within an Australian pregnancy cohort, the Mercy Pregnancy and Emotional Wellbeing Study. Women video-recorded interacting with their infants at six months postpartum were included, with the quality of their interactions assessed using the EA Scales (EAS). Depression was measured symptomatically and diagnostically at three time points from early pregnancy to six-months postpartum. Maternal trauma was specified as childhood trauma, childbirth experience and also included stressful life events. Observational data regarding pacifier use was collected by the viewing of each interaction, with the fourth translational study including a systematic review of the EA literature to facilitate integration of the EAS into clinical practice. First, results showed a small negative association between antenatal depressive symptoms and maternal EA. Second, moderate to severe childhood trauma and current stressful life events were negatively associated with maternal EA. Third, maternal EA status was associated with pacifier use during the mother-infant interaction. This dissertation highlights that beyond women with depression or trauma, there are other women experiencing reduced EA at six months postpartum. Given maternal EA could be a protective factor for both child outcomes, and the future mother-child relationship, consideration of integrating the EAS into a clinical setting should be explored

Enantioselective Organocatalytic Cyclopropanations. The Identification of a New Class of Iminium Catalyst Based upon Directed Electrostatic Activation

A new method for enantioselective organocatalytic cyclopropanation is described. This study outlines the identification of a new class of iminium catalyst based on the concept of directed electrostatic activation (DEA). This novel organocatalytic mechanism exploits dual activation of ylide and enal substrates through a proposed electrostatic activation and stereodirected protocol. Formation of trisubstituted cyclopropanes with high levels of enantio- and diastereoinduction is accomplished for a variety of α,β-unsaturated aldehydes and sulfonium ylides. In addition, mechanistic studies have found that this cyclopropanation reaction exhibits enantioselectivity and reactivity profiles that are in accord with the proposed DEA step

Total Synthesis of Brasoside and Littoralisone

The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed α-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2

Rapid access to Asp/Glu sidechain hydrazides as thioester precursors for peptide cyclization and glycosylation

Head-to-sidechain macrocylic peptides, and neoglycopeptides, were readily prepared by site-specific amidation of aspartic and glutamic acid sidechain hydrazides. Hydrazides, serving as latent thioesters, were introduced through regioselective opening of the corresponding Na-Fmoc protected anhydride precursors

Enantioselective Organocatalytic Amine Conjugate Addition

The first enantioselective organocatalytic amine conjugate addition has been successfully developed. The application of LUMO-lowering iminium catalysis has enabled the highly chemo- and enantioselective 1,4-addition of a rationally designed N-silyloxycarbamate nucleophile (HOMO-raised) to α,β-unsaturated aldehydes. Imidazolidinone 2•pTSA was found to catalyze the addition of various orthogonally N-protected silyloxycarbamate nucleophiles to a range of α,β-unsaturated aldehydes, affording synthetically useful β-amino aldehyde intermediates. The synthetic utility of the protocol was demonstrated in the rapid synthesis of enantioenriched β-amino acids in one operation and 1,3-amino alcohol derivatives in three operations

Roles of domain-general auditory processing in spoken second-language vocabulary attainment in adulthood

Recently, scholars have begun to explore the hypothesis that individual differences in domain-general auditory perception, which has been identified as an anchor of L1 acquisition, could explain some variance in postpubertal L2 learners’ segmental and suprasegmental learning in immersive settings. The current study set out to examine the generalizability of the topic to the acquisition of higher-level linguistic production skills—that is the appropriate use of diverse, rich, and abstract vocabulary. The speech of 100 Polish-English bilinguals was elicited using an interview task, submitted to corpus-/rater-based linguistic analyses, and linked to their ability to discriminate sounds based on individual acoustic dimensions (pitch, duration, and amplitude). According to the results, those who attained more advanced L2 lexical proficiency demonstrated not only more relevant experience (extensive immersion and earlier age of arrival), but also more precise auditory perception ability

Models of gravitational lens candidates from Space Warps CFHTLS

We report modelling follow-up of recently-discovered gravitational-lens candidates in the Canada France Hawaii Telescope Legacy Survey. Lens modelling was done by a small group of specially-interested volunteers from the SpaceWarps citizen-science community who originally found the candidate lenses. Models are categorised according to seven diagnostics indicating (a) the image morphology and how clear or indistinct it is, (b) whether the mass map and synthetic lensed image appear to be plausible, and (c) how the lens-model mass compares with the stellar mass and the abundance-matched halo mass. The lensing masses range from ~10^11 Msun to >10^13 Msun. Preliminary estimates of the stellar masses show a smaller spread in stellar mass (except for two lenses): a factor of a few below or above ~10^11 Msun. Therefore, we expect the stellar-to-total mass fraction to decline sharply as lensing mass increases. The most massive system with a convincing model is J1434+522 (SW05). The two low-mass outliers are J0206-095 (SW19) and J2217+015 (SW42); if these two are indeed lenses, they probe an interesting regime of very low star-formation efficiency. Some improvements to the modelling software (SpaghettiLens), and discussion of strategies regarding scaling to future surveys with more and frequent discoveries, are included.Comment: 16 pages, 10 figures, 1 table, online supplement table_1.csv contains additional detailed numbers shown in table 1 and figure

Gravitational lens modelling in a citizen science context

We develop a method to enable collaborative modelling of gravitational lenses and lens candidates, that could be used by non-professional lens enthusiasts. It uses an existing free-form modelling program (glass), but enables the input to this code to be provided in a novel way, via a user-generated diagram that is essentially a sketch of an arrival-time surface. We report on an implementation of this method, SpaghettiLens, which has been tested in a modelling challenge using 29 simulated lenses drawn from a larger set created for the Space Warps citizen science strong lens search. We find that volunteers from this online community asserted the image parities and time ordering consistently in some lenses, but made errors in other lenses depending on the image morphology. While errors in image parity and time ordering lead to large errors in the mass distribution, the enclosed mass was found to be more robust: the model-derived Einstein radii found by the volunteers were consistent with those produced by one of the professional team, suggesting that given the appropriate tools, gravitational lens modelling is a data analysis activity that can be crowd-sourced to good effect. Ideas for improvement are discussed, these include (a) overcoming the tendency of the models to be shallower than the correct answer in test cases, leading to systematic overestimation of the Einstein radius by 10 per cent at present, and (b) detailed modelling of arcs.Comment: 10 pages, 12 figure