Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent

Thia-Claisen rearrangements have been carried out using N-benzylpyrrolidine-2-thione and chiral allylic bromides derived from D-mannitol. Introduction of a bromine atom onto the double bond of the allylic bromide reverses the sense of diastereoselectivity in the [3,3]-sigmatropic rearrangement. Density functional theory calculations lead us to rationalise the observed selectivity in terms of a Cíeplak effect

Iron availability influences the tolerance of Southern Ocean phytoplankton to warming and elevated irradiance

The Southern Ocean is responsible for approximately 40% of oceanic carbon uptake through biological and physical processes. In the Southern Ocean, phytoplankton growth is limited by low iron (Fe) and light supply. Climate model projections for the Southern Ocean indicate that temperature, underwater irradiance and Fe supply are likely to change simultaneously in the future due to increasing anthropogenic carbon dioxide emissions. The individual effects of these environmental properties on phytoplankton physiology have been extensively researched, and culturing studies using Southern Ocean phytoplankton have shown that temperature and Fe will play a key role on setting growth under future conditions. To explore the potential responses of Southern Ocean phytoplankton to these environmental changes, we cultured the haptophyte Phaeocystis antarctica and the diatoms Chaetoceros flexuosus, Proboscia inermis, and Thalassiosira antarctica under two light and iron combinations and over a range of temperatures. Our study revealed that the thermal response curves of key Southern Ocean phytoplankton are diverse, with the highest growth rates measured at 5°C (the annual temperature range at the isolation sites is currently 1–4°C). Warming had species-specific effects on the photochemical efficiency of photosystem II (PSII; Fv/Fm), the functional absorption cross-section of PSII (σPSII), carbon:nitrogen ratio and cellular Chlorophyll a concentrations. Iron availability increased species’ ability to tolerate warmer conditions by increasing the upper limit for growth and subsequently increasing the thermal niche that each species inhabit

Some observations on the biogeochemical cycling of zinc in the Australian sector of the Southern Ocean: a dedication to Keith Hunter

In this study we investigated the distribution of dissolved and particulate zinc (dZn and pZn respectively) and its isotopes in the Subantarctic Zone as part of a Geotraces Process voyage. dZn and pZn depth profiles contrasted each other, with dZn showing depletion within the euphotic zone while pZn profiles showed enrichment. Fitting a power law equation to the pZn profiles produced an attenuation factor of 0.82, which contrasted values for particulate phosphorus, cadmium and copper. The results indicate that zinc has a longer regeneration length scale than phosphorus and cadmium, but shorter than copper. The differential regeneration of pZn relative to that of particulate phosphorus likely explains why dZn appears to have a deeper regeneration profile than that of phosphate. The dZn isotope (δ66Zndissolved) profiles collected across the Subantarctic Zone showed differing profile structures. For one station collected within an isolated cold-core eddy (CCE), δ66Zndissolved showed surface enrichment relative to deep waters. The corresponding pZn isotope profiles within the CCE did not show enrichment; rather, they were subtly depleted in surface waters and then converged to similar values at depth. Zinc isotope fractionation can be explained through a combination of fractionation processes associated with uptake by phytoplankton, zinc complexation by natural organic ligands and zinc regeneration from particulate matter

Distinct iron cycling in a Southern Ocean eddy

Mesoscale eddies are ubiquitous in the iron-limited Southern Ocean, controlling ocean-atmosphere exchange processes, however their influence on phytoplankton productivity remains unknown. Here we probed the biogeochemical cycling of iron (Fe) in a cold-core eddy. In-eddy surface dissolved Fe (dFe) concentrations and phytoplankton productivity were exceedingly low relative to external waters. In-eddy phytoplankton Fe-to-carbon uptake ratios were elevated 2–6 fold, indicating upregulated intracellular Fe acquisition resulting in a dFe residence time of ~1 day. Heavy dFe isotope values were measured for in-eddy surface waters highlighting extensive trafficking of dFe by cells. Below the euphotic zone, dFe isotope values were lighter and coincident with peaks in recycled nutrients and cell abundance, indicating enhanced microbially-mediated Fe recycling. Our measurements show that the isolated nature of Southern Ocean eddies can produce distinctly different Fe biogeochemistry compared to surrounding waters with cells upregulating iron uptake and using recycling processes to sustain themselves

Birthplace in New South Wales, Australia: An analysis of perinatal outcomes using routinely collected data

Background: The outcomes for women who give birth in hospital compared with at home are the subject of ongoing debate. We aimed to determine whether a retrospective linked data study using routinely collected data was a viable means to compare perinatal and maternal outcomes and interventions in labour by planned place of birth at the onset of labour in one Australian state.Methods: A population-based cohort study was undertaken using routinely collected linked data from the New South Wales Perinatal Data Collection, Admitted Patient Data Collection, Register of Congenital Conditions, Registry of Birth Deaths and Marriages and the Australian Bureau of Statistics. Eight years of data provided a sample size of 258,161 full-term women and their infants. The primary outcome was a composite outcome of neonatal mortality and morbidity as used in the Birthplace in England study.Results: Women who planned to give birth in a birth centre or at home were significantly more likely to have a normal labour and birth compared with women in the labour ward group. There were no statistically significant differences in stillbirth and early neonatal deaths between the three groups, although we had insufficient statistical power to test reliably for these differences.Conclusion: This study provides information to assist the development and evaluation of different places of birth across Australia. It is feasible to examine perinatal and maternal outcomes by planned place of birth using routinely collected linked data, although very large data sets will be required to measure rare outcomes associated with place of birth in a low risk population, especially in countries like Australia where homebirth rates are low. © 2014 Homer et al.; licensee BioMed Central Ltd

Maternal and perinatal outcomes by planned place of birth in Australia 2000 - 2012: A linked population data study

© Author(s) (or their employer(s)) 2019. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ. Objective To compare perinatal and maternal outcomes for Australian women with uncomplicated pregnancies according to planned place of birth, that is, in hospital labour wards, birth centres or at home. Design A population-based retrospective design, linking and analysing routinely collected electronic data. Analysis comprised χ 2 tests and binary logistic regression for categorical data, yielding adjusted ORs. Continuous data were analysed using analysis of variance. Setting All eight Australian states and territories. Participants Women with uncomplicated pregnancies who gave birth between 2000 and 2012 to a singleton baby in cephalic presentation at between 37 and 41 completed weeks' gestation. Of the 1 251 420 births, 1 171 703 (93.6%) were planned in hospital labour wards, 71 505 (5.7%) in birth centres and 8212 (0.7%) at home. Main outcome measures Mode of birth, normal labour and birth, interventions and procedures during labour and birth, maternal complications, admission to special care/high dependency or intensive care units (mother or infant) and perinatal mortality (intrapartum stillbirth and neonatal death). Results Compared with planned hospital births, the odds of normal labour and birth were over twice as high in planned birth centre births (adjusted OR (AOR) 2.72; 99% CI 2.63 to 2.81) and nearly six times as high in planned home births (AOR 5.91; 99% CI 5.15 to 6.78). There were no statistically significant differences in the proportion of intrapartum stillbirths, early or late neonatal deaths between the three planned places of birth. Conclusions This is the first Australia-wide study to examine outcomes by planned place of birth. For healthy women in Australia having an uncomplicated pregnancy, planned births in birth centres or at home are associated with positive maternal outcomes although the number of homebirths was small overall. There were no significant differences in the perinatal mortality rate, although the absolute numbers of deaths were very small and therefore firm conclusions cannot be drawn about perinatal mortality outcomes

Maternal and perinatal outcomes by planned place of birth among women with low-risk pregnancies in high-income countries: A systematic review and meta-analysis

© 2018 The Author(s) Background: The comparative safety of different birth settings is widely debated. Comparing research across high-income countries is complex, given differences in maternity service provision, data discrepancies, and varying research techniques and quality. Studies of births planned at home or in birth centres have reported both better and poorer outcomes than planned hospital births. Previous systematic reviews have focused on outcomes from either birth centres or home births, with inconsistent attention to quality appraisal. Few have attempted to synthesise findings. Objective: To compare maternal and perinatal outcomes from different places of birth via a systematic review of high-quality research, and meta-analysis of appropriate data (Prospero registration CRD42016042291). Design: Reviewers searched CINAHL, Embase, Maternity and Infant Care, Medline and PsycINFO databases to identify studies comparing selected outcomes by place of birth among women with low-risk pregnancies in high-income countries. They critically appraised identified studies using an instrument specific to birth place research and then combined outcome data via meta-analysis, using RevMan software. Findings: Twenty-eight articles met inclusion criteria, yielding comparative data on perinatal mortality, mode of birth, maternal morbidity and/or NICU admissions. Meta-analysis indicated that women planning hospital births had statistically significantly lower odds of normal vaginal birth than in other planned settings. Women experienced severe perineal trauma or haemorrhage at a lower rate in planned home births than in obstetric units. There were no statistically significant differences in infant mortality by planned place of birth, although most studies had limited statistical power to detect differences for rare outcomes. Differences in location, context, quality and design of identified studies render results subject to variation. Conclusions and implications for practice: High-quality evidence about low-risk pregnancies indicates that place of birth had no statistically significant impact on infant mortality. The lower odds of maternal morbidity and obstetric intervention support the expansion of birth centre and home birth options for women with low-risk pregnancies

Exploring mechanisms for spring bloom evolution: contrasting 2008 and 2012 blooms in the southwest Pacific Ocean

Observations from two research cruises made in 2008 and 2012 to east of New Zealand are put into context with satellite data to contrast and compare surface chlorophyll a evolution in the two years in order to explore mechanisms of phytoplankton bloom development in the southwest Pacific Ocean. In 2008, surface chlorophyll a largely followed the long-term climatological cycle, and 2008 can be considered a canonical year, where the autumn bloom is triggered by increasing vertical mixing at the end of summer and the spring bloom is triggered by decreasing vertical mixing at the end of winter. In contrast, 2012 was anomalous in that there was no autumn bloom, and in early spring there were several periods of sustained increase in surface chlorophyll a that did not become fully developed spring blooms. (In this region, we consider spring blooms to occur when surface chlorophyll a exceeds 0.5 mg m-3). These events can be related to alternating episodes of increased or decreased vertical mixing. The eventual spring bloom in October was driven by increased ocean cooling and wind stress (i.e. increased mixing) and paradoxically was driven by mechanisms considered more appropriate for autumn rather than spring blooms.New Zealand Government (National Institute of Water and Atmospheric Research to S.M.C., K.S. and P.W.B.); Australian Research Council (DP110100108, DP0770820 and DP130100679 to R.S. and M.J.E.); Natural Environmental Research Council (NERC NE/H004475/1 awarded to Maeve Lohan to support A.M.); Government of the Principality of Monaco (S.G.S.)

Transitioning global change experiments on Southern Ocean phytoplankton from lab to field settings: insights and challenges

The influence of global change on Southern Ocean productivity will have major ramifications for future management of polar life. A prior laboratory study investigated the response of a batch-cultured subantarctic diatom to projected change simulating conditions for 2100 (increased temperature/CO2/irradiance/iron; decreased macronutrients), showed a twofold higher chlorophyll-derived growth rate driven mainly by temperature and iron. We translated this design to the field to understand the phytoplankton community response, within a subantarctic foodweb, to 2100 conditions. A 7-d shipboard study utilizing 250-liter mesocosms was conducted in March 2016. The outcome mirrors lab-culture experiments, yielding twofold higher chlorophyll in the 2100 treatment relative to the control. This trend was also evident for intrinsic metrics including nutrient depletion. Unlike the lab-culture study, photosynthetic competence revealed a transient effect in the 2100 mesocosm, peaking on day 3 then declining. Metaproteomics revealed significant differences in protein profiles between treatments by day 7. The control proteome was enriched for photosynthetic processes (c.f. 2100) and exhibited iron-limitation signatures; the 2100 proteome exposed a shift in cellular energy production. Our findings of enhanced phytoplankton growth are comparable to model simulations, but underlying mechanisms (temperature, iron, and/or light) differ between experiments and models. Batch-culture approaches hinder cross-comparison of mesocosm findings to model simulations (the latter are akin to “continuous-culture chemostats”). However, chemostat techniques are problematic to use with mesocosms, as mesozooplankton will evade seawater flow-through, thereby accumulating. Thus, laboratory, field, and modeling approaches reveal challenges to be addressed to better understand how global change will alter Southern Ocean productivity