Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride

Under-ice phytoplankton blooms inhibited by spring convective mixing in refreezing leads

Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 123 (2018): 90–109, doi:10.1002/2016JC012575.Spring phytoplankton growth in polar marine ecosystems is limited by light availability beneath ice-covered waters, particularly early in the season prior to snowmelt and melt pond formation. Leads of open water increase light transmission to the ice-covered ocean and are sites of air-sea exchange. We explore the role of leads in controlling phytoplankton bloom dynamics within the sea ice zone of the Arctic Ocean. Data are presented from spring measurements in the Chukchi Sea during the Study of Under-ice Blooms In the Chukchi Ecosystem (SUBICE) program in May and June 2014. We observed that fully consolidated sea ice supported modest under-ice blooms, while waters beneath sea ice with leads had significantly lower phytoplankton biomass, despite high nutrient availability. Through an analysis of hydrographic and biological properties, we attribute this counterintuitive finding to springtime convective mixing in refreezing leads of open water. Our results demonstrate that waters beneath loosely consolidated sea ice (84–95% ice concentration) had weak stratification and were frequently mixed below the critical depth (the depth at which depth-integrated production balances depth-integrated respiration). These findings are supported by theoretical model calculations of under-ice light, primary production, and critical depth at varied lead fractions. The model demonstrates that under-ice blooms can form even beneath snow-covered sea ice in the absence of mixing but not in more deeply mixed waters beneath sea ice with refreezing leads. Future estimates of primary production should account for these phytoplankton dynamics in ice-covered waters.National Science Foundation (NSF) Grant Numbers: PLR-1304563 , PLR-1303617; KEL; NSF Graduate Research Fellowship Program Grant Number: DGE-06459622018-07-0

The influence of winter water on phytoplankton blooms in the Chukchi Sea

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 118 (2015): 53-72, doi:10.1016/j.dsr2.2015.06.006.The flow of nutrient-rich winter water (WW) through the Chukchi Sea plays an important and previously uncharacterized role in sustaining summer phytoplankton blooms. Using hydrographic and biogeochemical data collected as part of the ICESCAPE program (June-July 2010-11), we examined phytoplankton bloom dynamics in relation to the distribution and circulation of WW (defined as water with potential temperature ≤ -1.6°C) across the Chukchi shelf. Characterized by high concentrations of nitrate (mean: 12.3 ± 5.13 μmol L-1) that typically limits primary production in this region, WW was correlated with extremely high phytoplankton biomass, with mean chlorophyll a concentrations that were three-fold higher in WW (8.64 ± 9.75 μg L-1) than in adjacent warmer water (2.79 ± 5.58 μg L-1). Maximum chlorophyll a concentrations (~30 μg L-1) were typically positioned at the interface between nutrient-rich WW and shallower, warmer water with more light availability. Comparing satellite-based calculations of open water duration to phytoplankton biomass, nutrient concentrations, and oxygen saturation revealed widespread evidence of under-ice blooms prior to our sampling, with biogeochemical properties indicating that blooms had already terminated in many places where WW was no longer present. Our results suggest that summer phytoplankton blooms are sustained for a longer duration along the pathways of nutrient-rich WW and that biological hotspots in this region (e.g. the mouth of Barrow Canyon) are largely driven by the flow and confluence of these extremely productive pathways of WW that flow across the Chukchi shelf.This material is based upon work supported by the National Aeronautic and Space Administration (NASA) under Grant No. NNX10AF42G and the National Science Foundation Graduate Research Fellowship under Grant No. DGE-0645962 to K.E. Lowry

Protocol for the melatools skin self-monitoring trial: a phase II randomised controlled trial of an intervention for primary care patients at higher risk of melanoma.

INTRODUCTION: Melanoma is the fifth most common cancer in the UK. Incidence rates have quadrupled over the last 30 years and continue to rise, especially among younger people. As routine screening of the general population is not currently recommended in the UK, a focus on secondary prevention through early detection and prompt treatment in individuals at increased risk of melanoma could make an important contribution to improve melanoma outcomes. This paper describes the protocol for a phase II, multisite, randomised controlled trial, in the primary care setting, for patients at increased risk of melanoma. A skin self-monitoring (SSM) smartphone 'App' was used to improve symptom appraisal and encourage help seeking in primary care, thereby promoting early presentation with skin changes suspicious of melanoma. METHODS AND ANALYSIS: We aim to recruit 200 participants from general practice waiting rooms in the East of England. Eligible patients are those identified at higher melanoma risk (using a real-time risk assessment tool), without a personal history of melanoma, aged 18 to 75 years. Participants will be invited to a primary care nurse consultation, and randomised to the intervention group (standard written advice on skin cancer detection and sun protection, loading of an SSM 'App' onto the participant's smartphone and instructions on use including self-monitoring reminders) or control group (standard written advice alone). The primary outcomes are consultation rates for changes to a pigmented skin lesion, and the patient interval (time from first noticing a skin change to consultation). Secondary outcomes include patient sun protection behaviours, psychosocial outcomes, and measures of trial feasibility and acceptability. ETHICS AND DISSEMINATION: NHS ethical approval has been obtained from Cambridgeshire and Hertfordshire research ethics committee (REC reference 16/EE/0248). The findings from the MelaTools SSM Trial will be disseminated widely through peer-reviewed publications and scientific conferences. TRIAL REGISTRATION NUMBER: ISCTRN16061621.This work was supported by FMW’s Clinician Scientist award (RG 68235) from the National Institute for Health Research (NIHR). ... The paper also presents independent research funded/supported by the National Institute for Health Research (NIHR) Collaboration for Leadership in Applied Health Research & Care (CLAHRC) East of England, at Cambridgeshire and Peterborough NHS Foundation Trust

A randomised controlled trial to assess the effectiveness of a single session of nurse administered massage for short term relief of chronic non-malignant pain

Background: Massage is increasingly used to manage chronic pain but its benefit has not been clearly established. The aim of the study is to determine the effectiveness of a single session of nurse-administered massage for the short term relief of chronic non-malignant pain and anxiety. Methods: A randomised controlled trial design was used, in which the patients were assigned to a massage or control group. The massage group received a 15 minute manual massage and the control group a 15 minute visit to talk about their pain. Adult patients attending a pain relief unit with a diagnosis of chronic pain whose pain was described as moderate or severe were eligible for the study. An observer blind to the patients' treatment group carried out assessments immediately before (baseline), after treatment and 1, 2, 3 and 4 hours later. Pain was assessed using 100 mm visual analogue scale and the McGill Pain Questionnaire. Pain Relief was assessed using a five point verbal rating scale. Anxiety was assessed with the Spielberger short form State-Trait Anxiety Inventory. Results: 101 patients were randomised and evaluated, 50 in the massage and 51 in the control group. There were no statistically significant differences between the groups at baseline interview. Patients in the massage but not the control group had significantly less pain compared to baseline immediately after and one hour post treatment. 95% confidence interval for the difference in mean pain reduction at one hour post treatment between the massage and control groups is 5.47 mm to 24.70 mm. Patients in the massage but not the control group had a statistically significant reduction in anxiety compared to baseline immediately after and at 1 hour post treatment. Conclusion: Massage is effective in the short term for chronic pain of moderate to severe intensity

The effect of a lifestyle intervention in obese pregnant women on gestational metabolic profiles: findings from the UK Pregnancies Better Eating and Activity Trial (UPBEAT) randomised controlled trial

Background: Pregnancy is associated with widespread change in metabolism, which may be more marked in obese women. Whether lifestyle interventions in obese pregnant women improve pregnancy metabolic profiles remains unknown. Our objectives were to determine the magnitude of change in metabolic measures during obese pregnancy, to indirectly compare these to similar profiles in a general pregnant population, and to determine the impact of a lifestyle intervention on change in metabolic measures in obese pregnant women. Methods: Data from a randomised controlled trial of 1158 obese (BMI ≥ 30 kg/m2) pregnant women recruited from six UK inner-city obstetric departments were used. Women were randomised to either the UPBEAT intervention, a tailored complex lifestyle intervention focused on improving diet and physical activity, or standard antenatal care (control group). UPBEAT has been shown to improve diet and physical activity during pregnancy and up to 6-months postnatally in obese women and to reduce offspring adiposity at 6-months; it did not affect risk of gestational diabetes (the primary outcome). Change in the concentrations of 158 metabolic measures (129 lipids, 9 glycerides and phospholipids, and 20 low-molecular weight metabolites), quantified three times during pregnancy, were compared using multilevel models. The role of chance was assessed with a false discovery rate of 5% adjusted p values. Results: All very low-density lipoprotein (VLDL) particles increased by 1.5–3 standard deviation units (SD) whereas intermediate density lipoprotein and specific (large, medium and small) LDL particles increased by 1–2 SD, between 16 and 36 weeks’ gestation. Triglycerides increased by 2–3 SD, with more modest changes in other metabolites. Indirect comparisons suggest that the magnitudes of change across pregnancy in these obese women were 2- to 3-fold larger than in unselected women (n = 4260 in cross-sectional and 583 in longitudinal analyses) from an independent, previously published, study. The intervention reduced the rate of increase in extremely large, very large, large and medium VLDL particles, particularly those containing triglycerides. Conclusion: There are marked changes in lipids and lipoproteins and more modest changes in other metabolites across pregnancy in obese women, with some evidence that this is more marked than in unselected pregnant women. The UPBEAT lifestyle intervention may contribute to a healthier metabolic profile in obese pregnant women, but our results require replication. Trial Registration: UPBEAT was registered with Current Controlled Trials, ISRCTN89971375, on July 23, 2008 (prior to recruitment)

Performance of a prehospital HEART score in patients with possible myocardial infarction: a prospective evaluation

Introduction The History, Electrocardiogram (ECG), Age, Risk Factors and Troponin (HEART) score is commonly used to risk stratify patients with possible myocardial infarction as low risk or high risk in the Emergency Department (ED). Whether the HEART score can be used by paramedics to guide care were high-sensitivity cardiac troponin testing available in a prehospital setting is uncertain. Methods In a prespecified secondary analysis of a prospective cohort study where paramedics enrolled patients with suspected myocardial infarction, a paramedic Heart, ECG, Age, Risk Factors (HEAR) score was recorded contemporaneously, and a prehospital blood sample was obtained for subsequent cardiac troponin testing. HEART and modified HEART scores were derived using laboratory contemporary and high-sensitivity cardiac troponin I assays. HEART and modified HEART scores of ≤3 and ≥7 were applied to define low-risk and high-risk patients, and performance was evaluated for an outcome of major adverse cardiac events (MACEs) at 30 days. Results Between November 2014 and April 2018, 1054 patients were recruited, of whom 960 (mean 64 (SD 15) years, 42% women) were eligible for analysis and 255 (26%) experienced a MACE at 30 days. A HEART score of ≤3 identified 279 (29%) as low risk with a negative predictive value of 93.5% (95% CI 90.0% to 95.9%) for the contemporary assay and 91.4% (95% CI 87.5% to 94.2%) for the high-sensitivity assay. A modified HEART score of ≤3 using the limit of detection of the high-sensitivity assay identified 194 (20%) patients as low risk with a negative predictive value of 95.9% (95% CI 92.1% to 97.9%). A HEART score of ≥7 using either assay gave a lower positive predictive value than using the upper reference limit of either cardiac troponin assay alone. Conclusions A HEART score derived by paramedics in the prehospital setting, even when modified to harness the precision of a high-sensitivity assay, does not allow safe rule-out of myocardial infarction or enhanced rule-in compared with cardiac troponin testing alone. https://emj.bmj.com/content/40/7/474 This is an Open Access article distributed in accordance with the Creative Commons Attribution Non Commercial (CC BY-NC 4.0) license, which permits others to distribute, remix, adapt, build upon this work non-commercially, and license their derivative works on different terms, provided the original work is properly cited and the use is non-commercial. See: http://creativecommons.org/licenses/by-nc/4.0

Nitrogen Limitation of the Summer Phytoplankton and Heterotrophic Prokaryote Communities in the Chukchi Sea

Major changes to Arctic marine ecosystems have resulted in longer growing seasons with increased phytoplankton production over larger areas. In the Chukchi Sea, the high productivity fuels intense benthic denitrification creating a nitrogen (N) deficit that is transported through the Arctic to the Atlantic Ocean, where it likely fuels N fixation. Given the rapid pace of environmental change and the potentially globally significant N deficit, we conducted experiments aimed at understanding phytoplankton and microbial N utilization in the Chukchi Sea. Ship-board experiments tested the effect of nitrate (NO3-) additions on both phytoplankton and heterotrophic prokaryote abundance, community composition, photophysiology, carbon fixation and NO3- uptake rates. Results support the critical role of NO3- in limiting summer phytoplankton communities to small cells with low production rates. NO3- additions increased particulate concentrations, abundance of large diatoms, and rates of carbon fixation and NO3- uptake by cells >1 μm. Increases in the quantum yield and electron turnover rate of photosystem II in +NO3- treatments suggested that phytoplankton in the ambient dissolved N environment were N starved and unable to build new, or repair damaged, reaction centers. While some increases in heterotrophic prokaryote abundance and production were noted with NO3- amendments, phytoplankton competition or grazers likely dampened these responses. Trends toward a warmer more stratified Chukchi Sea will likely enhance summer oligotrophic conditions and further N starve Chukchi Sea phytoplankton communities

Designing interactive newsprint

The possibility of linking paper to digital information is enhanced by recent developments in printed electronics. In this article we report the design and evaluation of a local newspaper augmented with capacitive touch regions and an embedded Bluetooth chip working with an adjunct device. These allowed the interactive playback of associated audio and the registration of manual voting actions on the web. Design conventions inherited from paper and the web were explored by showing four different versions of an interactive newspaper to 16 community residents. The diverse responses of residents are described, outlining the potential of the approach for local journalism and recommendations for the design of interactive newsprint