Zinc calixarene complexes for the ring opening polymerization of cyclic esters

Reaction of Zn(C₆F₅)₂·toluene (two equivalents) with 1,3-dipropoxy-p-tert-butyl-calix[4]arene (L¹H₂) led to the isolation of the complex [{Zn(C₆F₅)}₂L¹] (1), whilst similar use of Zn(Me)₂ resulted in the known complex [{Zn(Me)}₂L¹] (2). Treatment of L¹H₂ with in situ prepared Zn{N(SiMe₃)₂}₂ in refluxing toluene led to the isolation of the compound [(Na)ZnN(SiMe₃)₂L¹] (3). The stepwise reaction of L¹H₂ and sodium hydride, followed by ZnCl₂ and finally NaN(SiMe₃)₂ yielded the compound [Zn{N(SiMe₃)₂}₂L¹] (4). The reaction between three equivalents of Zn(C₆F₅)₂·toluene and oxacalix[3]arene (L²H₃) at room temperature formed the compound {[Zn(C₆F₅)]₃L²} (5); heating of 5 in acetonitrile caused the ring opening of the parent oxacalix[3]arene and rearrangement to afford the complex [(L²)Zn₆(C₆F₅)(R)(RH)OH]·5MeCN R = C₆F₅CH₂-(p-ᵗBuPhenolate-CH₂OCH₂–)₂–p-ᵗBuPhenolate-CH₂O⁻)³⁻ (6). The molecular structures of the new complexes 1, 3 and 6, together with that of the known complex 2, whose solid state structure has not previously been reported, have been determined. Compounds 1, 3–5 have been screened for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide. Compounds featuring a Zn–C₆F₅ fragment were found to be poor ROP pre-catalysts as they did not react with benzyl alcohol to form an alkoxide. By contrast, compound 4, which contains a zinc silylamide linkage, was the most active of the zinc-based calix[4]arene compounds screened and was capable of ROP at ambient temperature with 65% conversion over 4 h

Evidence-Based Dialogue Maps as a research tool to evaluate the quality of school pupils’ scientific argumentation

This pilot study focuses on the potential of Evidence-based Dialogue Mapping as a participatory action research tool to investigate young teenagers’ scientific argumentation. Evidence-based Dialogue Mapping is a technique for representing graphically an argumentative dialogue through Questions, Ideas, Pros, Cons and Data. Our research objective is to better understand the usage of Compendium, a Dialogue Mapping software tool, as both (1) a learning strategy to scaffold school pupils’ argumentation and (2) as a method to investigate the quality of their argumentative essays. The participants were a science teacher-researcher, a knowledge mapping researcher and 20 pupils, 12-13 years old, in a summer science course for “gifted and talented” children in the UK. This study draws on multiple data sources: discussion forum, science teacher-researcher’s and pupils’ Dialogue Maps, pupil essays, and reflective comments about the uses of mapping for writing. Through qualitative analysis of two case studies, we examine the role of Evidence-based Dialogue Maps as a mediating tool in scientific reasoning: as conceptual bridges for linking and making knowledge intelligible; as support for the linearisation task of generating a coherent document outline; as a reflective aid to rethinking reasoning in response to teacher feedback; and as a visual language for making arguments tangible via cartographic conventions

Modelling the impact of specific food policy options on coronary heart disease and stroke deaths in Ireland

Objective: To estimate the potential reduction in cardiovascular (CVD) mortality possible by decreasing salt, trans fat and saturated fat consumption, and by increasing fruit and vegetable (F/V) consumption in Irish adults aged 25–84years for 2010. Design: Modelling study using the validated IMPACT Food Policy Model across two scenarios. Sensitivity analysis was undertaken. First, a conservative scenario: reductions in dietary salt by 1 g/day, trans fat by 0.5% of energy intake, saturated fat by 1% energy intake and increasing F/V intake by 1 portion/day. Second, a more substantial but politically feasible scenario: reductions in dietary salt by 3 g/day, trans fat by 1% of energy intake, saturated fat by 3% of energy intake and increasing F/V intake by 3 portions/day. Setting: Republic of Ireland. Outcomes: Coronary heart disease (CHD) and stroke deaths prevented. Results: The small, conservative changes in food policy could result in approximately 395 fewer cardiovascular deaths per year; approximately 190 (minimum 155, maximum 230) fewer CHD deaths in men, 50 (minimum 40, maximum 60) fewer CHD deaths in women, 95 (minimum 75, maximum 115) fewer stroke deaths in men, and 60 (minimum 45, maximum 70) fewer stroke deaths in women. Approximately 28%, 22%, 23% and 26% of the 395 fewer deaths could be attributable to decreased consumptions in trans fat, saturated fat, dietary salt and to increased F/V consumption, respectively. The 395 fewer deaths represent an overall 10% reduction in CVD mortality. Modelling the more substantial but feasible food policy options, we estimated that CVD mortality could be reduced by up to 1070 deaths/year, representing an overall 26% decline in CVD mortality. Conclusions: A considerable CVD burden is attributable to the excess consumption of saturated fat, trans fat, salt and insufficient fruit and vegetables. There are significant opportunities for Government and industry to reduce CVD mortality through effective, evidence-based food policies

Unwind: Interactive Fish Straightening

The ScanAllFish project is a large-scale effort to scan all the world's 33,100 known species of fishes. It has already generated thousands of volumetric CT scans of fish species which are available on open access platforms such as the Open Science Framework. To achieve a scanning rate required for a project of this magnitude, many specimens are grouped together into a single tube and scanned all at once. The resulting data contain many fish which are often bent and twisted to fit into the scanner. Our system, Unwind, is a novel interactive visualization and processing tool which extracts, unbends, and untwists volumetric images of fish with minimal user interaction. Our approach enables scientists to interactively unwarp these volumes to remove the undesired torque and bending using a piecewise-linear skeleton extracted by averaging isosurfaces of a harmonic function connecting the head and tail of each fish. The result is a volumetric dataset of a individual, straight fish in a canonical pose defined by the marine biologist expert user. We have developed Unwind in collaboration with a team of marine biologists: Our system has been deployed in their labs, and is presently being used for dataset construction, biomechanical analysis, and the generation of figures for scientific publication

Conservation physiology can inform threat assessment and recovery planning processes for threatened species

Conservation physiology has emerged as a discipline with many success stories. Yet, it is unclear how it is currently integrated into the activities of the IUCN and other bodies which undertake international, national, or regional species threat assessments and work with partners to develop recovery plans. Here we argue that conservation physiology has much to offer for the threat assessment process and we outline the ways in which this can be operationalized. For instance, conservation physiology is effective in revealing causal relationships and mechanisms that explain observed patterns, such as population declines. Identifying the causes of population declines is a necessary precursor to the design of actions to reverse or mitigate such threats. Conservation physiology can also identify complex interactions and support modeling activities that consider emerging threats. When a population or species is deemed threatened and recovery plans are needed, physiology can be used to predict how organisms will respond to the conservation intervention and future threats. For example, if a recovery plan was focused on translocation, understanding how to safely translocate organisms would be necessary, as would ensuring that the recipient habitat provides the necessary environmental characteristics to meet the fundamental physiological needs/tolerances of that organism. Our hope is that this paper will clarify ways in which physiological data can make an important contribution to the conservation activities of bodies like the IUCN that are engaged in threat assess

Introduction of Macromolecules into Bovine Adrenal Medullary Chromaffin Cells and Rat Pheochromocytoma Cells (PC12) by Permeabilization with Streptolysin O: Inhibitory Effect of Tetanus Toxin on Catecholamine Secretion

Conditions are described for controlled plasma membrane permeabilization of rat pheochromocytoma cells (PC12) and cultured bovine adrenal chromaffin cells by Streptolysin O (SLO). The transmembrane pores created by SLO invoke rapid efflux of intracellular 86Rb+ and ATP, and also permit passive diffusion of proteins, including immunoglobulins, into the cells. SLO-permeabilized PC12 cells release [3H]dopamine in response to micromolar concentrations of free Ca2+. Permeabilized adrenal chromaffin cells present a similar exocytotic response to Ca2+ in the presence of Mg2+/ ATP. Permeabilized PC12 cells accumulate antibodies against synaptophysin and calmodulin, but neither antibody reduces the Ca2+-dependent secretory response. Reduced tetanus toxin, although ineffective when applied to intact chromaffin cells, inhibits Ca2+-induced exocytosis by both types of permeabilized cells studied. Omission of dithiothreitol, toxin inactivation by boiling, or preincubation with neutralizing antibodies abolishes the inhibitory effect. The data indicate that plasma membrane permeabilization by Streptolysin O is a useful tool to probe and define cellular components that are involved in the final steps of exocytosis

The MINERν\nuA Data Acquisition System and Infrastructure

MINER$\nu$A (Main INjector ExpeRiment $\nu$-A) is a new few-GeV neutrino cross section experiment that began taking data in the FNAL NuMI (Fermi National Accelerator Laboratory Neutrinos at the Main Injector) beam-line in March of 2010. MINER$\nu$A employs a fine-grained scintillator detector capable of complete kinematic characterization of neutrino interactions. This paper describes the MINER$\nu$A data acquisition system (DAQ) including the read-out electronics, software, and computing architecture.Comment: 34 pages, 16 figure

Lignocellulose degradation mechanisms across the Tree of Life.

Organisms use diverse mechanisms involving multiple complementary enzymes, particularly glycoside hydrolases (GHs), to deconstruct lignocellulose. Lytic polysaccharide monooxygenases (LPMOs) produced by bacteria and fungi facilitate deconstruction as does the Fenton chemistry of brown-rot fungi. Lignin depolymerisation is achieved by white-rot fungi and certain bacteria, using peroxidases and laccases. Meta-omics is now revealing the complexity of prokaryotic degradative activity in lignocellulose-rich environments. Protists from termite guts and some oomycetes produce multiple lignocellulolytic enzymes. Lignocellulose-consuming animals secrete some GHs, but most harbour a diverse enzyme-secreting gut microflora in a mutualism that is particularly complex in termites. Shipworms however, house GH-secreting and LPMO-secreting bacteria separate from the site of digestion and the isopod Limnoria relies on endogenous enzymes alone. The omics revolution is identifying many novel enzymes and paradigms for biomass deconstruction, but more emphasis on function is required, particularly for enzyme cocktails, in which LPMOs may play an important role.The work of the teams at York, Portsmouth and Cambridge on development of ideas expressed in this review was supported by grants from BBSRC (BB/H531543/1, BB/L001926/1, BB/1018492/1, BB/K020358/1). The workshop was supported by a US Partnering grant from BBSRC (BB/G016208/1) to Cragg and a BBSRC/FAPESP grant to Bruce (BB/1018492/1). Watts was supported by Marie Curie FP7-RG 276948. Goodell acknowledges support from USDA Hatch Project S-1041 VA-136288. Distel acknowledges support from NSF Award IOS1442759 and NIH Award Number U19 TW008163. Beckham thanks the US Department of Energy Bioenergy Technologies Office for funding. We appreciated the hospitality of the Linnean Society in allowing us to meet in inspirational surroundings under portraits of Linnaeus, Darwin and Wallace.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.cbpa.2015.10.01

Partnership, ownership and control: the impact of corporate governance on employment relations

Prevailing patterns of dispersed share ownership and rules of corporate governance for UK listed companies appear to constrain the ability of managers to make credible, long-term commitments to employees of the kind needed to foster effective labour-management partnerships. We present case study evidence which suggests that such partnerships can nevertheless emerge where product market conditions and the regulatory environment favour a stakeholder orientation. Proactive and mature partnerships may also be sustained where the board takes a strategic approach to mediating between the claims of different stakeholder groups, institutional investors are prepared to take a long-term view of their holdings, and strong and independent trade unions are in a position to facilitate organisational change

The Effectiveness of Alcohol Screening and Brief Intervention in Emergency Departments: A Multicentre Pragmatic Cluster Randomized Controlled Trial

BACKGROUND: Alcohol misuse is common in people attending emergency departments (EDs) and there is some evidence of efficacy of alcohol screening and brief interventions (SBI). This study investigated the effectiveness of SBI approaches of different intensities delivered by ED staff in nine typical EDs in England: the SIPS ED trial. METHODS AND FINDINGS: Pragmatic multicentre cluster randomized controlled trial of SBI for hazardous and harmful drinkers presenting to ED. Nine EDs were randomized to three conditions: a patient information leaflet (PIL), 5 minutes of brief advice (BA), and referral to an alcohol health worker who provided 20 minutes of brief lifestyle counseling (BLC). The primary outcome measure was the Alcohol Use Disorders Identification Test (AUDIT) status at 6 months. Of 5899 patients aged 18 or more presenting to EDs, 3737 (63·3%) were eligible to participate and 1497 (40·1%) screened positive for hazardous or harmful drinking, of whom 1204 (80·4%) gave consent to participate in the trial. Follow up rates were 72% (n?=?863) at six, and 67% (n?=?810) at 12 months. There was no evidence of any differences between intervention conditions for AUDIT status or any other outcome measures at months 6 or 12 in an intention to treat analysis. At month 6, compared to the PIL group, the odds ratio of being AUDIT negative for brief advice was 1·103 (95% CI 0·328 to 3·715). The odds ratio comparing BLC to PIL was 1·247 (95% CI 0·315 to 4·939). A per protocol analysis confirmed these findings. CONCLUSIONS: SBI is difficult to implement in typical EDs. The results do not support widespread implementation of alcohol SBI in ED beyond screening followed by simple clinical feedback and alcohol information, which is likely to be easier and less expensive to implement than more complex interventions