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A low-cost, scalable and reproducible approach for the mass production of screen-printed electrode (SPE) platforms that have varying percentage mass incorporations of 2D hexagonal boron nitride (2D-hBN) (2D-hBN/SPEs) is demonstrated herein. These novel 2D-hBN/SPEs are explored as a potential metal-free electrocatalysts towards oxygen reduction reactions (ORRs) within acidic media where their performance is evaluated. A 5% mass incorporation of 2D-hBN into the SPEs resulted in the most beneficial ORR catalysis, reducing the ORR onset potential by ca. 200 mV in comparison to bare/unmodified SPEs. Furthermore, an increase in the achievable current of 83% is also exhibited upon the utilisation of a 2D-hBN/SPE in comparison to its unmodified equivalent. The screen-printed fabrication approach replaces the less-reproducible and time-consuming drop-casting technique of 2D-hBN and provides an alternative approach for the large-scale manufacture of novel electrode platforms that can be utilised in a variety of applications.

BACKGROUND: The critical shoulder angle (CSA) is a radiographic measurement that provides an assessment of both glenoid inclination and acromial length. Higher values may correlate with the presence of rotator cuff tears. However, it is difficult to obtain a high-quality true anteroposterior (AP) radiograph of the shoulder, with any excess scapular version or flexion/extension resulting in deviation from the true CSA value. Three-dimensional (3D) bony reconstructions of computed tomography (CT) shoulder scans may be able to be rotated to obtain a similar view to that of true AP radiographs. AIM: To compare CSA measurements performed on 3D bony CT reconstructions, with those on corresponding true AP radiographs. METHODS: CT shoulder scans were matched with true AP radiographs that were classified as either Suter-Henninger type A or C quality. 3D bony reconstructions were segmented from the CT scans, and rotated to replicate an ideal true AP view. Two observers performed CSA measurements using both CT and radiographic images. Measurements were repeated after a one week interval. Reliability was assessed using intraclass correlation coefficients (ICCs) and Bland-Altman plots [bias, limits of agreement (LOA)]. RESULTS: Twenty CT shoulder scans were matched. The mean CSA values were 32.55° (± 4.26°) with radiographs and 29.82° (± 3.49°) with the CT-based method [mean difference 2.73° (± 2.86°); P < 0.001; bias +2.73°; LOA -2.17° to +7.63°]. There was a strong correlation between the two methods (r = 0.748; P < 0.001). Intra-observer reliability was similar, but the best intra-observer values were achieved by the most experienced observer using the CT-based method [ICC: 0.983 (0.958-0.993); bias +0.03°, LOA -1.28° to +1.34°]. Inter-observer reliability was better with the CT-based method [ICC: 0.897 (0.758-0.958), bias +0.24°, LOA -2.93° to +3.41°]. CONCLUSION: The described CT-based method may be a suitable alternative for critical shoulder angle measurement, as it overc

Endocrine therapy resistance frequently develops in estrogen receptor positive (ER+) breast cancer, but the underlying molecular mechanisms are largely unknown. Here, we show that 3-dimensional (3D) chromatin interactions both within and between topologically associating domains (TADs) frequently change in ER+ endocrine-resistant breast cancer cells and that the differential interactions are enriched for resistance-associated genetic variants at CTCF-bound anchors. Ectopic chromatin interactions are preferentially enriched at active enhancers and promoters and ER binding sites, and are associated with altered expression of ER-regulated genes, consistent with dynamic remodelling of ER pathways accompanying the development of endocrine resistance. We observe that loss of 3D chromatin interactions often occurs coincidently with hypermethylation and loss of ER binding. Alterations in active A and inactive B chromosomal compartments are also associated with decreased ER binding and atypical interactions and gene expression. Together, our results suggest that 3D epigenome remodelling is a key mechanism underlying endocrine resistance in ER+ breast cancer.

BACKGROUND: The proportion of births via cesarean section (CS) varies worldwide and in many countries exceeds WHO-recommended rates. Long-term health outcomes for children born by CS are poorly understood, but limited data suggest that CS is associated with increased infection-related hospitalisation. We investigated the relationship between mode of birth and childhood infection-related hospitalisation in high-income countries with varying CS rates. METHODS AND FINDINGS: We conducted a multicountry population-based cohort study of all recorded singleton live births from January 1, 1996 to December 31, 2015 using record-linked birth and hospitalisation data from Denmark, Scotland, England, and Australia (New South Wales and Western Australia). Birth years within the date range varied by site, but data were available from at least 2001 to 2010 for each site. Mode of birth was categorised as vaginal or CS (emergency/elective). Infection-related hospitalisations (overall and by clinical type) occurring after the birth-related discharge date were identified in children until 5 years of age by primary/secondary International Classification of Diseases, 10th Revision (ICD-10) diagnosis codes. Analysis used Cox regression models, adjusting for maternal factors, birth parameters, and socioeconomic status, with results pooled using meta-analysis. In total, 7,174,787 live recorded births were included. Of these, 1,681,966 (23%, range by jurisdiction 17%-29%) were by CS, of which 727,755 (43%, range 38%-57%) were elective. A total of 1,502,537 offspring (21%) had at least 1 infection-related hospitalisation. Compared to vaginally born children, risk of infection was greater among CS-born children (hazard ratio (HR) from random effects model, HR 1.10, 95% confidence interval (CI) 1.09-1.12, p < 0.001). The risk was higher following both elective (HR 1.13, 95% CI 1.12-1.13, p < 0.001) and emergency CS (HR 1.09, 95% CI 1.06-1.12, p < 0.001). Increased risks persisted to 5 years an

© 2019 Hydrogen Energy Publications LLC We present a facile methodology for the synthesis of a novel 2D-MoS2, graphene and CuNi2S4 (MoS2-g-CuNi2S4) nanocomposite that displays highly efficient electrocatalytic activity towards the production of hydrogen. The intrinsic hydrogen evolution reaction (HER) activity of MoS2 nanosheets was significantly enhanced by increasing the affinity of the active edge sites towards H+ adsorption using transition metal (Cu and Ni2) dopants, whilst also increasing the edge sites exposure by anchoring them to a graphene framework. Detailed XPS analysis reveals a higher percentage of surface exposed S at 17.04%, of which 48.83% is metal bonded S (sulfide). The resultant MoS2-g-CuNi2S4 nanocomposites are immobilized upon screen-printed electrodes (SPEs) and exhibit a HER onset potential and Tafel slope value of – 0.05 V (vs. RHE) and 29.3 mV dec−1, respectively. These values are close to that of the polycrystalline Pt electrode (near zero potential (vs. RHE) and 21.0 mV dec−1, respectively) and enhanced over a bare/unmodified SPE (– 0.43 V (vs. RHE) and 149.1 mV dec−1, respectively). Given the efficient, HER activity displayed by the novel MoS2-g-CuNi2S4/SPE electrochemical platform and the comparatively low associated cost of production for this nanocomposite, it has potential to be a cost-effective alternative to Pt within electrolyser technologies.

© 2019 Additive manufacturing (AM)/3D printing technology provides a novel platform for the rapid prototyping of low cost 3D platforms. Herein, we report for the first time, the fabrication, characterisation (physicochemical and electrochemical) and application (electrochemical sensing) of bespoke nanographite (NG)-loaded (25 wt%) AM printable (via fused deposition modelling) NG/PLA filaments. We have optimised and tailored a variety of NG-loaded filaments and their AM counterparts in order to achieve optimal printability and electrochemical behaviour. Two AM platforms, namely AM macroelectrodes (AMEs) and AM 3D honeycomb (macroporous) structures are benchmarked against a range of redox probes and the simultaneous detection of lead (II) and cadmium (II). This proof-of-concept demonstrates the impact that AM can have within the area of electroanalytical sensors.

© 2019 Manchester Metropolitan University. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The first entirely AM/3D-printed sodium-ion (full-cell) battery is reported herein, presenting a paradigm shift in the design and prototyping of energy-storage architectures. AM/3D-printing compatible composite materials are developed for the first time, integrating the active materials NaMnO 2 and TiO 2 within a porous supporting material, before being AM/3D-printed into a proof-of-concept model based upon the basic geometry of commercially existing AA battery designs. The freestanding and completely AM/3D-fabricated device demonstrates a respectable performance of 84.3 mAh g −1 with a current density of 8.43 mA g −1 ; note that the structure is typically comprised of 80% thermoplastic, but yet, still works and functions as an energy-storage platform. The AM/3D-fabricated device is critically benchmarked against a battery developed using the same active materials, but fabricated via a traditional manufacturing method utilizing an ink-based/doctor-bladed methodology, which is found to exhibit a specific capacity of 98.9 mAh m −2 (116.35 mAh g −1 ). The fabrication of fully AM/3D-printed energy-storage architectures compares favorably with traditional approaches, with the former providing a new direction in battery manufacturing. This work represents a paradigm shift in the technological and design considerations in battery and energy-storage architectures.

© 2019, The Author(s). The electroanalytical detection of the neurotransmitter dopamine (DA) in the presence of uric acid (UA) is explored for the first time using commercially procured nanodiamonds (NDs). These are electrically wired via surface modification upon screen-printed graphite macroelectrodes (SPEs). The surface coverage of the NDs on the SPEs was explored in order to optimize electroanalytical outputs to result in well-resolved signals and in low limits of detection. The (electro)analytical outputs are observed to be more sensitive than those achieved at bare (unmodified) SPEs. Such responses, previously reported in the academic literature have been reported to be electrocatalytic and have been previously attributed to the presence of surface sp 2 carbon and oxygenated species on the surface of the NDs. However, XPS analysis reveals the commercial NDs to be solely composed of nonconductive sp 3 carbon. The low/negligible electroconductivity of the NDs was further confirmed when ND paste electrodes were fabricated and found to exhibit no electrochemical activity. The electroanalytical enhancement, when using NDs electronically wired upon SPEs, is attributed not to the NDs themselves being electrocatalytic, as reported previously, but rather changes in mass transport where the inert NDs block the underlying electroactive SPEs and create a random array of graphite microelectrodes. The electrode was applied to simultaneous sensing of DA and UA at pH 5.5. Figures of merit include (a) low working potentials of around 0.27 and 0.35 V (vs. Ag/AgCl); and (b) detection limits of 5.7 × 10 −7 and 8.9 × 10 −7 M for DA and UA, respectively. [Figure not available: see fulltext.].

We report the fabrication, characterisation (SEM/EDX, TEM, XRD, XPS and Raman spectroscopy) and electrochemical properties of graphite and graphene paste electrodes with varying lateral flake sizes. The fabricated paste electrodes are electrochemically analysed using both outer-sphere and inner-sphere redox probes, namely; hexaammineruthenium(iii) chloride, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), potassium ferrocyanide(ii) and ammonium ferrous(ii) sulphate. Upon comparison of different graphite paste electrodes, a clear correlation between the lateral flake sizes (La), ranging from 1.5 mm-0.5 μm, and electrochemical activity (heterogeneous electron transfer (HET) kinetics) is evident, where an improvement in the HET is observed at smaller lateral flake sizes. We infer that the beneficial response evident when employing laterally smaller flakes is due to an increased number of edge plane like-sites/defects available upon the electrode surface, facilitating electron transfer. Interestingly, given that the overall lateral flake sizes of the graphenes utilised (10.0-1.3 μm) were significantly smaller than those studied previously, an improvement in HET kinetics was also evident with the reduction of lateral flake size; the extent to which is redox-probe dependent. Improvements are observed up to a distinct point, termed the 'lateral size threshold' (ca. ≤2 μm) where the electrochemical reversible limit is approached. Further support is provided from density functional theory (DFT), exploring the electronic structure (i.e. HOMO-LUMO) as a function of flake size, which demonstrates that the coverage of edge plane like-sites/defects comprising the geometric structure of the relatively small graphene flakes is such that effectively the entire flake has become electrochemically active. In this study, the importance of lateral flake size with respect to electrochemical reactivity at carbon-based electrodes has been demonstrated alongside a structural relationship upo

The fabrication, characterization, and energy storage capacity of a graphene-oxide (GO)-based supercapacitor device is reported. This device is fabricated via a facile screen-printing technique, providing a highly reproducible and flexible symmetrical supercapacitor device. The capacitive properties of these GO devices are investigated in both aqueous electrolytes and room temperature ionic liquids. The GO devices are shown to improve the capacitive performance from 0.82 F g−1 displayed by a graphitic screen, to a competitive 423 F g−1, representing a ca. 500-fold increase. The GO supercapacitor device also exhibits an impressive power handling capability of up to 13.9 kW kg−1 and an energy density of 11.6 Wh kg−1. This work demonstrates that GO, before it has been reduced to graphene, is a high performance supercapacitor material of its own right.

© 2017 American Chemical Society. Two-dimensional molybdenum disulfide (2D-MoS 2 ) screen-printed electrodes (2D-MoS 2 -SPEs) have been designed, fabricated, and evaluated toward the electrochemical oxygen reduction reaction (ORR) within acidic aqueous media. A screen-printable ink has been developed that allows for the tailoring of the 2D-MoS 2 content/mass used in the fabrication of the 2D-MoS 2 -SPEs, which critically affects the observed ORR performance. In comparison to the graphite SPEs (G-SPEs), the 2D-MoS 2 -SPEs are shown to exhibit an electrocatalytic behavior toward the ORR which is found, critically, to be reliant upon the percentage mass incorporation of 2D-MoS 2 in the 2D-MoS 2 -SPEs; a greater percentage mass of 2D-MoS 2 incorporated into the 2D-MoS 2 -SPEs results in a significantly less electronegative ORR onset potential and a greater signal output (current density). Using optimally fabricated 2D-MoS 2 -SPEs, an ORR onset and a peak current of approximately +0.16 V [vs saturated calomel electrode (SCE)] and -1.62 mA cm -2 , respectively, are observed, which exceeds the -0.53 V (vs SCE) and -635 μA cm -2 performance of unmodified G-SPEs, indicating an electrocatalytic response toward the ORR utilizing the 2D-MoS 2 -SPEs. An investigation of the underlying electrochemical reaction mechanism of the ORR within acidic aqueous solutions reveals that the reaction proceeds via a direct four-electron process for all of the 2D-MoS 2 -SPE variants studied herein, where oxygen is electrochemically favorably reduced to water. The fabricated 2D-MoS 2 -SPEs are found to exhibit no degradation in the observed achievable current over the course of 1000 repeat scans. The production of such inks and the resultant mass-producible 2D-MoS 2 -SPEs mitigates the need to modify post hoc an electrode via the drop-casting technique that has been previously shown to result in a loss of achievable current over the course of 1000 repeat scans. The 2D-MoS 2 -SPEs designed, fabri

Type 2 diabetes (T2D) is a global pandemic. Currently, the drugs used to treat T2D improve hyperglycemic symptom of the disease but the underlying mechanism causing the high blood glucose levels have not been fully resolved. Recently published data showed that salt form of niclosamide improved glucose metabolism in high fat fed mice via mitochondrial uncoupling. However, based on our previous work we hypothesised that niclosamide might also improve glucose metabolism via inhibition of the glucagon signalling in liver in vivo. In this study, mice were fed either a chow or high fat diet containing two different formulations of niclosamide (niclosamide ethanolamine salt - NENS or niclosamide - Nic) for 10 weeks. We identified both forms of niclosamide significantly improved whole body glucose metabolism without altering total body weight or body composition, energy expenditure or insulin secretion or sensitivity. Our study provides evidence that inhibition of the glucagon signalling pathway contributes to the beneficial effects of niclosamide (NENS or Nic) on whole body glucose metabolism. In conclusion, our results suggest that the niclosamide could be a useful adjunctive therapeutic strategy to treat T2D, as hepatic glucose output is elevated in people with T2D and current drugs do not redress this adequately.

© 2017 The Authors. The modification of electrode surfaces is widely implemented in order to try and improve electron transfer kinetics and surface interactions, most recently using graphene related materials. Currently, the use of ‘as is’ graphene oxide (GO) has been largely overlooked, with the vast majority of researchers choosing to reduce GO to graphene or use it as part of a composite electrode. In this paper, ‘as is’ GO is explored and electrochemically characterized using a range of electrochemical redox probes, namely potassium ferrocyanide(II), N′, N′, N′, N′-tetramethyl-pphenylenediamine (TMPD), dopamine hydrochloride and epinephrine. Furthermore, the electroanalytical efficacy of GO is explored towards the sensing of dopamine hydrochloride and epinephrine via cyclic voltammetry. The electrochemical response of GO is benchmarked against pristine graphene and edge plane-/basal plane pyrolytic graphite (EPPG and BPPG respectively) alternatives, where the GO shows an enhanced electrochemical/electroanalytical response. When using GO as an electrode material, the electrochemical response of the analytes studied herein deviate from that expected and exhibit altered electrochemical responses. The oxygenated species encompassing GO strongly influence and dominate the observed voltammetry, which is crucially coverage dependent. GO electrocatalysis is observed, which is attributed to the presence of beneficial oxygenated species dictating the response in specific cases, demonstrating potential for advantageous electroanalysis to be realized. Note however, that crucial coverage based regions are observed at GO modified electrodes, owing to the synergy of edge plane sites and oxygenated species. We report the true beneficial electrochemistry of GO, which has enormous potential to be beneficially used in various electrochemical applications ‘as is’ rather than be simply used as a precursor to making graphene and is truly a fascinating member of the graphene family.

Surfactant-exfoliated 2D hexagonal boron nitride (2D-hBN) nanosheets are fabricated using the surfactant sodium cholate in aqueous media and are explored towards the electrochemical reduction of oxygen (oxygen reduction reaction) within acidic media for the first time. Large quantifiable voltammetric signatures are observed at significantly reduced potentials compared to traditional graphitic-based electrodes indicating 2D-hBN's possible electrocatalytic activity towards the oxygen reduction reaction, therefore having the potential as a useful electrode platform within fuel cell technology. We also demonstrate, for the first time, that surfactant-exfoliated 2D-hBN is an effective electrochemical supercapacitor material with a specific capacitance value of up to 1745 F g -1 . A full analysis of the electrochemical properties of 2D-hBN is performed, including the application of a novel capacitive circuit applied to galvanostatic charge/discharge analysis, which provides an unambiguous analysis of the capacitance of the 2D-hBN. Furthermore, a diverse range of methods are introduced and utilised to calculate the specific capacitance, a substantially overlooked and misinterpreted parameter within the literature allowing standardisation in the academic literature to be achieved. In both examples, we demonstrate through control experiments in the form of surfactant modified graphite electrodes, sodium cholate is the major contributing factor to the aforementioned electrocatalytic and capacitive behaviour, which has yet to be reported. © The Royal Society of Chemistry 2017

We demonstrate a facile, low cost and reproducible methodology for the production of electrocatalytic 2D-MoSe2 incorporated/bulk modified screen-printed electrodes (MoSe2-SPEs). The MoSe2-SPEs outperform traditional carbon based electrodes, in terms of their electrochemical activity, towards the Hydrogen Evolution Reaction (HER). The electrocatalytic behaviour towards the HER of the 2D-MoSe2 within the fabricated electrodes is found to be mass dependent, with an optimal mass ratio of 10% 2D-MoSe2 to 90% carbon ink. MoSe2-SPEs with this optimised ratio exhibit a HER onset, Tafel value and a turn over frequency of ca. −460 mV (vs. SCE), 47 mV dec−1 and 1.48Image ID:c6se00115g-t1.gif respectively. These values far exceed the HER performance of graphite (unmodified) SPEs, that exhibit a greater electronegative HER onset and Tafel value of ca. −880 mV and 120 mV dec−1 respectively. It is clear that impregnation of 2D-MoSe2 into the MoSe2-SPEs bulk ink/structure significantly increases the performance of SPEs with respect to their electrocatalytic activity towards the HER. When compared to SPEs that have been modified via a drop-casting technique, the fabricated MoSe2-SPEs exhibit excellent cycling stability. After 1000 repeat scans, a 10% modified MoSe2-SPE displayed no change in its HER onset potential of −450 mV (vs. SCE) and an increase of 31.6% in achievable current density. Conversely, a SPE modified via drop-casting with 400 mg cm−2 of 2D-MoSe2 maintained its HER onset potential of −480 mV (vs. SCE), however exhibited a 27.4% decrease in its achievable current density after 1000 scans. In addition to the clear performance benefits, the production of MoSe2-SPEs mitigates the need to post hoc modify an electrode via the drop-casting technique. We anticipate that this facile production method will serve as a powerful tool for future studies seeking to utilise 2D materials in order to mass-produce SPEs/surfaces with unique electrochemical properties whilst providing su

Surfactant exfoliated 2D hexagonal Boron Nitride (2D-hBN) nanosheets are explored as a potential electrochemical sensing platform and evaluated towards the electroanalytical sensing of dopamine (DA) in the presence of the common interferents, ascorbic acid (AA) and uric acid (UA). Surfactant exfoliated 2D-hBN nanosheets (2-4 layers) fabricated using sodium cholate in aqueous media are electrically wired via a drop-casting modification process onto disposable screen-printed graphite electrodes (SPEs). We critically evaluate the performance of these 2D-hBN modified SPEs and demonstrate the effect of 'mass coverage' towards the detection of DA, AA and UA. Previous studies utilising surfactant-free (pristine) 2D-hBN modified SPEs have shown a beneficial effect towards the detection of DA, AA and UA when compared to the underlying/unmodified graphite-based electrode. We show that the fabrication route utilised to prepare 2D-hBN is a vital experimental consideration, such that the beneficial effect previously reported is considerably reduced when surfactant exfoliated 2D-hBN is utilised. We demonstrate for the first time, through implementation of control experiments in the form of surfactant modified graphite electrodes, that sodium cholate is a major contributing factor to the aforementioned detrimental behaviour. The significance here is not in the material per se, but the fundamental knowledge of the surfactant and surface coverage changing the electrochemical properties of the material under investigation. Given the wide variety of ionic and non-ionic surfactants that are utilised in the manufacture of novel 2D materials, the control experiments reported herein need to be performed in order to de-convolute the electrochemical response and effectively evaluate the 'underlying surface/surfactant/2D materials' electrocatalytic contribution.

© 2017 Human Kinetics, Inc. Aerobic exercise (AE) and strength exercise (SE) are reported to induce discrete and specific appetite-related responses; however, the effect of combining AE and SE (i.e., combined exercise; CE) remains relatively unknown. Twelve inactive overweight men (age: 48 ± 5 y; BMI: 29.9 ± 1.9 kg·m2) completed four conditions in a random order: 1) nonexercise control (CON) (50 min seated rest); 2) AE (50 min cycling; 75% VO2peak); 3) SE (10 × 8 leg extensions; 75% 1RM); and 4) CE (50% SE + 50% AE). Perceived appetite, and appetiterelated peptides and metabolites were assessed before and up to 2 h postcondition (0P, 30P, 60P, 90P, 120P). Perceived appetite did not differ between trials (p < .05). Acylated ghrelin was lower at 0P in AE compared with CON (p = .039), while pancreatic polypeptide (PP) was elevated following AE compared with CON and CE. Glucose-dependent insulinotropic peptide (GIPtotal) was greater following all exercise conditions compared with CON, as was glucagon, although concentrations were generally highest in AE (p < .05). Glucose was acutely increased with SE and AE (p < .05), while insulin and C-peptide were higher after SE compared with all other conditions (p < .05). In inactive, middle-aged men AE, SE and CE each have their own distinct effects on circulating appetite-related peptides and metabolites. Despite these differential exercise-induced hormone responses, exercise mode appears to have little effect on perceived appetite compared with a resting control in this population.

Recently, it has been found that glucagon is able to activate the β-catenin signalling pathway leading to increased cyclin D1 and c-Myc expression in liver. Therefore the main aim of the present study is to determine whether the effect of glucagon activating β-catenin signalling leading to increased target gene expression is mediated through cAMP activation of PKA (protein kinase A). Primary rat hepatocytes were incubated with insulin, glucagon or adrenaline (epinephrine) and a range of inhibitors of PI3K (phosphoinositide 3-kinase), Wnt, mitochondrial uncoupler (niclosamide) or PKA inhibitors to dissect out the pathway leading to increased Ser552 phosphorylation on β-catenin following glucagon exposure. In primary rat hepatocytes, we found that short exposure to glucagon or adrenaline caused a rapid increase in Ser552 phosphorylation on β-catenin that leads to increased cyclin D1 and c-Myc expression. A range of PI3K and Wnt inhibitors were unable to block the effect of glucagon phosphorylating β-catenin. Interestingly, both niclosamide and the PKA inhibitor H89 blocked the glucagon effect on β-catenin signalling, leading to a reduction in target gene expression. Likewise, niclosamide inhibited cAMP levels and the direct addition of db-cAMP (dibutyryl-cAMP sodium salt) also resulted in Ser552 phosphorylation of β-catenin. We have identified a new pathway via glucagon signalling that leads to increased β-catenin activity that can be reversed with the antihelminthic drug niclosamide, which has recently shown promise as a potential treatment of T2D (Type 2 diabetes). This novel finding could be useful in liver cancer treatment, particularly in the context of T2D with increased β-catenin activity.

© 2016 by the authors. We explore the fabrication, physicochemical characterisation (SEM, Raman, EDX and XPS) and electrochemical application of hand-drawn pencil electrodes (PDEs) upon an ultra-flexible polyester substrate; investigating the number of draws (used for their fabrication), the pencil grade utilised (HB to 9B) and the electrochemical properties of an array of batches (i.e, pencil boxes). Electrochemical characterisation of the PDEs, using different batches of HB grade pencils, is undertaken using several inner- and outer-sphere redox probes and is critically compared to screen-printed electrodes (SPEs). Proof-of-concept is demonstrated for the electrochemical sensing of dopamine and acetaminophen using PDEs, which are found to exhibit competitive limits of detection (3σ) upon comparison to SPEs. Nonetheless, it is important to note that a clear lack of reproducibility was demonstrated when utilising these PDEs fabricated using the HB pencils from different batches. We also explore the suitability and feasibility of a pencil-drawn reference electrode compared to screen-printed alternatives, to see if one can draw the entire sensing platform. This article reports a critical assessment of these PDEs against that of its screen-printed competitors, questioning the overall feasibility of PDEs' implementation as a sensing platform.

© 2016 The Royal Society of Chemistry.Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.

Crystalline 2D hexagonal Boron Nitride (2D-hBN) is explored as a potential electrocatalyst towards the oxygen reduction reaction (ORR) when electrically wired via a drop-casting approach upon a range of carbon based electrode surfaces; namely, glassy carbon (GC), boron-doped diamond (BDD), and screen-printed graphitic electrodes (SPEs). We consider the ORR in acidic conditions and critically evaluate the performance of unmodified and 2D-hBN modified electrodes, implementing coverage studies (commonly neglected in the literature) in order to ascertain the true impact of this novel nanomaterial. The behaviour of 2D-hBN towards the ORR is shown to be highly dependent upon both the underlying carbon substrate and the coverage/mass utilised. 2D-hBN modified SPEs are found to exhibit the most beneficial response towards the ORR, reducing the peak potential by ca. 0.28V when compared to an unmodified/bare SPE. Such improvements at this supporting substrate are inferred due to favourable 2D-hBN interaction with ridged surfaces exposing a high proportion of edge regions/sites, where conversely, we show that relatively smooth substrate surfaces (such as GC) are less conducive towards successful 2D-hBN immobilisation. In this paper, we reveal for the first time (in the specific case of using a rough supporting substrate) that 2D-hBN gives rise to beneficial electrochemical behaviour towards the ORR. Unfortunately, this material is not considered an electrocatalyst for use within fuel cells given that the estimated number of electrons transferred during the ORR ranges between 1.90-2.45 for different coverages, indicating that the ORR at 2D-hBN predominantly produces hydrogen peroxide. 2D-hBN does however have potential and should be explored further by those designing, fabricating and consequently electrochemically testing modified electrocatalysts towards the ORR.

A reagentless pH sensor based upon disposable and economical graphite screen-printed electrodes (GSPEs) is demonstrated for the first time. The voltammetric pH sensor utilizes GSPEs which are chemically pretreated to form surface immobilized oxygenated species that, when their redox behavior is monitored, give a Nernstian response over a large pH range (1-13). An excellent experimental correlation is observed between the voltammetric potential and pH over the entire pH range of 1-13 providing a simple approach with which to monitor solution pH. Such a linear response over this dynamic pH range is not usually expected but rather deviation from linearity is encountered at alkaline pH values; absence of this has previously been attributed to a change in the pKa value of surface immobilized groups from that of solution phase species. This non-deviation, which is observed here in the case of our facile produced reagentless pH sensor and also reported in the literature for pH sensitive compounds immobilized upon carbon electrodes/surfaces, where a linear response is observed over the entire pH range, is explained alternatively for the first time. The performance of the GSPE pH sensor is also directly compared with a glass pH probe and applied to the measurement of pH in "real" unbuffered samples where an excellent correlation between the two protocols is observed validating the proposed GSPE pH sensor.

We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode’s individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.

BACKGROUND: Uncertainty exists about benefits and harms of a planned vaginal birth after caesarean (VBAC) compared with elective repeat caesarean (ERC). We conducted a prospective restricted cohort study consisting of a patient preference cohort study, and a small nested randomised trial to compare benefits and risks of a planned ERC with planned VBAC. METHODS AND FINDINGS: 2,345 women with one prior caesarean, eligible for VBAC at term, were recruited from 14 Australian maternity hospitals. Women were assigned by patient preference (n = 2,323) or randomisation (n = 22) to planned VBAC (1,225 patient preference, 12 randomised) or planned ERC (1,098 patient preference, ten randomised). The primary outcome was risk of fetal death or death of liveborn infant before discharge or serious infant outcome. Data were analysed for the 2,345 women (100%) and infants enrolled. The risk of fetal death or liveborn infant death prior to discharge or serious infant outcome was significantly lower for infants born in the planned ERC group compared with infants in the planned VBAC group (0.9% versus 2.4%; relative risk [RR] 0.39; 95% CI 0.19-0.80; number needed to treat to benefit 66; 95% CI 40-200). Fewer women in the planned ERC group compared with women in the planned VBAC had a major haemorrhage (blood loss ≥ 1,500 ml and/or blood transfusion), (0.8% [9/1,108] versus 2.3% [29/1,237]; RR 0.37; 95% CI 0.17-0.80). CONCLUSIONS: Among women with one prior caesarean, planned ERC compared with planned VBAC was associated with a lower risk of fetal and infant death or serious infant outcome. The risk of major maternal haemorrhage was reduced with no increase in maternal or perinatal complications to time of hospital discharge. Women, clinicians, and policy makers can use this information to develop health advice and make decisions about care for women who have had a previous caesarean. TRIAL REGISTRATION: Current Controlled Trials ISRCTN53974531

Results are presented from a new web application called OceanDIVA — Ocean Data Intercomparison and Visualization Application. This tool reads hydrographic profiles and ocean model output and presents the data on either depth levels or isotherms for viewing in Google Earth, or as probability density functions (PDFs) of regional model-data misfits. As part of the CLIVAR Global Synthesis and Observations Panel, an intercomparison of water mass properties of various ocean syntheses has been undertaken using OceanDIVA. Analysis of model-data misfits reveals significant differences between the water mass properties of the syntheses, such as the ability to capture mode water properties.

OBJECTIVE: To assess psychosocial morbidity in women with breast cancer and to compare the differential rates between women with early stage and advanced disease. METHOD: In this report, 303 women with early stage breast cancer, psychiatrically assessed at baseline (as part of a study of cognitive-existential group therapy during adjuvant chemotherapy), are compared with 200 women with advanced breast cancer (similarly assessed in a trial of supportive-expressive group therapy). A structured psychiatric interview plus self-report measures were used to assess psychiatric morbidity, quality of life and cognitive attitude to cancer. RESULTS: The early stage patients, whose mean age was 46 years, were on average 3 months post-surgery and had an overall prevalence of DSM-IV psychiatric diagnosis of 45%. The metastatic patients, whose mean age was 51 years, were on average 63 months post-primary diagnosis and had an overall prevalence of DSM-IV diagnosis of 42%; the difference between the two rates was not statistically significant. Of women with early stage breast cancer, 36.7% had mood disorders, 9.6% suffering from major depression and 27.1% from minor depression. In the metastatic sample 31% had mood disorders, 6.5% having major depression and 24.5% with minor depression. Anxiety disorders were present in 8.6% of the early stage group and 6% of women with advanced disease. Fatigue, a past history of depression, and cognitive attitudes of helplessness, hopelessness or resignation were significantly associated with depression in both groups. The women from the metastatic sample were significantly less distressed by hair loss but more dissatisfied with body image, and had higher rates of lymphoedema and hot flushes than the early stage women. CONCLUSIONS: The rates of psychosocial distress are high, and similar, across patients with both early and advanced stage breast cancer, although the illness related causes of distress are different. These data present a challenge t

Supportive-Expressive Group Therapy (SEGT) has been developed and manualised in the research setting, but there have been few clinical accounts of its utility. In this qualitative review of its application in the Melbourne-based randomised control trial (RCT) for women with advanced breast cancer, SEGT is considered from the perspective of the structure and framework of therapy, its therapists, the issues that develop in exploring its common themes and what constitutes a well functioning group. Groups move through identifiable developmental phases. The mature group process transforms existential ambivalence into creative living, evidenced by humour, celebration, assertiveness, altruism, new creative pursuits and eventually courageous acceptance of dying. Challenges and pitfalls include avoidance, non-containment of ambivalence, intolerance of difference, anti-group phenomena and splitting. A key element is the medicalization of the group culture whereby members and co-therapists explore health beliefs and attitudes about care. This promotes compliance with anti-cancer treatments, including both the initiation of and perseverance with chemotherapy. This mechanism could prove to be a potentially important pathway in promoting longer survival.