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For 160 years, Anthrenus pimpinellae isabellinus Kuster, 1848 has been considered a subspecies of A. pimpinellae Fabricius, 1775. However, habitus shape differs between the subspecies with A. p. isabellinus being broader than A. p. pimpinellae and resembling more closely A. dorsatus Mulsant & Rey, 1868. Here A. p. pimpinellae and A. p. isabellinus, are examined to look for evidence that they comprise a single taxonomic unit. Habitus and genital structures are considered, and the universal animal barcode region of the mitochondrial cytochrome oxidase I gene is sequenced. The results of the morphological, morphometric, and genetic analyses mirror each other perfectly and suggest that A. p. isabellinus is the same species as A. dorsatus rather than being a subspecies of A. pimpinellae. The very small intraspecific DNA sequence variation supports the view that A. dorsatus and A. p. isabellinus belong to a single species that diverges considerably from A. p. pimpinellae. Morphology, including genital structure, is congruent with the genetic data and provides a powerful way of resolving species organisation in these widespread beetles. In view of these findings, Anthrenus isabellinus Kuster, 1848 is restored to full species status and Anthrenus dorsatus Mulsant & Rey, 1868 becomes its new junior subjective synonym.

Additive manufacturing (AM) provides a unique platform for the rapid design and fabrication of complex structures. Printed structures can be used as is or as templates to be decorated with electrochemical deposited nanomaterials, which may be utilised as electrocatalytic sensing platforms. Novel methods are required to determine the electrochemical deposited morphology present on the electrode surfaces. Additively manufactured graphene macroelectrodes (AM-GMs) were fabricated using a commercially available feedstock and molybdenum (di)oxide (MoO2) was successfully electrochemically deposited onto the electrode surface. The electrochemically deposited MoO2 was analysed using scanning electron microscopy (SEM), optical interferometry, Raman spectroscopy and multifractal analysis (MFA). Although the electrochemical deposition of MoO2 nanowires were clearly visible using SEM, MFA enabled quantification of the MoO2 nanowires, deposited at a variety of time points (20 – 300 s). MFA was utilised to generate quantitative data, derived from ƒ(α) curves, to determine the area of the electrochemical deposited MoO2 nanowires, including coverage, density, dispersion and clustering. The AM-GMs which were subjected to 300 s (maximum time period) of MoO2 electrodeposition demonstrated the greatest percentage area coverage (20.14 %). The use of such mathematical systems offers an inexpensive method to characterise the parameters of electrochemically-deposited materials.

Additive manufacturing is a promising technology for the rapid and economical fabrication of portable electroanalytical devices. In this paper we seek to determine how our bespoke additive manufacturing feedstocks act as the basis of an electrochemical sensing platform towards the sensing of manganese(ii) via differential pulse cathodic stripping voltammetry (DPCSV), despite the electrode comprising only 25 wt% nanographite and 75 wt% plastic (polylactic acid). The Additive Manufactured electrodes (AM-electrodes) are also critically compared to graphite screen-printed macroelectrodes (SPEs) and both are explored in model and real tap-water samples. Using optimized DPCSV conditions at pH 6.0, the analytical outputs using the AM-electrodes are as follows: limit of detection, 1.6 × 10-9 mol L-1 (0.09 μg L-1); analytical sensitivity, 3.4 μA V μmol-1 L; linear range, 9.1 × 10-9 mol L-1 to 2.7 × 10-6 mol L-1 (R2 = 0.998); and RSD 4.9% (N = 10 for 1 μmol L-1). These results are compared to screen-printed macroelectrodes (SPEs) giving comparable results providing confidence that AM-electrodes can provide the basis for useful electrochemical sensing platforms. The proposed electroanalytical method (both AM-electrodes and SPEs) is shown to be successfully applied for the determination of manganese(ii) in tap water samples and in the analysis of a certified material (drinking water). The proposed method is feasible to be applied for in-loco analyses due to the portability of sensing; in addition, the use of AM-printed electrodes is attractive due to their low cost.

Monolayer hexagonal-boron nitride films (2D-hBN) are typically reported within the literature to be electrochemically inactive due to their considerable band gap (ca. 5.2–5.8 eV). It is demonstrated herein that introducing physical linear defects (PLDs) upon the basal plane surface of 2D-hBN gives rise to electrochemically useful signatures. The reason for this transformation from insulator to semiconductor (inferred from physicochemical and computational characterisation) is likely due to full hydrogenation and oxygen passivation of the boron and/or nitrogen at edge sites. This results in a decrease in the band gap (from ca. 6.11 to 2.36/2.84 eV; theoretical calculated values, for the fully hydrogenated oxygen passivation at the N or B respectively). The 2D-hBN films are shown to be tailored through the introduction of PLDs, with the electrochemical behaviour dependent upon the surface coverage of edge plane-sites/defects, which is correlated with electrochemical performance towards redox probes (hexaammineruthenium(III) chloride and Fe2+/3+) and the hydrogen evolution reaction. This manuscript de-convolutes, for the first time, the fundamental electron transfer properties of 2D-hBN, demonstrating that through implementation of PLDs, one can beneficially tailor the electrochemical properties of this nanomaterial.

The origin of electron transfer at Chemical Vapour Deposition (CVD) grown monolayer graphene using a polymer-free transfer methodology is explored through the selective electrodeposition of Molybdenum (di)oxide (MoO2). The electrochemical decoration of CVD monolayer graphene with MoO2 is shown to originate from the edge plane like- sites/defects. Edge plane decoration of MoO2 nanowires upon monolayer graphene is observed via electrochemical deposition over short time periods only (ca. −0.6 V for 1 second (vs. Ag/AgCl)). At more electrochemically negative potentials (ca. −1.0 V) or longer deposition times, a large MoO2 film is created/deposited on the graphene sheet, originating and expanding from the original nucleation points at edge plane like- sites/defects/wrinkles. Nanowire fabrication along the edge plane like- sites/defects of graphene is confirmed with Cyclic Voltammetry, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Raman Spectroscopy. Monitoring the electrochemical response towards [Ru(NH3)6]3+/2+ and comparing the heterogeneous electron transfer (HET) kinetics at CVD grown monolayer graphene prior and post nanowire fabrication reveals key understandings into the fundamental electrochemical properties of carbon materials. The HET kinetics ($${{\boldsymbol{k}}}_{{\boldsymbol{obs}}}^{{\bf{0}}}$$ k obs 0 ) at MoO2 nanowire decorated monolayer graphene sheets, when edge plane like- sites/defects have been coated/blocked with MoO2, are significantly reduced in comparison to the unmodified graphene alternative. Interestingly, MoO2 nucleation originates on the edge plane like- sites/defects of the graphene sheets, where the basal plane sites remain unaltered until the available edge plane like- sites/defects have been fully utilised; after which MoO2 deposition propagates towards and onto the basal planes, eventually covering the entire surface of the monolayer graphene surface. In such instances, there is no longer an observable electrochemical response. This work demonstrates the distinct electron transfer properties of edge and basal plane sites on CVD grown monolayer graphene, inferring favourable electrochemical reactivity at edge plane like- sites/defects and clarifying the origin of graphene electro-activity.

The emergence of a new class of novel psychoactive substances, N-benzyl-substituted phenethylamine derivatives so-called “NBOMes” or “Smiles”, in the recreational drug market has forced the development of new sensitive analytical methodologies for their detection and quantitation. NBOMes’ hallucinogenic effects mimic those of the illegal psychedelic drug lysergic acid diethylamide (LSD) and are typically sold as LSD on blotter papers, resulting in a remarkable number of fatalities worldwide. In this article, four halide derivatives of NBOMe, namely, 2-(4-fluoro-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethan-1-amine, 2-(4-chloro-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethan-1-amine, 2-(4-bromo-2,5-dimethoxyphenyl)-N-(2- methoxybenzyl)ethan-1-amine, and 2-(4-iodo-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethan-1-amine, were detected and quantified simultaneously using a high-performance liquid chromatographic method, and two detection systems were compared: photodiode array detection (detection system I) and amperometric detection via a commercially available impinging jet flow-cell system incorporating embedded graphite screen-printed macroelectrodes (detection system II). Under optimized experimental conditions, linear calibration plots were obtained in the concentration range of 10−300 and 20−300 μg mL−1 , for detection systems I and II, respectively. Detection limit (limit of detection) values were between 4.6−6.7 and 9.7−18 μg mL−1, for detection systems I and II, respectively. Both detectors were employed for the analysis of the four NBOMe derivatives in the bulk form, in the presence of LSD and adulterants commonly found in street samples (e.g. paracetamol, caffeine, and benzocaine). Furthermore, the method was applied for the analysis of simulated blotter papers, and the obtained percentage recoveries were satisfactory, emphasizing its advantageous applicability for the routine analysis of NBOMes in forensic laboratories.

Context\ud Maintaining biodiversity in multifunction landscapes is a significant challenge. Planning for the impacts of change requires knowledge of how species respond to landscape heterogeneity. Some insect groups are known to respond to heterogeneity at the mesoscale, defined here as hundreds of metres. However, for many taxa these effects are poorly known.\ud \ud Objectives\ud To identify key elements of mesoscale landscape heterogeneity influencing community composition in flower-visiting beetles, and whether landscape explains any variation in beetle communities beyond that driven by immediate habitat cover.\ud \ud Methods\ud Flower-visiting beetles were sampled from 36 transects, laid out using a 6 km2 grid located in southern Britain. Landscape heterogeneity was measured for 30 and 200 m buffers around the transects and the relative response of beetle communities to each assessed using ordination analyses followed by variation partitioning.\ud \ud Results\ud The composition of immediately adjacent habitat (30 m) and mesoscale landscape heterogeneity (200 m) explained unique portions of the variation in flower-visiting beetle communities. A number of species, including those affiliated with deadwood habitats, were positively linked to tree cover in the surrounding mesoscale landscape. Gardens covered a smaller area than trees but modified beetle communities to the same extent.\ud \ud Conclusions\ud The local abundance of some flower-visiting beetles is modified by the composition of the surrounding landscape. Results highlight the importance of tree cover for maintaining insect biodiversity in agricultural landscapes, while suggesting that gardens associated with small urban areas may have a disproportionate influence on biodiversity.

The carpet beetle Anthrenus dorsatus has previously been recorded from North Africa and Malta. During a recent visit to the island of Mallorca several Anthrenus species were collected which included a number of Anthrenus dorsatus specimens. This record adds a new species both to the island of Mallorca and to the Spanish checklist. These records extend our knowledge of the distribution of A. dorsatus and provide more evidence of range expansion in the pimpinellae species group across Europe, possibly because of global climate change.

Over recent years there has been a progressive increase in the adulteration of common illicit street drugs, such as heroin and cocaine, with fentanyl and its derivatives (fentalogues) being the cause of over doses ending with fatal repercussions. Consequently, there is a need for the development of sensitive, selective and reliable analytical protocols for their separation and quantification. Herein, we report for the first time, a combination of high-performance liquid chromatography with a dual-diode array and electrochemical (amperometric) detector achieved for the simultaneous detection and quantification of heroin (HRN), fentanyl and ten fentalogues; the amperometric detection is achieved using a commercially available impinging jet flow-cell that incorporates in-house screen-printed graphite macroelectrodes (SPEs). Both protocols are analytically compared and contrasted in terms of their experimental parameters and chromatographic conditions with the separation and quantification being optimized, with these protocols demonstrating a high sensitivity and reproducibility. The proposed methods were successfully applied for the analysis of the investigated drugs of abuse, in the presence of common adulterants (e.g. caffeine, paracetamol and benzocaine), co-formulated excipients (starch, lactose, aerosil 200, etc.) and simultaneously within seized street samples.

Although the impacts of urbanisation on biodiversity are well studied, the precise response of some invertebrate groups remains poorly known. Dung-associated beetles are little studied in an urban context, especially in temperate regions. We considered how landscape heterogeneity, assessed at three spatial scales (250, 500 and 1000 m radius), mediates the community composition of coprophilous beetles on a broad urban gradient. Beetles were sampled using simple dung-baited traps, placed at 48 sites stratified across three distance bands around a large urban centre in England. The most urban sites hosted the lowest abundance of saprophagous beetles, with a lower mean body length relative to the least urban sites. Predicted overall species richness and the richness of saprophagous species were also lowest at the most urban sites. Ordination analyses followed by variation partitioning revealed that landscape heterogeneity across the urban gradient explained a small but significant proportion of community composition. Heterogeneity data for a 500-m radius around each site provided the best fit with beetle community data. Larger saprophagous species were associated with lower amounts of manmade surface and improved grassland. Some individual species, particularly predators, appeared to be positively associated with urban or urban fringe sites. This study is probably the first to examine the response of the whole coprophilous beetle community to urbanisation. Our results suggest that the response of this community to urbanisation matches expectations based on other taxonomic groups, whilst emphasising the complex nature of this response, with some smaller-bodied species potentially benefitting from urbanisation.

© 2018 Most of the reported MoSe 2 electrode materials are suffered from tended stacking, large volume expansion and relatively low capacity. As shown the experiences of Li/Na-Se batteries, the encapsulating of the exfoliated MoSe 2 into carbon nanospheres are successfully constructed with the introduction of C-O-Mo bonds and larger layer distance (0.89 nm). Interestingly, the C-O-Mo bonds stayed on the surface of the Se-O insulation layer can improve the rate of ions transfer and also promote the reversible conversion of MoSe 2 . The first-principles calculations demonstrated that the frontier molecular orbitals of C-O-Mo interface structure are mainly localized on the MoSe 2 sheet fragment with an appropriate HOMO-LUMO gap ( < 4 eV), proving that its conductivity is being greatly enhanced with higher stability. Utilized as an anode for LIBs, it delivers Li-storage capacities of 1208 mAh g −1 after 150 cycles at 1.0 A g −1 and 519 mAh g −1 after 200 cycles at 4.0 A g −1 . Also note that the Na-storage capacities are found to be 543, 491 mAh g −1 after 120 cycles at 0.1, 1.0 A g −1 , respectively. Through the analysis of CV, the reduced particles might improve the capacitive behaviors, further leading to the higher rate performances. Ex-situ techniques showed that the emerging Se during the electrochemical process was constrained uniformly in the carbon matrix. More greatly, the controlling of by-product Se plays key roles in achieving high-rate capability and cycling stability, which would open up a potential avenue for these metal-selenide anodes designs of battery storage systems.

Screen-printed electrodes (SPEs) are ubiquitous with the field of electrochemistry allowing researchers to translate sensors from the laboratory to the field. In this paper, we report an electrochemically driven intercalation process where an electrochemical reaction uses an electrolyte as a conductive medium as well as the intercalation source, which is followed by exfoliation and heating/drying via microwave irradiation, and applied to the working electrode of screen-printed electrodes/sensors (termed EDI-SPEs) for the first time. This novel methodology results in an increase of up to 85% of the sensor area (electrochemically active surface area, as evaluated using an outer-sphere redox probe). Upon further investigation, it is found that an increase in the electroactive area of the EDI-screen-printed based electrochemical sensing platforms is critically dependent upon the analyte and its associated electrochemical mechanism (i.e. adsorption vs. diffusion). Proof-of-concept for the electrochemical sensing of capsaicin, a measure of the hotness of chillies and chilli sauce, within both model aqueous solutions and a real sample (Tabasco sauce) is demonstrated in which the electroanalytical sensitivity (a plot of signal vs. concentration) is doubled when utilising EDI-SPEs over that of SPEs.

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The utilisation of screen-printing technology allows for a mass scalable approach for the production of electrochemical screen-printed electrodes (SPEs) and the presence of a redox mediator can add new possibilities to the electrochemical properties of the SPEs. Among the materials used as redox mediators, cyanidoferrates polymers can be used for electro-oxidation of cysteine. In this work, two monomers, namely, [Fe(CN) 6 ] 4− and [Fe(CN) 5 NH 3 ] 3− were used to produce Prussian blue (PB) and Prussian blue-Ammine (PB-Ammine), respectively. In addition, two modification methods were compared, firstly via a drop-casting and secondly by the incorporation of these materials into a printable ink. The SPE modified by PB-Ammine (drop-casting) exhibits the highest electroactive area, however the highest heterogeneous rate constant was found with the SPE modified by PB-Ammine that was incorporated into the ink. The highest value of the constant of electro-oxidation of cysteine and lowest limit of detection was also observed in the SPE modified by PB incorporated into the ink. These studies suggest that the electrocatalytic properties of SPE modified by PB and PB-Ammine are dependent upon the availability of Fe 3+ catalytic sites and the increased kinetics of the chemical reaction between the catalytic sites and the analyte.

Calixarene bulk modified screen-printed electrodes (SPCCEs) have been designed, fabricated and utilized as one-shot disposable electrochemical sensors towards the simultaneous measurement of toxic metal ions lead(II), copper(II) and mercury(II) within environmental samples. These SPCCEs have been fabricated upon polyester strips, which have been modified over a range of different calixarene compositions. These bespoke sensors have been utilized as disposable electrochemical sensors and quantified in model aqueous solution of 0.1 M HCl giving rise to the simultaneous sensing of lead(II), copper(II) and mercury(II) using cyclic voltammetry and differential pulse anodic stripping voltammetry techniques. These SPCCEs have additionally been applied for the sensing of lead(II), copper(II) and mercury(II) within industrial and environmental samples such as industrial effluents and wastewater samples, furthermore the presented method has been subjected to a comprehensive interference study and further validated with an atomic absorption spectrometric method.

© 2017 Elsevier Ltd A screen-printed amperometric sensor based on a carbon ink bulk-modified with MnO2 decorated graphene oxide (MnO2/GO-SPE) nanocomposite was investigated for its ability to serve as a sensor towards nitrite. The composite was prepared by simple ultrasonication and reflux methodology and was characterized by FT-IR spectroscopy, transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, atomic force microscopy and electrochemically using cyclic voltammetry, chronoamperometry and differential pulse voltammetry techniques. The MnO2/GO-SPE was found to exhibit an electro-catalytic activity for the electrochemical oxidation of nitrite in 0.1 M phosphate buffer solution (pH 7.4). The electrochemical oxidation of nitrite occurs at +0.55 V (Vs. Ag/AgCl) with a limit of detection (3σ) found to be 0.09 μM and with two linear ranges of 0.1 μM to 1 μM and 1 μM to 1000 μM with sensitivities of 1.25 μAμM−1 cm−2 and 0.005 μAμM−1 cm−2 respectively. Furthermore, the MnO2/GO-SPE showed an excellent anti-interference ability towards a range of commonly encountered electroactive species and metal ions. Additionally, the fabricated MnO2/GO-SPE nitrite sensor presented an excellent selectivity, reproducibility and stability. The presented study widens the scope of applications of graphene-based nanocomposite materials for on-site monitoring of nitrite.

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

An effective electrochemical sensing platform for the simultaneous determination of benzocaine (BEN) and antipyrine (ANT) based upon titanium dioxide nanoparticle (TiO2)/graphene oxide nanosheet (GO) bulk modified carbon paste electrodes (TiO2-GO/CPE) is reported. The TiO2-GO/CPE electrochemical sensing platform is found to exhibit linear ranges from 1.0 × 10-6 to 1.0 × 10-4 M and 1.2 × 10-8 to 8.0 × 10-5 M for BEN and ANT, respectively. The TiO2-GO/CPE sensor is explored towards the analysis of BEN and ANT in oral fluid (saliva) and pharmaceutical products. The synergy between the graphene oxide nanosheets and titanium dioxide nanoparticles results in a dramatic enhancement in the sensitivity of the sensor through a combination of increased surface area and improved electron transfer kinetics compared to other electrode alternatives. The fabricated TiO2-GO/CPE exhibits high sensitivity and good stability towards the sensing of BEN and ANT and has the potential to be utilised as a clinical assay and QA in pharmaceutical products.

We enhance the current capability of additive manufacturing (AM)/(3D printing) to produce electronic devices by presenting a facile methodology for the production of electroconductive/electrocatalytic AM polylactic acid (PLA) filaments containing electrocatalytic materials; 2D-MoSe2 (M), electro-conductive carbon (C) and 20% Pt on carbon (Pt/C). The AM printed structures/electrodes (AMEs) produced using these filaments display bespoke electrochemical signals, in this case, efficient catalysis towards the major reactions that occur within a water electrolyser, namely the hydrogen evolution reaction (HER) on the cathode and the oxygen evolution reaction (OER) on the anode without the need for any post-production treatments. Various percentage mass incorporations, of the additives, into the PLA filaments were explored, with a 25% mass incorporation representing an ideal compromise between electroactivity and printability. Utilizing the optimized M10%–C15%-AME and Pt/C25%-AME as the cathode and anode, respectively, whilst a commercially available alkaline battery applied a potential of 1.5 V, water-splitting was achieved with obvious effervescence occurring at each electrode. This AM technique could mitigate the need for complex fabrication procedures, allowing researchers, industry and any interested individuals to rapidly go from ‘desktop designs’ to workable electrochemical prototype devices.

Monolayer hexagonal-boron nitride films (2D-hBN) are typically reported within the literature to be electrochemically inactive due to their considerable band gap (

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.

Herein, we report the fabrication and application of Li‐ion anodes for utilisation within Li‐ion batteries, which are fabricated via additive manufacturing/3D printing (fused deposition modelling) using a bespoke graphene/polylactic acid (PLA) filament, where the graphene content can be readily tailored and controlled over the range 1–40 wt. %. We demonstrate that a graphene content of 20 wt. % exhibits sufficient conductivity and critically, effective 3D printability for the rapid manufacturing of 3D printed freestanding anodes (3DAs); simplifying the components of the Li‐ion battery negating the need for a copper current collector. The 3DAs are physicochemically and electrochemically characterised and possess sufficient conductivity for electrochemical studies. Critically, it is found that if the 3DAs are used in Li‐ion batteries the specific capacity is very poor but can be significantly improved through the use of a chemical pre‐treatment. Such treatment induces an increased porosity, which results in a 200‐fold increase (after anode stabilisation) of the specific capacity (ca. 500 mAh g−1 at a current density of 40 mA g−1). This work significantly enhances the field of additive manufacturing/3D printed graphene based energy storage devices demonstrating that useful 3D printable batteries can be realised.

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, Funding from the Engineering and Physical Sciences Research Council (Reference: EP/N001877/1). The Manchester Fuel Cell Innovation Centre is funded by the European Regional Development Fund

The demand for grid-scale energy storage systems has rapidly grown over recent years, to meet the requirements of structural innovation within the energy industry. Due to their inexpensive manufacturing and operating costs, and the similar electrochemical mechanism with the well-established lithium-ion batteries (LIBs), sodium ion batteries (SIBs) have been considered as an attractive candidate for grid-scale energy storage systems. A variety of cobalt-based cathode and anode materials, including cobalt oxides, cobalt chalcogenides and layered sodium cobaltates, have been synthesized and evaluated for sodium storage within the academic literature. In this article, we present a comprehensive review of the recent progress with cobalt-based electrodes (both as an anode and cathode material) used in SIBs. In detail, the electrochemical mechanisms, advantages and disadvantages, the relationship between crystalline structure and electrochemical performance and strategies to enhance the overall electrochemical performance of cobalt-based cathode and anode materials are discussed. Up to now, some cathode materials have already reached a high energy density, which is comparable to commercial LIBs. Furthermore, some cobalt-based materials can maintain a high Coulombic efficiency of over 99% with high reversible capacity during long cycling life. These encouraging results, allow such cobalt-based electrode materials to be a potential solution for grid-scale SIB systems.

The accurate detection of biological materials has remained at the forefront of scientific research for decades. This includes the detection of molecules, proteins, and bacteria. Biomimetic sensors look to replicate the sensitive and selective mechanisms that are found in biological systems and incorporate these properties into functional sensing platforms. Molecularly imprinted polymers (MIPs) are synthetic receptors that can form high affinity binding sites complementary to the specific analyte of interest. They utilise the shape, size, and functionality to produce sensitive and selective recognition of target analytes. One route of synthesizing MIPs is through electropolymerization, utilising predominantly constant potential methods or cyclic voltammetry. This methodology allows for the formation of a polymer directly onto the surface of a transducer. The thickness, morphology, and topography of the films can be manipulated specifically for each template. Recently, numerous reviews have been published in the production and sensing applications of MIPs; however, there are few reports on the use of electrosynthesized MIPs (eMIPs). The number of publications and citations utilising eMIPs is increasing each year, with a review produced on the topic in 2012. This review will primarily focus on advancements from 2012 in the use of eMIPs in sensing platforms for the detection of biologically relevant materials, including the development of increased polymer layer dimensions for whole bacteria detection and the use of mixed monomer compositions to increase selectivity toward analytes.

The constant and persistent synthesis and abuse of new psychoactive substances have sparked the requirement for rapid, on-site, sensitive analytical protocols for their sensing and quantification. Mephedrone (4-MMC) is currently one of the most popular legal highs among recreational drug abusers and imposes a serious public health problem. In this paper, the electrochemical sensing of two metabolites of 4-MMC, namely, nor-mephedrone (4-methylcathinone, 4-MC) and dihydromephedrone (4-methylephedrine, 4-MMC-R), utilizing screen-printed graphite electrodes is performed. The accessible linear ranges by cyclic voltammetry were found to correspond to 40–300 μg mL–1 for 4-MC in both phosphate buffer solution (PBS, pH 7.0) and spiked diluted human urine, whereas in the case of 4-MMC-R, the linearity ranges are 15–300 μg mL–1 (PBS, pH 3.0) and 25–300 μg mL–1 (spiked diluted human urine). To maximize the assay sensitivity, differential pulse voltammetry (DPV) was performed toward the sensing of 4-MC, which exhibited a linear response over the range 10–250 and 10–300 μg mL–1 in PBS pH 7.0 and spiked diluted human urine, respectively. However, 4-MMC-R demonstrated slightly higher sensitivity over the range 5–300 μg mL–1 in both PBS pH 3.0 and spiked diluted human urine. Using DPV, the limits of detection (3σ) were calculated and found to correspond to ca. 3.97 and 3.64 μg mL–1 for 4-MC and 4-MMC-R (PBS, pH 7.0 and 3.0), respectively, and ca. 6.34 and 3.87 μg mL–1 for 4-MC and 4-MMC-R (spiked diluted human urine), respectively. The potential interference of adulterants’ metabolites commonly found in NPS street samples was also explored (at both pH 7.0 and 3.0). The electrochemical approach reported herein provides a novel laboratory tool for the identification and quantification of synthetic cathinone metabolites and has potential for the basis of a portable analytical sensor for their fast, cheap, reliable, and accessible determination in the field.

Molecularly Imprinted Polymers (MIPs) are synthesized for the selective detection of caffeine. The polymerization process, monomer and crosslinker monomer composition are varied to determine the optimal synthesis procedure via batch rebinding experiments evaluated with optical detection. The selectivity is tested by comparing the response of caffeine to compounds with similar chemical structures (theophylline and theobromine) and dopamine, another neurotransmitter. Subsequently, the MIP polymer particles are integrated into bulk modified MIP screen-printed electrodes (MIP-modified SPEs). The sensors are used to measure caffeine content in various samples employing the Heat-Transfer Method (HTM), a low-cost and simple thermal detection method that is based on differences in thermal resistance at the solid-liquid interface. At first, the noise is minimized by adjusting the settings of temperature feedback loop. Second, the response of the MIP-modified SPE is studied at various temperatures ranging from 37 to 50 and 85 °C. The binding to MIP-modified SPEs has never been studied at elevated temperatures since most biomolecules are not stable at those temperatures. Using caffeine as proof-of-concept, it is demonstrated that at 85 °C the detection limit is significantly enhanced due to higher signal to noise ratios and enhanced diffusion of the biomolecule. Thermal wave transport analysis (TWTA) is also optimized at 85 °C producing a limit of detection of ∼1 nM. Next, MIP-modified SPEs are used to measure the caffeine concentration in complex samples including caffeinated beverages, spiked tap water and waste water samples. The use of MIP-modified SPEs combined with thermal detection provides sensors that can be used for fast and low-cost detection performed on-site, which holds great potential for the determination of contaminants in environmental samples. The platform is generic and by adapting the MIP layer, we can expand to this a range of relevant targets.

Thiol-containing compounds such as l-cysteine have been demonstrated to play an important role in metabolism and cellular growth, acting as powerful antioxidants. Consequently, their analytical determination in biological media has received a considerable amount of attention. In this work, an electrochemical sensor for the accurate electroanalytical determination of l-cysteine is proposed, based upon a Co(II)-phthalocyanine bulk modified disposable screen-printed graphite electrode (CoPc-SPE). Cyclic (CV) and Square Wave (SWV) voltammetry experiments have demonstrated an excellent electrocatalytic activity towards the electrochemical oxidation of l-cysteine using CoPc-SPEs within optimum neutral or basic pH. Moreover, the SWV response of l-cysteine is found to exhibit a linear range of 2.6–200 μM, with a low limit of detection of 4 μM (S/N = 3) and a sensitivity of 0.78 μA cm− 2 μM− 1. Coefficient of variation for reproducibility and repeatability of l-cysteine determination using the CoPc-SPE are 3 and 0.4%, respectively. The effect of inherent interferences such as naturally occurring amino acids, cystine and cysteic acid has been also evaluated. Finally, the applicability of the l-cysteine electrochemical sensor based upon CoPc-SPEs has been successfully demonstrated for the first time for the assessment of l-cysteine in a complex embryo cell culture medium. J. Iniesta thanks the programme Salvador de Madariaga from the Ministerio de Economía y Competitividad, grant number PRX14/00363. This work has been also financially supported by the MICINN-FEDER (Spain) through the projects CTQ2013-48280-C3-3-R.

The development of electroanalytical methods for the detection and quantification of nucleotides in DNA offers vital implications in assessing the degree of oxidation or epigenetic modification in DNA. Unfortunately, the electrochemical response of oligonucleotides is strongly influenced by the size, composition and nucleic base sequence. In this article, an optimized analytical procedure for the enzymatically breakdown of the oligonucleotides to their corresponding nucleotides for the evaluation of the electrochemical response through the use of square wave voltammetry (SWV) is presented. Enzymatic digestion of oligonucleotides has been optimized in terms of buffer composition, digestion time, strategy for stopping the enzymatic reaction and filtration requirement for enzyme removal, and then compared to an established protocol. Under the optimized protocol SWV response of a number of untreated and enzymatically digested six-mer oligonucleotides, namely 5′-GGGGGG-3′, 5′-AAAAAA-3′, 5′-CGCGCG-3′ and 5′-AAACGC-3′ have been analysed, providing a higher sensitivity for the determination of guanosine and adenosine monophosphate species under digestion conditions with a more facile and cost effective procedure. The novel strategy for the enzymatically treated oligonucleotides in combination with the SWV response provides a proof of principle for feasible applications in the diagnosis of methylated guanosine in DNA as a potential biomarker due to its relation with cancer. This work has been also financially supported by the MINECO (Spain) through projects CTQ2013-48280-C3-3-R and CTQ2013-44083-P.

Context\ud Landscape heterogeneity (the composition and configuration of different landcover types) plays a key role in shaping woodland bird assemblages in wooded-agricultural mosaics. Understanding how species respond to landscape factors could contribute to preventing further decline of woodland bird populations.\ud Objective\ud To investigate how woodland birds with different species traits respond to landscape heterogeneity, and to identify whether specific landcover types are important for maintaining diverse populations in wooded-agricultural environments. \ud Methods\ud Birds were sampled from woodlands in 58 2 x 2 km tetrads across southern Britain. Landscape heterogeneity was quantified for each tetrad. Bird assemblage response was determined using redundancy analysis combined with variation partitioning and response trait analyses. \ud Results\ud For woodland bird assemblages, the independent explanatory importance of landscape composition and landscape configuration variables were closely interrelated. When considered simultaneously during variation partitioning, the community response was better represented by compositional variables. Different species responded to different landscape features and this could be explained by traits relating to woodland association, foraging strata and nest location. Ubiquitous, generalist species, many of which were hole-nesters or ground foragers, correlated positively with urban landcover while specialists of broadleaved woodland avoided landscapes containing urban areas. Species typical of coniferous woodland correlated with large conifer plantations.\ud Conclusions \ud At the 2 x 2 km scale, there was evidence that the availability of resources provided by proximate landcover types was highly important for shaping woodland bird assemblages. Further research to disentangle the effects of composition and configuration at different spatial scales is advocated.

© The Royal Society of Chemistry 2016.A mediatorless sulfide electrochemical sensing platform utilising a novel nanocopper-oxide screen-printed electrodes (CuSPE) is reported for the first time. The state-of-the-art screen-printed electrochemical sensors demonstrate their capability to quantify sulfide within both the presence and absence of an array of interferents with good levels of sensitivity and repeatability. The direct sensing (using linear sweep voltammetry) of sulfide utilising the CuSPEs provides a mediatorless approach for the detection of sulfide, yielding useful analytical signatures that can be successfully quantified. The proposed novel protocol using the CuSPEs is successfully applied to the sensing of sulfide within drinking water exhibiting a high level of recovery.

© 2016 The Royal Society of Chemistry. This is the first comprehensive analysis of paper-based supercapacitors, P-SCs, that are produced utilising commercially available pencils to draw an interdigitated design upon common household printing paper, developing cheap, green and reliable low profile electrical conductors and electrodes. The P-SCs are optimised in terms of the composition of pencil used, the number of layers and the analysis of single or double sided interdigitated electrode designs; such a comprehensive study is seldom explored in previous literature. A full analysis of the physical and electrochemical properties of the pencil drawn electrodes has been performed, including the application of a new capacitive testing/evaluation circuit applied to charge/discharge measurements/analysis, which provides a revolutionary and unambiguous analysis of the capacitance of the fabricated electrodes; an easy to use experiment guide is presented. The P-SCs are benchmarked using 0.1 M H 2 SO 4 as the aqueous electrolyte. The P-SCs demonstrate a specific capacitance of ∼10.6 μF mg -1 at a charge current of 0.46 A g -1 . The P-SCs are integrated into a novel pouch design, providing a flexible, cheap and easily manufactured supercapacitor, which demonstrates a capacitance of ∼101.4 μF, exhibiting a specific capacitance of ∼42.4 μF g -1 at a current density of 0.46 A g -1 , exhibiting energy and power densities of ∼0.45 J mg -1 (0.125 mW h mg -1 ) and ∼0.03 W mg -1 respectively. The pouch cell, fabricated from P-SCs, utilises five parallel double-sided pencil drawn electrodes, with paper separators, and retains 82.2% of its maximum capacitance, after 5121 charge/discharge cycles at a current density of 0.09 A g -1 . Last, a solid state P-SC is developed utilising a PVA-H 2 SO 4 solid electrolyte, which demonstrates a specific capacitance of 141.8 μF g -1 , at a charging current of 4.33 μA g -1 .

Screen-printed electrochemical sensing platforms, due to their scales of economy and high reproducibility, can provide a useful approach to translate laboratory-based electrochemistry into the field. An important factor when utilising screen-printed electrodes (SPEs) is the determination of their real electrochemical surface area, which allows for the benchmarking of these SPEs and is an important parameter in quality control. In this paper, we consider the use of cyclic voltammetry and chronocoulometry to allow for the determination of the real electrochemical area of screen-printed electrochemical sensing platforms, highlighting to experimentalists the various parameters that need to be diligently considered and controlled in order to obtain useful measurements of the real electroactive area.

Hierarchical nanoscale carbons have received wide interest as electrode materials for energy storage and conversion due to their fast mass transfer processes, outstanding electronic conductivity, and high stability. Here, heteroatom (S, P, and N) doped hierarchical vesicular carbon (HHVC) materials with a high surface area up to 867.5 m2 g−1 are successfully prepared using a surface polymerization of hexachloro‐cyclotriphosphazene (HCCP) and 4,4′‐sulfonyldiphenol (BPS) on the ZIF‐8 polyhedrons. Significantly, it is the first time to achieve a controllability of the wall thickness for this unique carbon, ranging from 18 to 52 nm. When utilized as anodes for sodium ion batteries, these novel carbon materials exhibit a high specific capacity of 327.2 mAh g−1 at 100 mA g−1 after 100 cycles, which can be attributed to the expanded interlayer distance and enhanced conductivity derived from the doping of heteroatoms. Importantly, a high capacity of 142.6 mAh g−1 can be obtained even at a high current density of 5 A g−1, assigning to fast ion/electronic transmission processes stemming from the unique hierarchical vesicular structure. This work offers a new route for the fabrication/preparation of multi‐heteroatom doped hierarchical vesicular materials.

We have developed high affinity Molecularly Imprinted Polymers (MIPs) for neurotransmitters such as dopamine, noradrenaline and caffeine. These polymer particles are mixed within the bulk of screen-printed ink allowing masss-producible bulk modified MIP Screen-Printed Electrodes (MIP-SPEs) to be realised. We have explored different SPE supporting surfaces, such as polyester, tracing paper and household-printing paper. The performance of those MIP-SPEs is studied using the Heat-Transfer Method (HTM), a patented thermal method. With the combination of screen-printing techniques and thermal detection, it is possible to develop a portable sensor platform that is capable of low-cost and straightforward detection of biomolecules on-site. In the future, this unique sensor architecture holds great promise for the use in biomedical devices.

© 2017 American Chemical Society. Cesium-gold (Cs-Au) nanoparticles are shown to be analytically advantageous for the electroanalytical sensing of dapoxetine (DPX), a serotonin reuptake inhibitor used for the treatment of premature ejaculation. The Cs-Au nanoparticles are electrically wired and supported upon mass producible, economical screen-printed electrochemical sensing platforms and are characterized electrochemically (cyclic voltammetry and electrochemical impedance spectroscopy) and physiochemically (field emission scanning electron microscopy and energy dispersive X-ray analysis). The face-centered design was applied to optimize the significant experimental factors by using square wave voltammetry. The Cs-Au-based sensor is found to exhibit a large linear range (10 -7 to 10 -4 M) with a good analytical linearity with the limits of detection and quantification corresponding to 2.50 - 10 -10 and 8.33 - 10 -8 M, respectively. The developed sensor was successfully applied in the quantification of DPX in the presence of sildenafil, both of which are commonly found within combined dose tablet pharmaceutical formulations. The proposed DPX electrochemical Cs-Au-based sensor has the advantages of being single-shot and disposable and is shown to be successful in determining DPX in pharmaceutical formulations, human urine, and serum samples with acceptable recoveries.

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.