Electroanalysis at discrete arrays of gold nanowire electrodes

The development of reliable nanosensors offers a number of potential advantages in nanoscale analytical science. A hybrid electron beam-photolithography process was used to fabricate robust and reliable electrochemical nanowire array devices, with highly reproducible critical dimensions, 100 ± 6 nm. Nanowire electrode arrays were designed to permit diffusional independence at each nanowire element in an array thereby maximising limiting currents for optimised electrochemical nanosensing. The electrochemical behaviour of discrete nanowire electrode arrays was investigated using cyclic voltammetry in ferrocenemonocarboxylic acid. Single nanowire devices yielded highly reproducible steady-state sigmoidal waveforms, with typical currents of 179 ± 16 pA. Higher steady-state currents were achieved at nanowire arrays, up to ∼1.2 nA for arrays consisting of six nanowire elements. At low and intermediate scan rates, sigmoidal waveforms were observed for nanowire arrays indicating very fast mass transport. However, voltammetric behaviour consistent with semi-infinite linear diffusion was observed at higher scan rates confirming the presence of overlapping diffusion profiles between neighbouring nanowires within an array. The existence of diffusion overlap between neighbouring nanowire elements was further demonstrated by deviation of measured steady-state currents from estimates, becoming more pronounced with increasing numbers on nanowire elements in the array. Finally capacitive charging of the electrodes was explored, and were found to exhibit very low capacitance typically ∼31 ± 3 nF cm−2 per device, three orders of magnitude less than that reported for conventional microelectrodes (∼20 μF cm−2)

Near-infrared electroluminescent devices based on colloidal HgTe quantum dot arrays

Crystalline 4.6 nm HgTe quantum dots, stabilized by 1-thioglycerol ligands, were synthesized by wet chemical methods. Room-temperature photoluminescencespectra of the dots, both in solution and as solid arrays, exhibited near-infrared emission. Light-emitting devices were fabricated by deposition of quantum dot layers onto glass∕indium tin oxide (ITO)∕3,4-polyethylene-dioxythiophene-polystyrene sulfonate (PEDOT) substrates followed by top contacting with evaporated aluminum. Room-temperature near-infraredelectroluminescence from 1mm2 ITO∕PEDOT∕HgTe∕Al devices, centered at ∼1600nm, with an external quantum efficiency of 0.02% and brightness of 150nW/mm2 at 50 mA and 2.5 V was achieved

Effect of floor type on performance, lying time and dirt scores of finishing beef cattle: A meta-analysis

peer-reviewedData from individual studies evaluating the effect of housing systems on performance, lying time and dirt scores of finishing beef cattle are conflicting. The objective of this study was to collate the data from previous animal housing studies and quantify, through meta-analysis, the effect of floor type on animal performance, lying time and dirt scores. From 38 peer-reviewed articles, published between 1969 and 2017, 18 were determined to be eligible for meta-analysis. Papers were included in the study if they contained information on the effect of floor surface on animal performance (average daily liveweight gain (ADG), feed conversion ratio (FCR) and carcass weight), lying behaviour or animal cleanliness. There was no difference (P > 0.10) in ADG, FCR or carcass weight between concrete slatted floors (CSF) and CSF overlaid with rubber mats (RM). Using RM had no effect (P > 0.10) on lying duration or dirt scores of cattle. There was no difference (P > 0.10) in the ADG, FCR, carcass weight, lying duration or cleanliness of cattle housed on CSF or straw bedding. It was concluded that using RM or straw instead of CSF had no effect on performance, lying time or dirt scores

Transparent polymer-based SERS substrates templated by a soda can

This paper demonstrates the reproducible fabrication of transparent Surface Enhanced Raman Scattering (SERS) substrates, fabricated by employing an aluminium soda can to template nanostructures on a flexible thermoplastic polymer surface, followed by deposition of a silver over layer. Electron microscopy and finite element modelling simulations strongly suggested the SERS response arose at regions of high electromagnetic field strength occurring between metallic clusters following illumination by monochromatic radiation. The sensors exhibited rapid, quantitative and high sensitivity, for example, 5 × 10−10 M (204 pg/mL) crystal violet detection in 10 min using a simple drop and dry method. We also show detection of glucose employing a chemically modified silver surface bearing a pre-deposited SAM layer. Furthermore, the transparent substrates permitted back excitation and collection through the substrate with corresponding spectra exhibiting clear and well-defined spectral SERS peaks. Finally, we present the detection of trace amounts of melamine in complex media solution (milk and infant formula). We benchmark the sensor performance using commercial analytical instrumentation (MS-MS) and show comparable sensitivity between the SERS substrates and MS-MS

Direct observation of mercury amalgamation on individual gold nanorods using spectroelectrochemistry

We report on the use of a spectroelectrochemical method for the investigation of mercury amalgamation on gold nanorods. Hg2+ was electrochemically reduced at gold nanorod electrodes, and the consequent optical changes resulting from deposition of mercury were monitored by dark-field microscopy. Nanorods displayed marked scattering color transitions from red to green and longitudinal surface plasmon resonance (LSPR) blue-shifts up to 197 nm. Corresponding cathodic voltammograms showed strong reduction peaks at potentials which were attributed to Hg2+ reduction. The highest optical blue-shifts were observed for working electrodes constituted by well-separated gold nanorods deposited on ITO substrates, which also showed transition from diffusion-limited to steady-state electrochemical behavior. Theoretical simulations were carried out to support experimental results and to obtain further insight into the diffusional behavior of mercury reduction at nanorod electrodes. Real time observation of the amalgamation process was performed by monitoring the evolution of spectral response from single nanorods in the presence of Hg2+ and subjected to either linear sweep voltammetry or chronoamperometry. The analysis confirmed a direct correlation between the occurrence of spectral changes and the formation of an amalgam resulting from deposition and subsequent diffusion of reduced mercury into the nanorods. This work shows the potential of this method for elucidation of reaction mechanisms occurring at nanoscale electrodes and for sensitive detection of mercury for environmental applications

Madden, Julia; O'Mahony, Conor; Thompson, Michael; O'Riordan, Alan; Galvin, Paul

This article explores recent advances in the development of electrochemical biosensors on microneedle platforms towards on-device sensing of biomarkers present in dermal interstitial fluid. The integration of a biosensor with a microneedle platform opens the possibility for minimally invasive bio-chemical detection or continuous monitoring within the dermal interstitial fluid. An introduction to interstitial fluid is provided placing emphasis on sampling methods that have been employed to extract and/or sample tissue fluid for analysis. We look briefly at microneedle technologies used to extract dermal interstitial fluid for subsequent analysis. Successive content will focus on microneedle technologies which have been integrated with electrochemical biosensors for the quantification of various metabolites, electrolytes and other miscellaneous entities known to be present in the dermal interstitial fluid. The review concludes with some of the key challenges and opportunities faced by this next-generation wearable sensing technology

Elimination of oxygen interference in the electrochemical detection of monochloramine, using in situ pH control at interdigitated electrodes

Disinfection of water systems by chloramination is a method frequently used in North America as an alternative to chlorination. In such a case, monochloramine is used as the primary chlorine source for disinfection. Regular monitoring of the residual concentrations of this species is essential to ensure adequate disinfection. An amperometric sensor for monochloramine would provide fast, reagent-free analysis; however, the presence of dissolved oxygen in water complicates sensor development. In this work, we used in-situ pH control as a method to eliminate oxygen interference by conversion of monochloramine to dichloramine. Unlike monochloramine, the electrochemical reduction of dichloramine occurs outside the oxygen reduction potential window and is therefore not affected by the oxygen concentration. Potential sweep methods were used to investigate the conversion of monochloramine to dichloramine at pH 3. The pH control method was used to calibrate monochloramine concentrations between 1 and 10 ppm, with a detection limit of 0.03 ppm. Tests were carried out in high alkalinity samples, wherein it was found that the sensitivity of this method effectively remained unchanged. Monochloramine was also quantified in the presence of common interferents (copper, phosphate, and iron) which also had no significant impact on the analysis

Electrochemical sensor for phosphate ions based on laser scriber reduced graphene oxide

This preliminary work shows a new and innovative way to produce laser scribed reduced graphene oxide (LSGO) electrodes using different porous substrates (ranging from paper to plastic and fabric). The obtained electrodes were also tested as electrochemical sensors towards the detection of phosphate ions in water. To obtain the electrodes, a water suspension of GO was filtered on top of substrate (such as Whatman® filter paper) and a complete sensor was obtained from its reduction using a CO2 laser. The electrode is composed of working and counter electrodes made of LSGO and a reference electrode of a Ag/AgCl obtained by using a commercial AgCl conductive paste. Phosphate ions were detected by exploiting the reaction between molybdate and phosphate ions in acidic media (known in literature as molybdenum blue method). This chemical reaction produces the Keggin-type complex (PMo12O40)3-, that can be reduced under applied potential. The obtained results show that phosphate ions can be detected in a wide linear range, from 0.001 mM to 1mM, in presence of 1mM molybdate with a very satisfying selectivity. We also tried to pre-treatment the paper substrate with acidic molybdate ions in order to obtain a ready-made sensor directly usable for the detection of phosphate ions in situ avoiding any kind of real sample manipulation For this aim, the paper substrate was soaked with sulphuric acid and molybdate solution and dried in order to desorb these chemicals directly into the water sample to be analyzed. Preliminary results, shows that the process of absorption and desorption can be carried out by optimizing the volume and concentration of the absorbed solution and thus can be used to obtain a portable, easy to use and fast phosphate sensor for in situ and real time monitoring of water quality

Removal of dissolved oxygen interference in the amperometric detection of monochloramine using a pH control method

Monochloramine amperometric determination was investigated using a pH control method to eliminate dissolved oxygen as an interferent. This method allowed local pH conditions to become more acidic, causing the production of dichloramine. This species showed an onset of electro-reduction at 450 mV, far outside of the oxygen reduction region. Monochloramine was calibrated using this method and showed good linearity (0.99) and a limit of detection of 0.03 ppm