Fabrication of carbon paste electrode containing a new inorganic–organic hybrid based on [SiW12O40]4− polyoxoanion and Nile blue and its electrocatalytic activity toward nitrite reduction

In this study, a new inorganic–organic hybrid compound consisting of a Keggin type polyoxometalate, H4SiW12O40 (SiW12), and Nile blue (NB) was synthesized and characterized. The (NB)2H2SiW12O40 (NB2SiW12) hybrid compound was characterized by Fourier transform infrared (FT-IR), elemental (CHNS) analysis, UV–Vis and thermogravimetry techniques, and used as a bulk modifier to fabricate a chemically modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior of the newly NB2SiW12 composite CPE was analyzed by cyclic voltammetry, and the electrode was applied for nitrite reduction, exhibiting high electrocatalytic activity. Determination of nitrite by fixed potential amperometry was done under various experimental conditions and, at the optimum conditions, the linear response ranged from 5 to 1200 μM with a high sensitivity of and a low detection limit. The electrode has the remarkable advantage of surface renewal owing to bulk modification, as well as simple preparation, good mechanical and chemical stability and reproducibility. No noticeable interferences from other ionic species usually found in natural water were observed. The new developed electrode has been successfully applied for detection of nitrite in real water samples

Design and application of a flow cell for carbon-film based electrochemical enzyme biosensors

A flow cell has been designed for use with an electrochemical enzyme biosensor, based on low-cost carbon-film electrodes. Three types of mediators were used: cobalt and copper hexacyanoferrates and poly(neutral red) (PNR), covered with glucose oxidase (GOx) immobilised by cross-linking with glutaraldehyde in the presence of bovine serum albumin or inside a oxysilane sol-gel network. Mixtures of sol-gel precursors were made from 3-aminopropyl-triethoxysilane (APTOS) together with methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), tetraethyloxysilane (TEOS) or 3-glycidoxypropyl-trimethoxysilane (GOPMOS), and the best chosen for encapsulation. Optimisation in batch mode, using amperometric detection at fixed potential, showed the PNR-GOx modified carbon-film electrodes to be best for flow analysis for both glutaraldehyde and sol-gel enzyme immobilisation. Both types of enzyme electrode were tested under flow conditions and the reproducibility and stability of the biosensors were evaluated. The biosensors were used for fermentation monitoring of glucose in grape must and interference studies were also performed.http://www.sciencedirect.com/science/article/B6THP-4M0BH9Y-2/1/306f5db86217ea276bf808fb05c0288

Behaviours, motivations and values: Validity, reliability, and utility of novice motorcyclist' self-report in road safety research

The continuing use of self-report methods demands consideration of the validity, reliability, and utility of self-report in road safety research. This thesis assesses self-report issues with respect to four key constructs in motorcycle safety research—exposure, on-road behaviours, riding motivations, and perceived value in a sample of Australian novice motorcycle riders. In Study 1 a comprehensive set of statistical analyses was performed to test the validity and reliability of various self-report measures of riding exposure. In Study 2 and Study 3 previously untested psychometric properties of stability, content validity, and predictive validity of the Motorcycle Rider Behaviour Questionnaire and the Motorcycle Rider Motivation Questionnaire in terms of police-recorded offences and crashes as well as previously assessed factor structure, internal consistency, and predictive validity in terms of self-reported crashes were examined. In Study 4 I demonstrated the utility of a contingent valuation (CV) survey in measuring, understanding, and therefore addressing the perceived value of rider training amongst novice riders. The four studies highlight that the appropriateness of self-report depends on not only the nature of the phenomenon under study but the extent to which the factors that contribute to validity and reliability are accounted for in the design of self-report measures

A Midsummer Night's Dream

A simple, economic, highly sensitive and highly selective method for the detection of caffeine has been developed at bare and Nafion-modified glassy carbon electrodes (GCE). The electrochemical behaviour of caffeine was examined in electrolyte solutions of phosphate buffer saline, sodium perchlorate, and in choline chloride plus oxalic acid, using analytical determinations by fixed potential amperometry, phosphate buffer saline being the best. Modifications of the GCE surface with poly(3,4-ethylenedioxythiophene) (PEDOT), Nafion, and multi-walled carbon nanotubes were tested in order to evaluate possible sensor performance enhancements, Nafion giving the most satisfactory results. The effect of interfering compounds usually found in samples containing caffeine was examined at GCE without and with Nafion coating, to exclude interferences, and the sensors were successfully applied to determine the caffeine content in commercial beverages and drugs

Sex difference and intra-operative tidal volume: Insights from the LAS VEGAS study

BACKGROUND: One key element of lung-protective ventilation is the use of a low tidal volume (VT). A sex difference in use of low tidal volume ventilation (LTVV) has been described in critically ill ICU patients.OBJECTIVES: The aim of this study was to determine whether a sex difference in use of LTVV also exists in operating room patients, and if present what factors drive this difference.DESIGN, PATIENTS AND SETTING: This is a posthoc analysis of LAS VEGAS, a 1-week worldwide observational study in adults requiring intra-operative ventilation during general anaesthesia for surgery in 146 hospitals in 29 countries.MAIN OUTCOME MEASURES: Women and men were compared with respect to use of LTVV, defined as VT of 8 ml kg-1 or less predicted bodyweight (PBW). A VT was deemed 'default' if the set VT was a round number. A mediation analysis assessed which factors may explain the sex difference in use of LTVV during intra-operative ventilation.RESULTS: This analysis includes 9864 patients, of whom 5425 (55%) were women. A default VT was often set, both in women and men; mode VT was 500 ml. Median [IQR] VT was higher in women than in men (8.6 [7.7 to 9.6] vs. 7.6 [6.8 to 8.4] ml kg-1 PBW, P < 0.001). Compared with men, women were twice as likely not to receive LTVV [68.8 vs. 36.0%; relative risk ratio 2.1 (95% CI 1.9 to 2.1), P < 0.001]. In the mediation analysis, patients' height and actual body weight (ABW) explained 81 and 18% of the sex difference in use of LTVV, respectively; it was not explained by the use of a default VT.CONCLUSION: In this worldwide cohort of patients receiving intra-operative ventilation during general anaesthesia for surgery, women received a higher VT than men during intra-operative ventilation. The risk for a female not to receive LTVV during surgery was double that of males. Height and ABW were the two mediators of the sex difference in use of LTVV.TRIAL REGISTRATION: The study was registered at Clinicaltrials.gov, NCT01601223

An alcohol oxidase biosensor using PNR redox mediator at carbon film electrodes

A new amperometric biosensor for ethanol monitoring has been developed and optimised. The biosensor uses poly(neutral red) (PNR), as redox mediator, which is electropolymerised on carbon film electrodes and alcohol oxidase (AlcOx) from Hansenula polymorpha as recognition element, immobilised by cross-linking with glutaraldehyde (GA) in the presence of bovine serum albumin (BSA) as carrier protein. Optimisation of variables affecting the system was performed and, for chronoamperometric measurements, a potential of -0.300 V versus saturated calomel electrode was chosen in 0.1 M sodium phosphate buffer saline at pH 7.5. The optimised biosensor showed a good sensitivity of 171.8 ± 14.8 nA mM-1 and the corresponding detection limit (signal-to-noise-ratio = 3) of 29.7 ± 1.5 [mu]M. Stability studies showed a good preservation of the bioanalytical properties of the sensor, 57.6% of its initial sensitivity remaining after 3 weeks (the sensor was used two to three times per week). No significant interferences were found from compounds usually present in wine. The biosensor was used for the determination of ethanol in Portuguese red and white wines.http://www.sciencedirect.com/science/article/B6THP-4PT7WW6-5/1/63b0a7a11cea967b9078c3d9acbee6e

Immobilized Antibodies on Mercaptophenylboronic Acid Monolayers for Dual-Strategy Detection of 20S Proteasome

A dual strategy for the electrochemical detection for 20S proteasome (20S) is proposed, based on the oriented immobilization of a capture monoclonal antibody (Abβ) on a self-assembled monolayer of 4-mercaptophenylboronic acid (4-MPBA) on gold electrodes, which led to the Au/4-MPBA/Abβ immunosensor. The methodology comprises the correlation of 20S concentration with (i) its proteolytic activity toward the Z-LLE-AMC substrate, using the Au/4-MPBA/Abβ/20S, and (ii) the enzymatic activity of an alkaline phosphatase (AlkP) from the AlkP-labeled secondary antibody (Abcore-AlkP), which involves the conversion of aminophenylphosphate to the electroactive aminophenol using Au/4-MPBA/Abβ/20S/Abcore-AlkP. The step-by-step construction of the immunosensor and the interactions at its surface were evaluated by surface plasmon resonance and gravimetric analysis with quartz crystal microbalance, showing a high affinity between both antibodies and 20S. Morphological analysis by scanning electron microscopy demonstrated a pattern of parallel lines upon immobilization of Abβ on 4-MPBA and morphological changes to a well-organized granular structure upon binding of 20S. A voltametric and impedimetric characterization was performed after each step in the immunosensor construction. The two detection strategies were evaluated. It was shown that the immunosensor responds linearly with 20S concentration in the range between 5 and 100 µg mL−1, which corresponds to proteasome levels in serum in the case of diverse pathological situations, and LoD values of 1.4 and 0.2 µg mL−1 were calculated for the detection strategies. The immunosensor was applied to the detection of 20S in serum samples with recovery values ranging from 101 to 103%

PC-12 Cell Line as a Neuronal Cell Model for Biosensing Applications

PC-12 cells have been widely used as a neuronal line study model in many biosensing devices, mainly due to the neurogenic characteristics acquired after differentiation, such as high level of secreted neurotransmitter, neuron morphology characterized by neurite outgrowth, and expression of ion and neurotransmitter receptors. For understanding the pathophysiology processes involved in brain disorders, PC-12 cell line is extensively assessed in neuroscience research, including studies on neurotoxicity, neuroprotection, or neurosecretion. Various analytical technologies have been developed to investigate physicochemical processes and the biosensors based on optical and electrochemical techniques, among others, have been at the forefront of this development. This article summarizes the application of different biosensors in PC-12 cell cultures and presents the modern approaches employed in neuronal networks biosensing

Development and characterization of layer-by-layer biosensors based on PEI(+)/GOx(-) layers using label-free methods

Biosensors, as analytical devices, demonstrate unique efficiency in translating biochemical events into easily measurable electrical signals by using biological recognition elements, especially enzymes. Of the possible enzyme immobilisation methods, the layer-by-layer (LBL) technique, based on electrostatic interactions between layers, has the advantages of low cost, using small amount of materials, and leads to the formation of highly ordered and reproducible biosensor architectures. In this study, LbL biosensor construction has been evaluated. The substrates used were Au surfaces and mediated carbon-ink screen-printed electrodes. The gold electrodes were first functionalized with amino moieties by covalent linkage of cysteamine (Cys) through Au-S bonds. These allowed the linking of polyethyleneimine (PEI) through hydrogen-bonding to the gold surface and increased the stability of subsequent multilayers. PEI was directly adsorbed on the SPE surface. PEI is a short chain polymer and thence an efficient electron carrier, and being positively charged, it allows the formation of LBL structures with negatively charged enzymes. The multilayer formation of PEI(+)/GOx(-) was monitored by cyclic voltammetry, electrochemical impedance spectroscopy, and gravimetry. The influence of each enzymatic layer on the performance of the developed biosensor was analysed by fixed potential amperometric measurements

Hybrid Nanocomposite Platform, Based on Carbon Nanotubes and Poly(Methylene Blue) Redox Polymer Synthesized in Ethaline Deep Eutectic Solvent for Electrochemical Determination of 5-Aminosalicylic Acid

A novel hybrid composite of conductive poly(methylene blue) (PMB) and carbon nanotubes (CNT) was prepared for the detection of 5-aminosalicylic acid (5-ASA). Electrosynthesis of PMB with glassy carbon electrode (GCE) or with carbon nanotube modified GCE was done in ethaline deep eutectic solvent of choline chloride mixed with ethylene glycol and a 10% v/v aqueous solution. Different sensor architectures were evaluated in a broad range of pH values in a Britton-Robinson (BR) buffer using electrochemical techniques, chronoamperometry (CA), and differential pulse voltammetry (DPV), to determine the optimum sensor configuration for 5-ASA sensing. Under optimal conditions, the best analytical performance was obtained with CNT/PMBDES/GCE in 0.04 M BR buffer pH 7.0 in the range 5–100 µM 5-ASA using the DPV method, with an excellent sensitivity of 9.84 μA cm−2 μM−1 (4.9 % RSD, n = 5) and a detection limit (LOD) (3σ/slope) of 7.7 nM, outclassing most similar sensors found in the literature. The sensitivity of the same sensor obtained in CA (1.33 μA cm−2 μM−1) under optimal conditions (pH 7.0, Eapp = +0.40 V) was lower than that obtained by DPV. Simultaneous detection of 5-ASA and its analogue, acetaminophen (APAP), was successfully realized, showing a catalytic effect towards the electro-oxidation of both analytes, lowering their oxidation overpotential, and enhancing the oxidation peak currents and peak-to-peak separation as compared with the unmodified electrode. The proposed method is simple, sensitive, easy to apply, and economical for routine analysis