Electrochemical sensing of toxic gases in room temperature ionic liquids

This study investigates the electrochemical behaviour of three highly toxic gases, methylamine, chlorine and hydrogen chloride in room temperature ionic liquids (RTILs) on both conventional electrodes and screen printed electrodes (SPEs). It was found that all gases give good analytical responses and comparable limits of detection on both electrodes. This suggests that low-cost SPEs can be used in conjunction with RTILs for amperometric gas detection, which would allow faster response times and cheaper manufacturing costs

Sensors for Highly Toxic Gases: Methylamine and Hydrogen Chloride Detection at Low Concentrations in an Ionic Liquid on Pt Screen Printed Electrodes

Commercially available Pt screen printed electrodes (SPEs) have been employed as possible electrode materials for methylamine (MA) and hydrogen chloride (HCl) gas detection. The room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) was used as a solvent and the electrochemical behaviour of both gases was first examined using cyclic voltammetry. The reaction mechanism appears to be the same on Pt SPEs as on Pt microelectrodes. Furthermore, the analytical utility was studied to understand the behaviour of these highly toxic gases at low concentrations on SPEs, with calibration graphs obtained from 10 to 80 ppm. Three different electrochemical techniques were employed: linear sweep voltammetry (LSV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV), with no significant differences in the limits of detection (LODs) between the techniques (LODs were between 1.4 to 3.6 ppm for all three techniques for both gases). The LODs achieved on Pt SPEs were lower than the current Occupational Safety and Health Administration Permissible Exposure Limit (OSHA PEL) limits of the two gases (5 ppm for HCl and 10 ppm for MA), suggesting that Pt SPEs can successfully be combined with RTILs to be used as cheap alternatives for amperometric gas sensing in applications where these toxic gases may be released

Oxygen reduction voltammetry on platinum macrodisk and screen-printed electrodes in ionic liquids: Reaction of the electrogenerated superoxide species with compounds used in the paste of Pt screen-printed electrodes?

Screen-printed electrodes (SPEs) are widely investigated as simple, three-electrode planar surfaces for electrochemical sensing applications, and may be ideal for gas sensing purposes when combined with non-volatile room temperature ionic liquids (RTILs). In this report the suitability of SPEs with RTIL solvents has been investigated for oxygen detection. Oxygen reduction has been studied on commercially available platinum SPEs in eight RTILs. Cyclic voltammetric wave shapes were found to be significantly different on Pt SPE surfaces compared to conventional solid Pt macroelectrodes, suggesting a possible reaction of the electrogenerated superoxide with the compounds that make up the ink/paste of the SPE surface. The only RTIL that did not show such drastically different voltammetry was one that contained a pyrrolidinium cation, suggesting a more chemically stable solvent environment compared to the other imidazolium and phosphonium cations studied. The analytical utility was then studied on four SPE surfaces (carbon, gold, platinum and silver) in two RTILs (one with a pyrrolidinium and one with an imidazolium cation) and linear responses were observed between current and % concentration in the range 10–100% O2. This suggests that SPEs may indeed be suitable for oxygen sensing in some RTILs, but significantly more pre-treatment of the surface is required to obtain reliable results. However, the reaction of superoxide with the SPE ink, together with a noticeable deterioration of the signal over time, suggests that this type of sensing platform may only be suitable for “single-use” oxygen sensing applications

Electrochemical Behavior of Chlorine on Platinum Microdisk and Screen-Printed Electrodes in a Room Temperature Ionic Liquid

As a result of the toxic and corrosive nature of chlorine gas, simple methods for its detection are required for monitoring and control purposes. In this paper, the electrochemical behavior of chlorine on platinum working electrodes in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) is reported, as a basis for simple sensor devices. Cyclic voltammetry (CV) and chronoamperometry (CA) on a Pt microelectrode revealed the two-electron reduction of Cl2 to chloride ions. On the CV reverse sweep, an oxidation peak due to the oxidation of chloride was observed. The reduction process was diffusion controlled at the concentrations studied (≤4.5% in the gas phase), in contrast to a previous report (J. Phys. Chem. C2008, 112, 19477), which examined only 100% chlorine. The diffusion-controlled currents were linear with gas-phase concentration. Fitting of the CA transients to the Shoup and Szabo expression gave a diffusion coefficient for chlorine in the RTIL of ca. 2.6 × 10–10 m2 s–1. Furthermore, determination of the equilibrium concentration of Cl2 in the RTIL phase as a function of gas-phase concentration enabled a value of 35 to be determined for the Henry’s law dimensionless volatility constant. The electrochemical behavior of chlorine on a Pt screen-printed electrode was also investigated, suggesting that these devices may be useful for chlorine detection in conjunction with suitable RTILs

Nanowire Array Breath Acetone Sensor for Diabetes Monitoring

Diabetic ketoacidosis (DKA) is a life-threatening acute complication of diabetes in which ketone bodies accumulate in the blood. Breath acetone (a ketone) directly correlates with blood ketones, such that breath acetone monitoring could be used to improve safety in diabetes care. In this work, we report the design and fabrication of a chitosan/Pt/InP nanowire array based chemiresistive acetone sensor. By implementing chitosan as a surface functionalization layer and a Pt Schottky contact for efficient charge transfer processes and photovoltaic effect, self-powered, highly selective acetone sensing has been achieved. This sensor has an ultra-wide detection range from sub-ppb to >100,000 ppm levels at room temperature, incorporating the range from healthy individuals (300-800 ppb) to those at high-risk of DKA (> 75 ppm). The nanowire sensor has been further integrated into a handheld breath testing prototype, the Ketowhistle, which can successfully detect different ranges of acetone concentrations in simulated breath. The Ketowhistle demonstrates immediate potential for non-invasive ketone testing and monitoring for persons living with diabetes, in particular for DKA prevention

ANFO vapour detection with conducting polymer percolation network sensors and GC/MS

Ammonium nitrate mixed with fuel oil (ANFO) is commonly used in improvised explosive devices (IEDs). The development of ANFO vapour sensors that are small, inexpensive, and easy to use will enable widespread IED detection in the context of security and humanitarian demining. Because of concealment and the low vapour pressures of most explosive materials, achieving sufficiently high sensitivity and low limits of detection are some of the main challenges of explosives vapour detection. Here ANFO chemiresistive vapour sensors based on polypyrrole (PPy) percolation networks are presented and compared to gas chromatography-mass spectroscopy (GC/MS) results for ANFO. Improved sensitivities are achieved by using a polymer percolation network instead of a thin film for the gas sensors. Vapour concentrations are detected of 13–180 ppb of ammonia emitted by a variety of different ammonium nitrate-containing fertilisers and fertiliser-diesel mixtures

The current understanding of precision medicine and personalised medicine in selected research disciplines:study protocol of a systematic concept analysis

INTRODUCTION: The terms ‘precision medicine’ and ‘personalised medicine’ have become key terms in health-related research and in science-related public communication. However, the application of these two concepts and their interpretation in various disciplines are heterogeneous, which also affects research translation and public awareness. This leads to confusion regarding the use and distinction of the two concepts. Our aim is to provide a snapshot of the current understanding of these concepts. METHODS AND ANALYSIS: Our study will use Rodgers’ evolutionary concept analysis to systematically examine the current understanding of the concepts ‘precision medicine’ and ‘personalised medicine’ in clinical medicine, biomedicine (incorporating genomics and bioinformatics), health services research, physics, chemistry, engineering, machine learning and artificial intelligence, and to identify their respective attributes (clusters of characteristics) and surrogate and related terms. A systematic search of the literature will be conducted for 2016–2022 using databases relevant to each of these disciplines: ACM Digital Library, CINAHL, Cochrane Library, F1000Research, IEEE Xplore, PubMed/Medline, Science Direct, Scopus and Web of Science. These are among the most representative databases for the included disciplines. We will examine similarities and differences in definitions of ‘precision medicine’ and ‘personalised medicine’ in the respective disciplines and across (sub)disciplines, including attributes of each term. This will enable us to determine how these two concepts are distinguished. ETHICS AND DISSEMINATION: Following ethical and research standards, we will comprehensively report the methodology for a systematic analysis following Rodgers’ concept analysis method. Our systematic concept analysis will contribute to the clarification of the two concepts and distinction in their application in given settings and circumstances. Such a broad concept analysis will contribute to non-systematic syntheses of the concepts, or occasional systematic reviews on one of the concepts that have been published in specific disciplines, in order to facilitate interdisciplinary communication, translational medical research and implementation science

A user preference analysis of commercial breath ketone sensors to inform the development of portable breath ketone sensors for diabetes management in young people

BACKGROUNDPortable breath ketone sensors may help people with Type 1 Diabetes Mellitus (T1DM) avoid episodes of diabetic ketoacidosis; however, the design features preferred by users have not been studied. We aimed to elucidate breath sensor design preferences of young people with T1DM (age 12 to 16) and their parents to inform the development of a breath ketone sensor prototype that would best suit their diabetes management needs.RESEARCH DESIGNS AND METHODSTo elicit foundational experiences from which design preference ideas could be generated, two commercially available breath ketone sensors, designed for ketogenic diet monitoring, were explored over one week by ten young people with T1DM. Participants interacted with the breath ketone sensing devices, and undertook blood ketone testing, at least twice daily for five days to simulate use within a real life and ambulatory care setting. Semi-structured interviews were conducted post-testing with the ten young participants and their caregivers (n = 10) to elicit preferences related to breath sensor design and use, and to inform the co-design of a breath ketone sensor prototype for use in T1DM self-management. We triangulated our data collection with key informant interviews with two diabetes educators working in pediatric care about their perspectives related to young people using breath ketone sensors.RESULTSParticipants acknowledged the non-invasiveness of breath sensors as compared to blood testing. Affordability, reliability and accuracy were identified as prerequisites for breath ketone sensors used for diabetes management. Design features valued by young people included portability, ease of use, sustainability, readability and suitability for use in public. The time required to use breath sensors was similar to that for blood testing. The requirement to maintain a 10-second breath exhalation posed a challenge for users. Diabetes educators highlighted the ease of use of breath devices especially for young people who tended to under-test using blood ketone strips.CONCLUSIONSBreath ketone sensors for diabetes management have potential that may facilitate ketone testing in young people. Our study affirms features for young people that drive usability of breath sensors among this population, and provides a model of user preference assessment.</p

Electrochemical Oxidation and Sensing of Methylamine Gas in Room Temperature Ionic Liquids

The electrochemical behaviour of methylamine gas in several room temperature ionic liquids (RTILs), [C2mim][NTf2], [C4mim][NTf2], [C6mim][FAP], [C4mpyrr][NTf2], [C4mim][BF4], and [C4mim][PF6] has been investigated on a Pt microelectrode using cyclic voltammetry. A broad oxidation wave at approximately 3 V, two reduction peaks and another oxidation peak was observed. A complicated mechanism is predicted based on the voltammetry obtained, with ammonia gas as a likely by-product. The currents obtained suggest that methylamine has a high solubility in RTILs, which is important for gas sensing applications. The analytical utility of methylamine was then studied in [C4mpyrr][NTf2] and [C2mim][NTf2]. A linear calibration graph with an R2 value of 0.99 and limits of detection of 33 and 34 ppm were obtained respectively, suggesting that RTILs are favourable non-volatile solvents for the electrochemical detection of highly toxic methylamine gas

SHEAR BEHAVIOUR OF REINFORCED AND PARTIALLY PRESTRESSED STEEL FIBRE CONCRETE BEAMS

Ph.DDOCTOR OF PHILOSOPH