Surface Functionalization and Texturing of Optical Metasurfaces for Sensing Applications.

Optical metasurfaces are planar metamaterials that can mediate highly precise light-matter interactions. Because of their unique optical properties, both plasmonic and dielectric metasurfaces have found common use in sensing applications, enabling label-free, nondestructive, and miniaturized sensors with ultralow limits of detection. However, because bare metasurfaces inherently lack target specificity, their applications have driven the development of surface modification techniques that provide selectivity. Both chemical functionalization and physical texturing methodologies can modify and enhance metasurface properties by selectively capturing analytes at the surface and altering the transduction of light-matter interactions into optical signals. This review summarizes recent advances in material-specific surface functionalization and texturing as applied to representative optical metasurfaces. We also present an overview of the underlying chemistry driving functionalization and texturing processes, including detailed directions for their broad implementation. Overall, this review provides a concise and centralized guide for the modification of metasurfaces with a focus toward sensing applications.

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.

An Outlook of Recent Advances in Chemiresistive Sensor-Based Electronic Nose Systems for Food Quality and Environmental Monitoring.

An electronic nose (Enose) relies on the use of an array of partially selective chemical gas sensors for identification of various chemical compounds, including volatile organic compounds in gas mixtures. They have been proposed as a portable low-cost technology to analyse complex odours in the food industry and for environmental monitoring. Recent advances in nanofabrication, sensor and microcircuitry design, neural networks, and system integration have considerably improved the efficacy of Enose devices. Here, we highlight different types of semiconducting metal oxides as well as their sensing mechanism and integration into Enose systems, including different pattern recognition techniques employed for data analysis. We offer a critical perspective of state-of-the-art commercial and custom-made Enoses, identifying current challenges for the broader uptake and use of Enose systems in a variety of applications.

Shapes of epitaxial gold nanocrystals on SrTiO3 substrates.

Morphological control of gold nanocrystals is important as their catalytic and optical properties are highly shape dependent. In this paper we report the shapes of gold nanocrystals which deviate from the equilibrium Wulff shape due to the influence of the SrTiO3 single crystal substrates. The gold crystals are characterized by scanning tunneling microscopy (STM) and scanning electron microscopy (SEM). The nanocrystals have an equilibrium shape of a truncated octahedron with {111} and {001} facets. On all three substrate surfaces, i.e., SrTiO3(001)-(2 × 1), SrTiO3(001)-c(4 × 2), and SrTiO3(111)-(4 × 4) + (6 × 6), the height-to-width ratio of the gold crystals is not a constant as would be expected for equilibrium crystals, but instead it increases with crystal height. We propose that as the crystals increase in size, their aspect ratio heightens to relax the interfacial strain. The ratio between the {111} and {001} surface areas of our gold crystals is found to differ on the three substrates, which we speculate is due to the selective adsorption of surfactants on the {111} and {001} gold facets resulting from the different substrate surfaces. Reentrant facets of gold crystals that should be present according to their Wulff shape are not observed because these concave sites typically grow out due to kinetic considerations. This study demonstrates the significant effect of the crystal facet termination and surface reconstruction of an oxide substrate on the shape of supported gold nanocrystals.

Interrogation of the Effect of Polymorphism of a Metal-Organic Framework Host on the Structure of Embedded Pd Guest Nanoparticles.

Metal-organic frameworks (MOFs) are very promising host materials for nanoscale guest materials. However, some MOFs such as MIL-53 are known to undergo phase transitions which can complicate the guest particle size control. In this study, Pd nanoparticles embedded in Al-MIL-53 were synthesised via (a) electrodeposition and (b) gas-phase reduction. A thorough structural investigation revealed that each synthesis method most likely favoured a different phase of Al-MIL-53, presenting the possibility of MOF phase selection as a technique for size control of embedded nanoparticles. For the first time, we hereby report the use of pair distribution function analysis to successfully investigate the structure and morphology of guest particles embedded in a MOF host.

Electrochemical studies of hydrogen chloride gas in several room temperature ionic liquids: mechanism and sensing.

The electrochemical behaviour of highly toxic hydrogen chloride (HCl) gas has been investigated in six room temperature ionic liquids (RTILs) containing imidazolium/pyrrolidinium cations and range of anions on a Pt microelectrode using cyclic voltammetry (CV). HCl gas exists in a dissociated form of H(+) and [HCl2](-) in RTILs. A peak corresponding to the oxidation of [HCl2](-) was observed, resulting in the formation of Cl2 and H(+). These species were reversibly reduced to H2 and Cl(-), respectively, on the cathodic CV scan. The H(+) reduction peak is also present initially when scanned only in the cathodic direction. In the RTILs with a tetrafluoroborate or hexafluorophosphate anion, CVs indicated a reaction of the RTIL with the analyte/electrogenerated products, suggesting that these RTILs might not be suitable solvents for the detection of HCl gas. This was supported by NMR spectroscopy experiments, which showed that the hexafluorophosphate ionic liquid underwent structural changes after HCl gas electrochemical experiments. The analytical utility was then studied in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) by utilising both peaks (oxidation of [HCl2](-) and reduction of protons) and linear calibration graphs for current vs. concentration for the two processes were obtained. The reactive behaviour of some ionic liquids clearly shows that the choice of the ionic liquid is very important if employing RTILs as solvents for HCl gas detection.

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.

Simultaneous electrochemical detection of glycated and human serum albumin for diabetes management.

Developing highly selective and sensitive biosensors for diabetes management blood glucose monitoring is essential to reduce the health risks associated with diabetes. Assessing the glycation (GA) of human serum albumin (HSA) serves as an indicator for medium-term glycemic control, making it suitable for assessing the efficacy of blood glucose management protocols. However, most biosensors are not capable of simultaneous detection of the relative fraction of GA to HSA in a clinically relevant range. Here, we report an effective miniaturised biosensor architecture for simultaneous electrochemical detection of HSA and GA across relevant concentration ranges. We immobilise DNA aptamers specific for the detection of HSA and GA on gold nanoislands (Au NIs) decorated screen-printed carbon electrodes (SPCEs), and effectively passivate the residual surface sites. We achieve a dynamic detection range between 20 and 60 mg/mL for HSA and 1-40 mg/mL for GA in buffer solutions. The analytical utility of our HSA and GA biosensor architectures are validated in mice serum indicating immediate potential for clinical applications. Since HSA and GA have similar structures, we extensively assess our sensor specificity, observing high selectivity of the HSA and GA sensors against each other and other commonly present interfering molecules in blood such as glucose, glycine, ampicillin, and insulin. Additionally, we determine the glycation ratio, which is a crucial metric for assessing blood glucose management efficacy, in an extensive range representing healthy and poor blood glucose management profiles. These findings provide strong evidence for the clinical potential of our biosensor architecture for point-of-care and self-assessment of diabetes management protocols.

High-Performance Optoelectronic Gas Sensing Based on All-Inorganic Mixed-Halide Perovskite Nanocrystals with Halide Engineering.

Gas sensors are of great interest to portable and miniaturized sensing technologies with applications ranging from air quality monitoring to explosive detection and medical diagnostics, but the existing chemiresistive NO2 sensors still suffer from issues such as poor sensitivity, high operating temperature, and slow recovery. Herein, a high-performance NO2 sensors based on all-inorganic perovskite nanocrystals (PNCs) is reported, achieving room temperature operation with ultra-fast response and recovery time. After tailoring the halide composition, superior sensitivity of ≈67 at 8 ppm NO2 is obtained in CsPbI2 Br PNC sensors with a detection level down to 2 ppb, which outperforms other nanomaterial-based NO2 sensors. Furthermore, the remarkable optoelectronic properties of such PNCs enable dual-mode operation, i.e., chemiresistive and chemioptical sensing, presenting a new and versatile platform for advancing high-performance, point-of-care NO2 detection technologies.

Nanowire Array Breath Acetone Sensor for Diabetes Monitoring.

Diabetic ketoacidosis (DKA) is a life-threatening acute complication of diabetes characterized by the accumulation of ketone bodies in the blood. Breath acetone, a ketone, directly correlates with blood ketones. Therefore, monitoring breath acetone can significantly enhance the safety and efficacy of diabetes care. In this work, the design and fabrication of an InP/Pt/chitosan nanowire array-based chemiresistive acetone sensor is reported. By incorporation of chitosan as a surface-functional layer and a Pt Schottky contact for efficient charge transfer processes and photovoltaic effect, self-powered, highly selective acetone sensing is achieved. The sensor has exhibited an ultra-wide acetone detection range from sub-ppb to >100 000 ppm level at room temperature, covering those in the exhaled breath from healthy individuals (300-800 ppb) to people at high risk of DKA (>75 ppm). The nanowire sensor has also been successfully integrated into a handheld breath testing prototype, the Ketowhistle, which can successfully detect different ranges of acetone concentrations in simulated breath samples. The Ketowhistle demonstrates the immediate potential for non-invasive ketone monitoring for people living with diabetes, in particular for DKA prevention.

A Self-Powered Portable Nanowire Array Gas Sensor for Dynamic NO2 Monitoring at Room Temperature.

The fast development of the Internet of Things (IoT) has driven an increasing consumer demand for self-powered gas sensors for real-time data collection and autonomous responses in industries such as environmental monitoring, workplace safety, smart cities, and personal healthcare. Despite intensive research and rapid progress in the field, most reported self-powered devices, specifically NO2 sensors for air pollution monitoring, have limited sensitivity, selectivity, and scalability. Here, a novel photovoltaic self-powered NO2 sensor is demonstrated based on axial p-i-n homojunction InP nanowire (NW) arrays, that overcome these limitations. The optimized innovative InP NW array device is designed by numerical simulation for insights into sensing mechanisms and performance enhancement. Without a power source, this InP NW sensor achieves an 84% sensing response to 1 ppm NO2 and records a limit of detection down to the sub-ppb level, with little dependence on the incident light intensity, even under <5% of 1 sun illumination. Based on this great environmental fidelity, the sensor is integrated into a commercial microchip interface to evaluate its performance in the context of dynamic environmental monitoring of motor vehicle exhaust. The results show that compound semiconductor nanowires can form promising self-powered sensing platforms suitable for future mega-scale IoT systems.

Structural Engineering Three-Dimensional Nano-Heterojunction Networks for High-Performance Photochemical Sensing.

Nanoscale heterojunction networks are increasingly regarded as promising functional materials for a variety of optoelectronic and photocatalytic devices. Despite their superior charge-carrier separation efficiency, a major challenge remains in the optimization of their surface properties, with surface defects playing a major role in charge trapping and recombination. Here, we report the effective engineering of the photocatalytic properties of nanoscale heterojunction networks via deep ultraviolet photoactivation throughout their cross-section. For the first time, in-depth XPS analysis of very thick (∼10 µm) NixOy-ZnO films reveals localized p-n nanoheterojunctions with tunable oxygen vacancies (Vo) originating from both NixOy and ZnO nanocrystals. Optimizing the amount of oxygen vacancies leads to a 30-fold increase in the photochemoresistive response of these networks, enabling the detection of representative analyte concentrations down to 2 and 20 ppb at an optimal temperature of 150 °C and room temperature, respectively. Density functional theory calculations reveal that this performance enhancement is presumably due to an 80% increase in the analyte adsorption energy. This flexible nanofabrication approach in conjunction with straightforward vacancy control via photoactivation provides an effective strategy for engineering the photocatalytic activity of porous metal oxide semiconductor networks with applications in chemical sensors, photodetectors, and photoelectrochemical cells.

Electrodetection of Small Molecules by Conformation-Mediated Signal Enhancement.

Electrochemical biosensors allow the rapid, selective, and sensitive transduction of critical biological parameters into measurable signals. However, current electrochemical biosensors often fail to selectively and sensitively detect small molecules because of their small size and low molecular complexity. We have developed an electrochemical biosensing platform that harnesses the analyte-dependent conformational change of highly selective solute-binding proteins to amplify the redox signal generated by analyte binding. Using this platform, we constructed and characterized two biosensors that can sense leucine and glycine, respectively. We show that these biosensors can selectively and sensitively detect their targets over a wide range of concentrations-up to 7 orders of magnitude-and that the selectivity of these sensors can be readily altered by switching the bioreceptor's binding domain. Our work represents a new paradigm for the design of a family of modular electrochemical biosensors, where access to electrode surfaces can be controlled by protein conformational changes.

Polypyrrole Percolation Network Gas Sensors: Improved Reproducibility through Conductance Monitoring during Polymer Growth.

Conducting-polymer-based electrical percolation networks are promising materials for use in high-sensitivity chemiresistive devices. An ongoing challenge is to create percolation networks that have consistent properties, so that devices based on these materials do not have to be individually calibrated. Here, an in situ conductance technique is used during the electrochemical growth of polypyrrole (PPy) percolation networks. The drain current (i d) across the interdigitated electrodes (IDEs) is a measure of the conductance of the PPy network during electrochemical polymerization. The i d curve is used to determine the percolation region. To improve the reproducibility of PPy percolation networks, an in situ conductance monitoring method based on the value of i d is used. A set of optimal ammonia gas percolation sensors was created using this method with an average sensitivity of ΔR/R 0 × 100% ppm-1 = 11.3 ± 1.2% ppm-1 and an average limit of detection of 15.0 ± 3.6 ppb.

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

BACKGROUND: Portable 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 METHODS: To 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. RESULTS: Participants 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. CONCLUSIONS: Breath 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.

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.

PEDOT percolation networks for reversible chemiresistive sensing of NO2.

Detection of NO2 plays an important role in various safety applications. However, sensitive and reversible sensing of NO2 remains a challenge. Here we demonstrate the use of poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer percolation networks for chemiresistive sensing of NO2. By adjusting the electrochemical polymerisation and doping conditions of the polymer, we show control over the relative contributions of oxidised and over-oxidised PEDOT to the sensing behaviour. Reversible NO2 sensors using only PEDOT as the sensor material are demonstrated. By operating the sensor near the electrical percolation threshold, a higher sensitivity is achieved compared to more traditional thin film based chemiresistive sensors. A limit of detection of 907 ± 102 ppb was achieved.