Development of a compact, IoT-enabled electronic nose for breath analysis

In this paper, we report on an in-house developed electronic nose (E-nose) for use with breath analysis. The unit consists of an array of 10 micro-electro-mechanical systems (MEMS) metal oxide (MOX) gas sensors produced by seven manufacturers. Breath sampling of end-tidal breath is achieved using a heated sample tube, capable of monitoring sampling-related parameters, such as carbon dioxide (CO2), humidity, and temperature. A simple mobile app was developed to receive real-time data from the device, using Wi-Fi communication. The system has been tested using chemical standards and exhaled breath samples from healthy volunteers, before and after taking a peppermint capsule. Results from chemical testing indicate that we can separate chemical standards (acetone, isopropanol and 1-propanol) and different concentrations of isobutylene. The analysis of exhaled breath samples demonstrate that we can distinguish between pre- and post-consumption of peppermint capsules; area under the curve (AUC): 0.81, sensitivity: 0.83 (0.59–0.96), specificity: 0.72 (0.47–0.90), p-value: <0.001. The functionality of the developed device has been demonstrated with the testing of chemical standards and a simplified breath study using peppermint capsules. It is our intention to deploy this system in a UK hospital in an upcoming breath research study

Dynamic operation, efficient calibration, and advanced data analysis of gas sensors : from modelling to real-world operation

This thesis demonstrates the use of dynamic operation, efficient calibration and advanced data analysis using metal oxide semiconductor (MOS) gas sensors as an example – from modeling to real-world operation. The necessary steps for an applicationspecific, selective indoor volatile organic compound (VOC) measurement system are addressed, analyzed and improved. Factors such as sensors, operation, electronics and calibration are considered. The developed methods and tools are universally transferable to other gas sensors and applications. The basis for selective measurement is temperature cyclic operation (TCO). The model-based understanding of a semiconductor gas sensor in TCO for the optimized development of operating modes and data evaluation is addressed and, for example, the tailored and stable detection of short gas pulses is developed. Two successful interlaboratory tests for the measurement of VOCs in independent laboratories are described. Selective measurements of VOCs in the laboratory and in the field are successfully demonstrated. Calibrations using the proposed techniques of randomized design of experiment (DoE), model-based data evaluation and calibration with machine learning methods are employed. The calibrated models are compared with analytical measurements using release tests. The high agreement of the results is unique in current research.Diese Thesis zeigt den Einsatz von dynamischem Betrieb, effizienter Kalibrierung, und fortschrittlicher Datenanalyse am Beispiel von Metalloxid Halbleiter (MOS) Gassensoren – von der Modellierung bis zum realen Betrieb. Die notwendigen Schritte für ein anwendungsspezifisches, selektives Messystem für flüchtige organische Verbindungen (VOC) im Innenraum werden adressiert, analysiert und verbessert. Faktoren wie z.B. Sensoren, Funktionsweise, Elektronik und Kalibrierung werden berücksichtigt. Die entwickelten Methoden und Tools sind universell auf andere Gassensoren und Anwendungen übertragbar. Grundlage für die selektive Messung ist der temperaturzyklische Betrieb (TCO). Auf das modellbasierte Verständnis eines Halbleitergassensors im TCO für die optimierte Entwicklung von Betriebsmodi und Datenauswertung wird eingegangen und z.B. die maßgeschneiderte und stabile Detektion von kurzen Gaspulsen entwickelt. Zwei erfolgreiche Ringversuche zur Messung von VOCs in unabhängigen Laboren werden beschrieben. Selektive Messungen verschiedener VOCs im Labor und im Feld werden erfolgreich demonstriert. Dabei kommen Kalibrierungen mit den vorgeschlagenen Techniken des randomisierten Design of Experiment (DoE), der modellbasierten Datenauswertung und Kalibrierung mit Methoden des maschinellen Lernens zum Einsatz. Die kalibrierten Modelle werden anhand von Freisetzungstests mit analytischen Messungen verglichen. Die hohe Übereinstimmung der Ergebnisse ist einzigartig in der aktuellen Forschung

Temperature programmed reductions and oxidations on cupric oxide: parametric sensitivity and investigations on thermal effects

In this thesis work, the Temperature Programmed Reduction (TPR) and Temperature Programmed Oxidation (TPO) techniques have been used to determine the cyclic reactivity of cupric oxide, based on the peak shape analysis and the total oxygen removed during reduction and regained during the oxidation processes.ope

Facile Quantification and Identification Techniques for Reducing Gases over a Wide Concentration Range Using a MOS Sensor in Temperature-Cycled Operation

Dedicated methods for quantification and identification of reducing gases based on model-based temperature-cycled operation (TCO) using a single commercial MOS gas sensor are presented. During high temperature phases the sensor surface is highly oxidized, yielding a significant sensitivity increase after switching to lower temperatures (differential surface reduction, DSR). For low concentrations, the slope of the logarithmic conductance during this low-temperature phase is evaluated and can directly be used for quantification. For higher concentrations, the time constant for reaching a stable conductance during the same low-temperature phase is evaluated. Both signals represent the reaction rate of the reducing gas on the strongly oxidized surface at this low temperature and provide a linear calibration curve, which is exceptional for MOS sensors. By determining these reaction rates on different low-temperature plateaus and applying pattern recognition, the resulting footprint can be used for identification of different gases. All methods are tested over a wide concentration range from 10 ppb to 100 ppm (4 orders of magnitude) for four different reducing gases (CO, H2, ammonia and benzene) using randomized gas exposures

Dynamic neural network architectures for on field stochastic calibration of indicative low cost air quality sensing systems

In the last few years, the interest in the development of new pervasive or mobile implementations of air quality multisensor devices has significantly grown. New application opportunities appeared together with new challenges due to limitations in dealing with rapid pollutants concentrations transients both for static and mobile deployments. In this work, we propose a Dynamic Neural Network (DNN) approach to the stochastic prediction of air pollutants concentrations by means of chemical multisensor devices. DNN architectures have been devised and tested in order to tackle the cross sensitivities issues and sensors inherent dynamic limitations. Testing have been performed using an on-field recorded dataset from a pervasive deployment in Cambridge (UK), encompassing several weeks. The results obtained with the dynamic model are compared with the response of the static neural network and the performance analysis indicates the capability of the on-field dynamic multivariate calibration to ameliorate the static calibration approach performance in this real world air quality monitoring scenario. Interestingly, results analysis also suggests that the improvements are more significant when pollutants concentration changes more rapidly.This work has been supported by an STSM (Short Term Scientific Mission) grant from COST Action TD1105 EuNetAir

Improving the performance of gas sensor systems with advanced data evaluation, operation, and calibration methods

In order to facilitate the widespread use of gas sensors, some challenges must still be overcome. Many of those are related to the reliable quantification of ultra-low concentrations of specific compounds in a background of other gases. This thesis focuses on three important items in the measurement chain: sensor material and operating modes, evaluation of the resulting data, and test gas generation for efficient sensor calibration. New operating modes and materials for gas-sensitive field-effect transistors have been investigated. Tungsten trioxide as gate oxide can improve the selectivity to hazardous volatile organic compounds like naphthalene even in a strong and variable ethanol background. The influence of gate bias and ultraviolet light has been studied with respect to the transport of oxygen anions on the sensor surface and was used to improve classification and quantification of different gases. DAV3E, an internationally recognized MATLAB-based toolbox for the evaluation of cyclic sensor data, has been developed and published as opensource. It provides a user-friendly graphical interface and specially tailored algorithms from multivariate statistics. The laboratory tests conducted during this project have been extended with an interlaboratory study and a field test, both yielding valuable insights for future, more complex sensor calibration. A novel, efficient calibration approach has been proposed and evaluated with ten different gas sensor systems.Vor der weitverbreiteten Nutzung von Gassensoren stehen noch einige Herausforderungen, insbesondere die zuverlässige Messung ultrakleiner Konzentrationen bestimmter Substanzen vor einem Hintergrund anderer Gase. Diese Arbeit konzentriert sich auf drei wichtige Glieder der erforderlichen Messkette: Material und Betriebsweise von Sensoren, Auswertung der anfallenden Daten sowie Generierung von Testgasen zur effizienten Kalibrierung. Neue Betriebsmodi und Materialien für gassensitive Feldeffekttransistoren wurden getestet. Wolframtrioxid kann als Gateoxid die Selektivität für flüchtige organische Verbindungen wie Naphthalin in einem variierenden Ethanolhintergrund verbessern. Der Einfluss von Gate-Bias und ultravioletter Strahlung auf die Bewegung von Sauerstoffionen auf der Oberfläche wurde untersucht und genutzt, um die Klassifizierung und Quantifizierung von Gasen zu verbessern. Eine international anerkannte MATLAB-Toolbox zur Auswertung zyklischer Sensordaten, DAV3E, wurde entwickelt und als open source veröffentlicht. Sie stellt eine nutzerfreundliche Oberfläche und speziell angepasste Algorithmen der multivariaten Statistik zur Verfügung. Die Laborexperimente wurden ergänzt durch vergleichende Messungen in zwei unabhängigen Laboren und einen Feldtest, womit wertvolle Erkenntnisse für die künftig notwendige, komplexe Kalibrierung von Sensoren gewonnen wurden. Ein neuartiger, effizienter Kalibrieransatz wurde vorgestellt und mit zehn unterschiedlichen Sensorsystemen evaluiert

Identifying origin of response in SnO2-based gas sensors via in operando NAP XPS with simultaneous resistance measurements

Conductometric gas sensors (CGS) are small, portable, easily mass-produced and provide a reproducible gas response at a low cost. However, they suffer from relatively poor detection characteristics, which stem from an insufficient understanding of their operating mechanism. This study aimed to develop a robust method for investigating gas sensors to provide insight into the atomistic interactions between the sensitive layer and the gas phase by means of the recently emerging technique of near-ambient pressure X-ray photoelectron spectroscopy (NAP XPS) using laboratory-based and synchrotron-based X-ray sources. Spectroscopic analysis with simultaneous resistance measurements was carried out on working sensors under temperature and pressure conditions close to their typical operating environment to produce a joint micro- and macroscopic picture of their operation, a hallmark of operando spectroscopy. The initial study of the interactions between SnO2, a prototype sensitive material, and O2, a ubiquitous gas central to the detection mechanisms of CGS, was extended to include interactions with CO and NO2 as examples of reducing and oxidising gases. The results of this study point to the importance of near-surface oxygen vacancies in the detection mechanisms governing the response of SnO2-based gas sensors and suggest that models based on variable surface vacancy density should be developed in place of the currently dominating ‘oxygen ionosorption’ description, for which there is no direct, convincing evidence despite decades of extensive research

Design and Application of Task-Specific Organic Salts for Chemical and Biochemical Sensing

There is an increasing demand for development of new sensors and sensor strategies for accurate detection and discrimination of various analytes. In this regard, colorimetric and fluorometric sensor approaches have attracted considerable attention, primarily because they represent facile and inexpensive analytical tools. In this dissertation, I discuss the design and application of sensors and sensor arrays using task specific organic salts: ionic liquids (ILs) and a group of uniform materials based on organic salts (GUMBOS). As compared to typical ionic compounds, these two classes of organic salts exhibit relatively lower melting points due to bulky organic cations and/or anions. Interestingly, the physicochemical properties of these compounds can be easily tuned by altering either the cation or the anion. Furthermore, the respective ions of ILs and GUMBOS can be independently tailored in order to obtain specific functionalities. The first part of this dissertation provides a general discussion on ILs and GUMBOS. In addition, the principle and application of sensors and sensor arrays are discussed. The second part of this dissertation is primarily focused on four different studies, which involve design and application of task-specific organic salts for chemical and biochemical sensing. All four of these studies, which appear in Chapters 2-5, report on novel sensor or sensor array approaches with distinct advantages for analytical measurements