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This research presents two laser-based photoacoustic approaches for analyzing exhaled breath isoprene and acetone. The integration of a PTR-ToF-MS as a reference device ensured the reliability and accuracy of the PAS systems that is based on an ICL for isoprene and a QCL for acetone detection. The calibration yielded limits of detection of 26.9 ppbV and 1.7 ppbV, respectively, and corresponding normalized noise equivalent absorption coefficients (NNEAs) of 5.0E-9 Wcm-1Hz-0.5 and 4.9E-9 Wcm-1Hz-0.5. Laboratory as well as real breath sample measurements from alveolar breath revealed a robust system performance, with only one outlier within the static isoprene measurements. However, discrepancies emerged under dynamic breath sampling conditions, emphasizing the need for further optimization. Especially by knowing the dynamic nature and endogenous origin of exhaled isoprene our findings highlight the potential of breath analysis for non-invasive physio-metabolic and pathophysiological monitoring towards point-of-care devices.
An inexpensive UV-LED photoacoustic based real-time sensor-system detecting exhaled trace-acetone
(2024)
n this research we present a low-cost system for breath acetone analysis based on UV-LED photoacoustic spectroscopy. We considered the end-tidal phase of exhalation, which represents the systemic concentrations of volatile organic compounds (VOCs) – providing clinically relevant information about the human health. This is achieved via the development of a CO2-triggered breath sampling system, which collected alveolar breath over several minutes in sterile and inert containers. A real-time mass spectrometer is coupled to serve as a reference device for calibration measurements and subsequent breath analysis. The new sensor system provided a 3σ detection limit of 8.3 ppbV and an NNEA of 1.4E-9 Wcm 1Hz 0.5. In terms of the performed breath analysis measurements, 12 out of 13 fell within the error margin of the photoacoustic measurement system, demonstrating the reliability of the measurements in the field.
An Inexpensive Uv-Led Photoacoustic Based Real-Time Sensor-System Detecting Exhaled Trace-Acetone
(2024)
In this research we present a low-cost system for breath acetone analysis based on UV-LED photoacoustic spectroscopy. We considered the end-tidal phase of exhalation, which represents the systemic concentrations of volatile organic compounds (VOCs) – providing clinically relevant information about the human health. This is achieved via the development of a CO2-triggered breath sampling system, which collected alveolar breath over several minutes in sterile and inert containers. A real-time mass spectrometer is coupled to serve as a reference device for calibration measurements and subsequent breath analysis. The new sensor system provided a 3σ detection limit of 6.4 ppbV and an NNEA of 1.1E-9 Wcm-1Hz-0.5. In terms of the performed breath analysis measurements, 12 out of 13 fell within the error margin of the photoacoustic measurement system, demonstrating the reliability of the measurements in the field.
In process analytics or environmental monitoring, the real-time recording of the composition of complex samples over a long period of time presents a great challenge. Promising solutions are label-free techniques such as surface plasmon resonance (SPR) spectroscopy. They are, however, often limited due to poor reversibility of analyte binding. In this work, we introduce how SPR imaging in combination with a semi-selective functional surface and smart data analysis can identify small and chemically similar molecules. Our sensor uses individual functional spots made from different ratios of graphene oxide and reduced graphene oxide, which generate a unique signal pattern depending on the analyte due to different binding affinities. These patterns allow four purine bases to be distinguished after classification using a convolutional neural network (CNN) at concentrations as low as 50 μM. The validation and test set classification accuracies were constant across multiple measurements on multiple sensors using a standard CNN, which promises to serve as a future method for developing online sensors in complex mixtures.
Artificial neural networks (ANNs) are used in quantitative infrared gas spectroscopy to predict concentrations on multi-component absorption spectra. Training of ANNs requires vast amounts of labelled training data which may be elaborate and time consuming to obtain. Additional data can be gained by the utilization of synthetically generated spectra, but at the cost of systematic deviations to measured data. Here, we present two approaches to train ANNs with a combination of comparatively small, measured data sets and synthetically generated data. For the first approach a neural network is trained hybridly with synthetically generated infrared absorption spectra of mixtures of N2O and CO and measured zero-gas spectra, taken with a mid-infrared dual comb spectrometer. This improves the mean absolute error (MAE) of the network predictions from 0.46 to 0.01 ppmV and 0.24 to 0.01 ppmV for the concentration predictions of N2O and CO respectively for zero-gas measurements which was previously observed for training with purely synthetic data. At the same time a similar performance on spectra from gas mixtures of 0–100 ppmV N2O and 0 to 60 ppmV CO was achieved. For the second approach an ANN pre-trained on synthetic infrared spectra of mixtures of acetone and ethanol is retrained on a small dataset consisting of 26 spectra taken with a mid-infrared photoacoustic spectrometer. In this case the MAE for the concentration predictions of ethanol and acetone are improved by 45 % and 20 % in comparison to purely synthetic training. This shows the capability of using synthetically generated data to train ANNs in combination with small amounts of measured data to further improve neural networks for gas sensing and the transferability between different sensing approaches.
Osteoporosis is a common disease of old age. However, in many cases, it can be very well prevented and counteracted with physical activity, especially high-impact exercises. Wearables have the potential to provide data that can help with continuous monitoring of patients during therapy phases or preventive exercise programs in everyday life. This study aimed to determine the accuracy and reliability of measured acceleration data at different body positions compared to accelerations at the pelvis during different jumping exercises. Accelerations at the hips have been investigated in previous studies with regard to osteoporosis prevention. Data were collected using an IMU-based motion capture system (Xsens) consisting of 17 sensors. Forty-nine subjects were included in this study. The analysis shows the correlation between impacts and the corresponding drop height, which are dependent on the respective exercise. Very high correlations (0.83–0.94) were found between accelerations at the pelvis and the other measured segments at the upper body. The foot sensors provided very weak correlations (0.20–0.27). Accelerations measured at the pelvis during jumping exercises can be tracked very well on the upper body and upper extremities, including locations where smart devices are typically worn, which gives possibilities for remote and continuous monitoring of programs.
To decrease the number of kilometers driven during the development of autonomous cars or driving assistance systems, performant simulation tools are necessary. Currently, domain distance effects between simulation and reality are limiting the successful application of rendering engines in data-driven perception tasks. In order to mitigate those domain distance effects, simulation tools have to be as close to reality as possible for the given task. For optical sensors like cameras, the luminance of the scene is essential. We provide within this paper a method to measure the luminance of rendered scenes within CARLA, an often used open-source simulation environment. Thereby, it is possible to validate the environment and weather models by taking real-world measurements with photometric sensors or with the help of open-source weather data, published e.g. by the German federal service for weather data (DWD - "Deutscher Wetterdienst"). Employing our proposed luminance measurement, the domain gap resulting from the simulation can be specified, which makes it possible to evaluate the statements about the safety of the automated driving system determined within the simulation. We show that the ratio between global and diffuse radiation modeled by the default atmosphere models within CARLA are under limited conditions similar to real-world measurements taken by the DWD. Nevertheless, we show, that the ratio’s temporal variability in real-world situations is not modeled by CARLA.
With an atmospheric concentration of approximately 2000 parts per billion (ppbV, 10−9) methane (CH4) is the second most abundant greenhouse gas (GHG) in the atmosphere after carbon dioxide (CO2). The task of long-term and spatially resolved GHG monitoring to verify whether climate policy actions are effective, is becoming more crucial as climate change progresses. In this paper we report the CH4 concentration readings of our photoacoustic (PA) sensor over a five day period at Hohenpeißenberg, Germany. As a reference device a calibrated cavity ringdown spectrometer Picarro G2301 from the meteorological observatory was employed. Trace gas measurements with photoacoustic instruments promise to provide low detection limits at comparably low costs. However, PA devices are often susceptible to cross-sensitivities related to environmental influences. The obtained results show that relaxation effects due to fluctuating environmental conditions, e.g. ambient humidity, are a non-negligible factor in PA sensor systems. Applying algorithm compensation techniques, which are capable of calculating the influence of relaxational effects on the photoacoustic signal, increase the accuracy of the photoacoustic sensor significantly. With an average relative deviation of 1.11 % from the G2301, the photoacoustic sensor shows good agreement with the reference instrument.
A comparative analysis of two different approaches developed to deal with molecular relaxation in photoacoustic spectroscopy is here reported. The first method employs a statistical analysis based on partial least squares regression, while the second method relies on the development of a digital twin of the photoacoustic sensor based on the theoretical modelling of the occurring relaxations. Methane detection within a gas matrix of synthetic air with variable humidity level is selected as case study. An interband cascade laser emitting at 3.345 µm is used to target methane absorption features. Two methane concentration ranges are explored targeting different absorptions, one in the order of part-per-million and one in the order of percent, while water vapor absolute concentration was varied from 0.3 % up to 2 %. The results achieved employing the detection techniques demonstrated the possibility to efficiently retrieve the target gas concentrations with accuracy > 95 % even in the case of strong influence of relaxation effects.
Trace gas analysis in breath is challenging due to the vast number of different components. We present a highly sensitive quantum cascade laser based photoacoustic setup for breath analysis. Scanning the range between 8263 and 8270 nm with a spectral resolution of 48 pm, we are able to quantify acetone and ethanol within a typical breath matrix containing water and CO2. We photoacoustically acquired spectra within this region of mid-infra-red light and prove that those spectra do not suffer from non-spectral interferences. The purely additive behavior of a breath sample spectrum was verified by comparing it with the independently acquired single component spectra using Pearson and Spearman correlation coefficients. A previously presented simulation approach is improved and an error attribution study is presented. With a 3σ detection limit of 6.5 ppbv in terms of ethanol and 250 pptv regarding acetone, our system is among the best performing presented so far.
With an atmospheric concentration of approximately 2000 parts per billion (ppbV, 10−9), methane (CH4) is the second most abundant greenhouse gas (GHG) in the atmosphere after carbon dioxide (CO2). The task of long-term and spatially resolved GHG monitoring to verify whether climate policy actions are effective is becoming more crucial as climate change progresses. In this paper we report the CH4 concentration readings of our photoacoustic (PA) sensor over a 5 d period at Hohenpeißenberg, Germany. As a reference device, a calibrated cavity ring-down spectrometer, Picarro G2301, from the meteorological observatory of the German Weather Service (DWD) was employed. Trace gas measurements with photoacoustic instruments promise to provide low detection limits at comparably low costs. However, PA devices are often susceptible to cross-sensitivities related to fluctuating environmental conditions, e.g. ambient humidity. The obtained results show that for PA sensor systems non-radiative relaxation effects induced by varying humidity are a non-negligible factor. Applying algorithm compensation techniques, which are capable of calculating the influence of non-radiative relaxation effects on the photoacoustic signal, increase the accuracy of the photoacoustic sensor significantly. With an average relative deviation of 1.11 % from the G2301, the photoacoustic sensor shows good agreement with the reference instrument.
Reliable and fast detection of pest in the food processing and pharmaceutical industry is crucial to ensure hygienically safe, pure and healthy products. This is why intelligent traps, that are able to detect insects automatically are needed.
For this, a capacitive PCB sensor is developed and tested, which could be a simplistic, low power solution to the problem. This includes design, footprint generation and simulation as well as testing different types of capacitve sensing against noise immunity and sensitivity to Blattella germanica, the German cockroach. It is shown that a single specimen can very well and reliably be detected by the developed sensor.
We present a sensitive and compact interband cascade laser (ICL) based photoacoustic setup for the detection of gaseous hydrocarbons and discuss its applicability towards trace gas analysis. We investigated the performance of the sensor for trace concentrations of methane, ethane and acetylene diluted in nitrogen. The excitation of methane and ethane was accomplished using one tunable diode laser, covering a range from 3360 to 3372 nm, which was replaced by a separate ICL at 3025 nm for acetylene detection. The influence of ambient parameters such as temperature, flow rate and pressure as well as potential cross-sensitivities towards O2 and H2O have been examined in terms of methane and acetylene detection. A series of simulations proved several of these influences to be attributed to relaxation effects. With a 3σ limit of detection (LoD) of 6.8 parts per billion (ppbV) in case of methane, 2.3 ppbV regarding ethane and 3.6 ppbV in terms of acetylene, the sensor demonstrates a great potential for applications in the field of trace gas analysis.
Successful transfer of photoacoustic gas sensors from laboratory to real-life applications requires knowledge about potential cross-sensitivities towards environmental and gas matrix changes. Multi-dimensional calibration in case of cross-sensitivities can become very complex or even unfeasible. To address this challenge, we present a novel algorithm to compute the collision based non-radiative efficiency and phase lag of energy relaxation on a molecular level (CoNRad) for photoacoustic signal calculation. This algorithmic approach allows to calculate the entire elaxation cascade of arbitrarily complex systems, yielding a theoretical photoacoustic signal. In this work the influence of varying bulk compositions, i.e. nitrogen (N2), oxygen (O2) and water (H2O) on the photoacoustic signal during methane (CH4) detection is demonstrated. The applicability of the algorithm to other photoacoustic setups is shown exemplary by applying it to the relaxational system investigated in [1]. Hayden et al. examined the effect of water on photoacoustic carbon monoxide (CO) detection.
A Deep Learning System to Transform Cross-Section Spectra to Varying Environmental Conditions
(2022)
Absorption cross-sections provide a basis for many gas sensing applications. Therefore, any error in molecular cross-sections caused by varying environmental conditions propagates to spectroscopic applications. Original molecular cross-sections in varying environmental conditions can only be simulated for some molecules, whereas for most multi-atom molecules, one must rely on high-precision measurements at certain environmental configurations. In this study, a deep learning system trained with simulated absorption cross-sections for predicting cross-sections at a different pressure configuration is presented. The system’s capability to transfer to measured, multi-atom cross-sections is demonstrated. Thus, it provides an alternative to (pseudo-) line lists whenever the required information for simulation is unavailable. The predictive performance of the system was evaluated on validation data via simulation, and its transfer learning capabilities were demonstrated on actual measurement chlorine nitrate data. From the comparison between the system and line lists, the system shows slightly worse performance than pseudo-line lists but its predictive quality is still deemed acceptable with less than 5% relative integral change with a highly localized error around the peak center. This opens a promising way for further research to use deep learning to simulate the effect of varying environmental conditions on absorption cross-sections.
Creating a Digital Twin of a Photoacoustic Gas Sensor for Methane Detection in Complex Gas Matrices
(2022)
We present the calculation results from a digital twin (DT) of our photoacoustic (PA) sensor for methane detection, regarding gas composition, temperature and pressure variations.
Stickstoffdioxid (NO2) wird hauptsächlich durch anthropogene Verbrennungsprozesse in Verkehr und Industrie in die Umgebungsluft eingebracht [1]. Die stark reaktive, oxidative Wirkung von NO2 kann bei Exposition mit höheren Konzentrationen Reizungen und allergische Reaktionen in den Atemwegen hervorrufen. Weiter führt NO2 zur Bildung von saurem Regen, Smog und Ozon (O3) die sich ebenso negativ auf die menschliche Gesundheit und Umwelt auswirken [2,3]. Aufgrund dieser Effekte wird die Spurengaskonzentration von NO2 in der Luft in Deutschland an ausgewählten, verkehrsreichen Orten gemessen.
Trace gas analysis in breath is challenging due to the vast number of different components. We present a highly sensitive quantum cascade laser based photoacoustic setup for breath analysis. Scanning the range between 8260 and 8270 nm with a spectral resolution of 48 pm, we are able to quantify acetone and ethanol within a typical breath matrix containing water and CO2. We photoacoustically acquired spectra within this region of mid-infra-red light and prove that those spectra do not suffer from non-spectral interferences. The purely additive behavior of a breath sample spectrum was verified by comparing it with the independently acquired single component spectra using Pearson and Spearman correlation coefficients. A previously presented simulation approach is improved and an error attribution study is presented. With a 3σ detection limit of 6.5 ppbV in terms of ethanol and 250 pptV regarding acetone, our system is among the best performing presented so far.
Miniaturisierte Sensoren basierend auf Oberflächenplasmonenresonanz, Chancen und Herausforderungen
(2021)
Derzeit gibt es zahlreiche Bereiche, wie Umwelt Monitoring und zivile Infrastruktur in denen geeignete Sensoren für die Überwachung der Systeme fehlen. SPR-basierte Sensoren haben das Potential diese Lücke zu schließen. Um für den Einsatz in der Umwelt tauglich zu werden, müssen die Sensoren noch robuster werden. Hier wird eine mögliche Lösung gezeigt.
The increasing popularity of nanoparticles in many applications has led to the fact that these persistent materials pollute our environment and threaten our health. An online sensor system for monitoring the presence of nanoparticles in fresh water would be highly desired. We propose a label-free sensor based on SPR imaging. The sensitivity was enhanced by a factor of about 100 by improving the detector by using a high-resolution camera. This revealed that the light source also needed to be improved by using LED excitation instead of a laser light source. As a receptor, different self-assembled monolayers have been screened. It can be seen that the nanoparticle receptor interaction is of a complex nature. The best system when taking sensitivity as well as reversibility into account is given by a dodecanethiol monolayer on the gold sensor surface. Lanthanide-doped nanoparticles, 29 nm in diameter and with a similar refractive index to the most common silica nanoparticles were detected in water down to 1.5 mu g mL(-1). The sensor can be fully regenerated within one hour without the need for any washing buffer. This sensing concept is expected to be easily adapted for the detection of nanoparticles of different size, shape, and composition, and upon miniaturization, suitable for long-term applications to monitor the quality of water.
We present a sensitive UV LED photoacoustic setup for the detection of gaseous acetone and discuss its applicability towards breath analysis. We investigated the performance of the sensor for low acetone concentrations down to 0.1 parts per million (ppmV). The influences of temperature, flow, pressure, optical power and LED duty cycle on the measured signal have been examined. To gain a better understanding of the different effects on the photoacoustic signal, correlation analysis was applied and feature importance was determined using a large measured dataset. Furthermore, the cross-sensitivities towards O2, CO2 and H2O have been studied extensively. Finally, the sensor’s performance to detect acetone between 0.1–1 ppmV within gas mixtures simulating breath exhale conditions has been investigated, too. With a limit of detection (LoD) of 12.5 parts per billion (ppbV) (3σ) measured under typical breath exhale gas mixture conditions, the sensor demonstrated a high potential for the application of acetone detection in human breath analysis.
The performance of a photoacoustic trace gas sensor for the detection of acetone in N2 and synthetic air is reported. The sensor system utilises an amplitude modulated UV LED. The light source has an emission maximum at 278 nm and a maximum CW output power of 300 mW according to the datasheet. Three different collimating and focusing approaches have been investigated to guide the highly divergent LED light into the acoustic resonator of the photoacoustic measurement cell. A 3D printed aluminium cell was designed to optimize light coupling by simultaneously minimizing the photoacoustic background signal generation. Hence, the diameter of the resonator was set to a comparable large diameter of 10 mm and the inner walls of the resonator were mirror polished. The additive manufacturing procedure allowed for integration of a spirally formed gas channel, enabling gas heating prior to detection. The sensor performance was investigated by measuring acetone in N2 and synthetic air at different concentrations. The UV LED current was set to 86 % of the maximum value according to the datasheet of the light source in order to increase the lifetime and thermal stability. An Allan-Werle deviation analysis validates a stable sensor performance. The limit of detection (LoD) was determined at a 3σ noise level with a 10 s lock-in amplifier time constant by sampling data points over 20 s with a data acquisition rate of 5 Hz. LoDs of 80.8 ppbV and 19.6 ppbV were obtained for acetone in N2 and synthetic air, respectively.
We describe how to build a homogeneous light source for Surface Plasmon Resonance Imaging (SPRi) which mainly finds its applications in pharmaceutical screening and biotechnology so far. SPR spectroscopy is a label-free, non-destructive and highly sensitive measurement principle for detecting changes in the refractive index in close vicinity of a gold surface. A transfer of this technology to a miniaturized sensor will broaden the range of possible applications. Commercial SPR assays are mainly working with a small number of sensing spots. In contrast, the SPR imaging system shown here will allow the use of an array of many sensing spots. In combination with chemical receptors designed as an artificial nose or an electronic tongue, the simultaneous detection of many analytes is envisioned. So far, lasers or other inhomogeneous light sources were used to illuminate the sensing surface, which is decreasing the systems sensitivity. We show a compact ( 300mm2) homogeneous top hat profile. The combination of a high bit-resolution camera with our new light source enables a reflectivity based surface plasmon resonance imaging system with a high refractive index unit (RIU) resolution.
Surface Plasmon Resonance (SPR) is a well-known and established technology in bioanalysis and pharmaceutical sciences. Due to the expensive instrumentation and the need of trained people, it is mainly limited to applications in laboratories. However, there are some areas like environmental monitoring, chemical processing and civil infrastructure, which urgently need new sensor technologies. SPR has the potential to serve these fields. In order to be qualified for a use in these areas SPR has to overcome some hurdles. The instrumentation has to be robust, small in size and cheap. A device, which fits these needs, will be a micro-opto-electro-mechanical system (MOEMS) with integrated intelligent algorithms. In this book chapter, examples of miniaturized SPR devices are introduced, the limitations which have to be overcome as well as the possibilities for future applications are proposed. Due to the manifold advantages of this technology and the dropping prices for imaging sensors, Surface Plasmon Resonance imaging (SPRi) might become one of the leading technologies for SPR smart sensor systems.
The analysis of surface water, groundwater, drinking water as well as sewage is important to get information about the contamination of the water cycle. Currently, these time-consuming investigations require special equipment, like for example hyphenated mass spectrometry. Surface plasmon resonance (SPR) is a faster alternative as it is highly sensitive to changes in the dielectric medium next to a thin metal layer and makes it a quasi-universal detector. Therefore, and due to the labelfree nature, SPR is a widely used sensing tool for real‐time monitoring of molecular interactions of various analytes. SPR imaging (SPRi) has several advantages to standard surface plasmon resonance, as it allows to observe many analytes in parallel as well as the integration of referencing technologies. However, the homogenous illumination of a large area (several millimeters) with a small light source is challenging and demands new approaches. Allopurinol, a drug used to lower the blood concentration of urate and hence decrease the affection of gout, gets metabolized to oxipurinol in the body and dropped out almost entirely by urinary excretion. After wastewater treatment, concentrations of oxipurinol up to 21.7 μg•L-1 are detected. Further tracking of oxipurinol in the urban water cycle showed its presence in rivers and streams or even in groundwater. Therefore, the high biological stability of oxipurinol allows this molecule to be used as a marker for domestic wastewater in the environment. For the detection of oxipurinol by SPR graphene was used as receptive layer, as the analyte can bind via π-stacking to this surface. An SPRi technique was developed and compared to conventional SPR system for the detection of oxipurinol.
Confidence in results of an Artificial Neural Networks (ANNs) is increased by preferring to reject data, that is not trustful, instead of risking a misclassification. For this purpose a model is proposed that is able to recognize data, which differs significantly from the training data, during inference. The proposed model observes all activations of the hidden layers, as well as input and output layers of an ANN in a grey-box view. To make ANNs more robust in safety critical applications, this model can be used to reject flawed data, that is suspected to decrease the accuracy of the model. If this information is logged during inference, it can be used to improve the model, by training it specifically with the missing information. An experiment on the MNIST dataset is conducted and its results are discussed.
Atemgasanalyse ist ein junges und vielversprechendes Feld im Bereich der diagnostischen Medizin. Der Ansatz verspricht einfach zugängliche und leicht wiederholbare Probennahme die zum einen non-invasiv ist und zugleich Rückschlüsse auf Vorgänge im menschlichen Körper und bspw. dessen Gesundheitszustand zulässt. Seit Ende des 20. Jahrhunderts gibt es Massenspektrometer die es ermöglicht haben mehrere Tausend verschiedene Stoffe in der Ausatemluft nachzuweisen. Diese Technologien verbessern sich stetig und ermöglichen es die Vorgänge und Zusammenhänge zwischen Zusammensetzung der Ausatemluft und systemischen Prozessen besser zu verstehen. Die bei Studien mit Massenspektrometern ermittelten Biomarker, deren qualitative und quantitative Detektion Gesundheitsdiagnosen ermöglichen, haben aber noch nicht den Weg in den klinischen Alltag gefunden. Das Problem sind meistens die hohen Anschaffungskosten, komplizierte Datenauswertung und zumeist geringe Verfügbarkeit und Immobilität dieser Messgeräte. Die photoakustische Spektroskopie ist eine selektive und hochsensitive Messmethode, die es ermöglichen soll den Biomarker „Aceton“, der grundsätzlich die Metabolisierung von Fetten widerspiegelt, schnell und reproduzierbar quantitativ zu detektieren. Dabei müssen Hindernisse wie Querempfindlichkeiten, ausgelöst durch die komplexe Zusammensetzung der Messmatrix Atemgas, bei gleichzeitig kleine Aceton Konzentrationen (200-800 parts-per-billion) überwunden werden. Verschiedene Wellenlängenbereiche mit unterschiedlichen Lichtquellen, akustisch resonante sowie innovative Messzellendesigns und anspruchsvolle Datenauswertung mittels komplexer Algorithmik sind nötig um das Ziel, die Entwicklung eines kompakten, günstigen und zuverlässigen Acetonsensors, zu erreichen.
We describe the miniaturization of the Surface Plasmon Resonance (SPR) technology which mainly finds its applications in pharmaceutical screening and biotechnology so far. SPR spectroscopy is a label-free, non-destructive and highly sensitive measurement principle detecting changes in the refractive index in striking distance to a gold surface. A transfer of this technology to a miniaturized sensor will broaden the range of possible applications. A promising feature which is included in the miniaturized system is the angle-dependent recording of the SPR signals without moving parts. Commercial SPR assays are mainly working with a small number of sensing spots. In contrast, the SPR imaging system shown here will allow to use an array of many sensing spots. In combination with chemical receptors designed as an artificial nose, the simultaneous detection of many analytes is envisioned for future applications.
We present the development and characterization as well as comprehensive interference studies of a photoacoustic NO2 trace gas detection system. The system is based on an off-beam quartz enhanced photoacoustic scheme (off-beam QEPAS) and signal generation was initiated by amplitude modulating a low-cost diode laser emitting at 450 nm. The QEPAS sensor element features double-resonant amplification, still it is only ∼ 5 × 5 × 2.5 mm in size. The individual and combined resonance characteristics were investigated and specified to 52 dB amplification, adding up 15 dB acoustic- and 37 dB mechanical-resonance amplification. The linearity of the photoacoustic signal dependency on the analyte concentration was verified from 200 ppbV to 100 ppmV NO2 in synthetic air. The detection limit (3σ) was determined to 1.8 ppbV using a lock-in time constant of 10 s and an averaging time of 20 s. The normalized noise equivalent absorption coefficient was specified to 2.5·10−8 W cm−1 Hz−0.5. The stability of the signal was investigated over time and a slight drift by 1‰ was observed after 30 min without temperature stabilizing the photoacoustic cell (PAC). Noise analysis was performed by means of Allan deviation and the inverse dependency of response time and precision of the system on the lock-in time constant was outlined. We performed interference analyses towards N2, O2, CO2, H2O and acoustic noise, respectively. Although neither spectral interferences nor losses due to slow NO2 VT-relaxation were observed, O2 was identified to cause a 15% signal drop due to VVNO2-O2-relaxation. Changing H2O concentrations were found to cause acoustic detuning, which cannot be compensated by adjusting the frequency of modulation, because of the double-resonant feature of the PAC. However, alternative approaches of compensation were discussed. Finally, we carried out heavy traffic noise simulations and determined the QEPAS setup to be 46 times less susceptible towards ambient noise compared to standard microphone-based photoacoustic setups.
Gezeigt wird die Miniaturisierung eines Messsystems für Oberflächenplasmonenresonanzspektroskopie (SPR), einer markierungs-, sowie zerstörungsfreien als auch hoch sensitiven Technologie. Aufgrund der hohen Kosten klassischer SPR-Geräte wird sie bisher jedoch vornehmlich in der Bio- und Medizintechnik eingesetzt. Das Messprinzip ermöglicht die Erfassung von Brechungsindexänderungen nahe einer Oberfläche. Der Transfer dieser Technologie von Laborgeräten hin zu einem miniaturisierten Sensorsystem senkt die Kosten, macht das System robuster und ermöglicht so ein wesentlich breiteres Anwendungsspektrum. Ein sehr vielversprechendes Merkmal des hier vorgestellten Systems ist die Möglichkeit den SPR-Effekt winkelabhängig zur Lichtquelle ohne bewegliche Bauteile zu verfolgen.
The miniaturization of Surface Plasmon Resonance (SPR) technology, which mainly finds its applications in pharmaceutical screening and biotechnology so far, is described. SPR spectroscopy is a label-free, non destructive and highly sensitive measurement principle which is capable of detecting changes in the refractive index in striking distance to a gold surface. A transfer of this technology to a miniaturized sensor will broaden the range of possible applications. A promising feature which is included in the miniaturized system is the angle-dependent recording of the SPR signals without moving parts.
Mit der Oberflächenplasmonenresonanzspektroskopie (SPR) können Brechungsindexänderungen eines Analyten von bis zu 10-6 RIU detektiert werden. Das SPR-Imaging bietet heute gegenüber der konventionellen SPR-Analyse die Möglichkeit, mehrere einzelne Messungen parallel durchführen zu können. Mit Hilfe eines zweidimensionalen Sensorchips und einer leistungsfähigen Boardlevelkamera können die Abbildungen des Chips direkt an einen Rechner übertragen und dort verarbeitet werden. Aufgrund unterschiedlicher Winkelstellungen und der Geometrie des Aufbaus entstehen Stauchungen und Streckungen des abgebildeten Sensorchips, die mit verschiedenen Ansätzen aus der Bildverarbeitung ausgeglichen werden, um die Bilder miteinander vergleichen zu können. Zudem wird die Güte der Referenz- und Messbereiche des Chips bestimmt. Diese Algorithmen sind nur möglich aufgrund der heutigen, leistungsfähigen Rechner und der immer größer werdenden Durchsatzraten der Kameras. Dabei kommt in dieser Anwendung der relativ neue Kamerastandard USB3 Vision zum Einsatz. Dieser zeichnet sich zusätzlich durch das Plug and Play und seinen Standardstecker, der an (fast) jedem Rechner vorhanden ist, aus.
Die Oberflächenplasmonenresonanzspektroskopie (SPR) wird aufgrund ihrer Vorzüge der zerstörungs- und markierungsfreien Messung, sowie der hohen Sensitivität sehr erfolgreich im Labormaßstab eingesetzt. Aufgrund der hohen Kosten geschieht dies bislang hauptsächlich in der Bioanalytik und dem Wirkstoffscreening. Gezeigt wird ein Ansatz, mit dem diese Technologie auf ein ultrakompaktes, kostengünstiges Sensorsystem übertragen wird, welches in der Lage ist, hoch-sensitiv Änderungen im Brechungsindex von 10-6 Einheiten (RIU) zu detektieren. Für Wasser bewirkt eine Temperaturschwankung von 1 K bereits eine Änderung von 1 mRIU. Daher wird durch ein integriertes Referenzsystem, sowie die Miniaturisierung erreicht, dass das System gegenüber Temperaturschwankungen, weitestgehend stabil ist. In dem MOEMS wird anstatt der konventionellen 1-Punkt bzw. 2-Punkt Messung ein bildgebendes Verfahren angewendet. Die Sensorfläche von 15 x 15 mm wird dabei mit einem handelsüblichen 4 Mio. Pixel CMOS Sensor ausgewertet. Um verlässliche Datenpunkte zu erhalten benötigt man eine Fläche von 10 x 10 Pixel. Demzufolge können auf dem Sensor theoretisch bis zu 40.000 Sensorspots parallel ausgewertet werden.
Surface plasmon resonance depends on the dielectric medium at the vicinity and makes it a quasi-universal detector. Therefore, and due to the label-free nature, SPR is a widely used sensing tool for real‐time monitoring molecular interactions of various analytes. However, detection of highly diluted analytes and small molecules (< 400 Da) is still challenging. Gold nanohole arrays provide plasmonic hotspots with improved surface sensitivity and 2D carbon nanomaterials enable binding near the surface. Both effects together are promising in the development of SPR sensors for the efficient determination of small molecules. Graphene is known for efficient binding of molecules with delocalized aromatic π-systems. Additionally, the electromagnetic field is locally enhanced and modulated by the interaction of graphene photonics with the plasmonics of metal nanostructures. The advantages of chemical vapor deposition (CVD) graphene over reduced graphene oxide (rGO) is illustrated by a proof of concept study. In comparison to substrates consisting of a continuous film the surface sensitivity is enhanced for a nanohole arrays and further improved for CVD graphene functionalization in contrast to rGO. The feasibility of the sensor was demonstrated for the detection of adenine down to a concentration of 0.9 μM.
Die Oberflächenplasmonenresonanzspektroskopie (SPR) ist eine hochempfindliche Messmethode, die es erlaubt, Gase und Flüssigkeiten zerstörungs- und markierungsfrei in Echtzeit zu analysieren. Bisher vornehmlich im Labormaßstab in der Bioanalytik und dem Wirkstoffscreening eingesetzt, soll diese Technologie nun miniaturisiert und für weitere Anwendungsgebiete zugänglich gemacht werden. Dazu wird ein kompakter Micro-Opto-Electro-Mechanical Systems Sensor (MOEMS) entwickelt, der mit Hilfe des SPR Imaging Änderungen der chemischen Zusammensetzung verschiedener Flüssigkeiten inline messen kann.
This work gives a detailed characterization of a laboratory setup for photoacoustic NO2 trace gas detection at the ppb level. The signal generation is based on the excitation of electronic 2B2 and 2B1 states using a low-cost semiconductor laser emitting at 450 nm. An acoustic resonator was used for signal amplification and the modulation frequency of the laser was determined to 3395 Hz in order to gain maximum signal amplification. The quality of resonant amplification was determined to 7.9. The gas samples were NO2 calibration gases diluted with pure nitrogen. The signal-to-noise ratio (SNR) dependency on the flow rate Q and the lock-in time constant τLIA was investigated, respectively, and the optimum values were specified to Q = 500 mL/min and τLIA = 2 s. In case of ambient noise, increasing τLIA to 10 s was evaluated as sufficient for SNR preservation. The noise level was measured in the absence of NO2 and it was determined to be composed of 51% electronic noise and 49% gas flow noise. With the analyte concentration ranging from 300 ppbV to 100 ppmV, the linear dependency of the photoacoustic amplitude on the NO2 concentration was specified, the sensitivity was determined to 110 μV/ppmV and the maximum measurement error was calculated to ±0.8%. The detection limit was determined to 2.0 ppbV. Furthermore, the stability of the signal was investigated and a maximum drift of ±1% was observed within a measuring period of 30 min. The response time τ90 was specified to 58 s. All results considered, this photoacoustic measuring system, which is based on low-cost signal generation and detection units, provides an excellent basis in view of developing a portable device for photoacoustic trace gas detection.
Photoacoustic spectroscopy is an efficient method to detect the concentration of trace gases with following advantages: short response time, high sensitivity, continuous and real-time monitoring and the option of miniaturization without the need of complex mirror-based multi-pass cell designs. A micromechanical cantilever is used as a key component in a two-part "Cantilever-Resonator" system that detects the weak photoacoustic signal. The resonance frequency of cantilever needs to be tuned to match the resonance frequency of resonator in order to achieve the maximum vibration amplitude of the "Cantilever-Resonator" system. This paper reports a post-fabrication method to tune the resonance frequency of cantilevers via focused ion beam (FIB) and a capacitive solution for the cantilever to transform the acoustic signal to electrical signal.
We present the development and the characterization of a photoacoustic NO2 trace gas detection system. The system is based on the implementation of low-cost components, i.e. a mass-produced blue diode laser and a standard MEMS microphone which is commonly built into smartphones, for example. An optimized cell design was realized by means of 3D printing. The linearity of the photoacoustic signal dependency on the analyte concentration was verified from 200 ppbV to 100 ppmV NO2. The detection limit (1σ) was determined to 33 pptV and the normalized noise equivalent absorption coefficient was calculated to 7.0 ∙ 10−10 W cm−1 Hz−1/2. The dynamic range of the system was verified to be linear over three magnitudes of order and the sensitivity was calculated to 814 μV/ppmV. The system was characterized in view of optimal operating parameters, i.e. lock-in time constant τLIA and total mass flow rate, optical performance and signal stability. The mass flow dependend response time of the system was specified to 19 s and an idealized step response to a quasi-Heaviside step function was quantified as a function of τLIA. The quality factor of acoustic resonance was determined to 21.9 and an empirical expression regarding acoustic node shifting is provided. The expression takes into account the radius of the resonator pipe and the radius of the hole, which was drilled into the pipe for microphone coupling. Furthermore, we studied the cross-sensitivity of the photoacoustic signal towards H2O and CO2, respectively.
The monitoring of partial pressures of the blood gases carbon dioxide (pCO2) and oxygen (pO2) is of great importance in clinical diagnostics. The measure of pCO2 and pO2 provides essential information about the patient’s metabolism, gas exchange, ventilation, and acid–base homeostasis. The conventional electrochemical methods for clinical blood gas analysis are based on the potentiometric Severinghaus sensor for carbon dioxide and the amperometric Clark sensor for oxygen. These techniques are well established and are only shortly discussed in this overview. However, in recent years a variety of modifications of these classical sensor concepts and new approaches of electrochemical sensing of pCO2 and pO2 have been introduced. This review summarizes recent developments in this field and discusses the potential for future applications in clinical blood gas analysis.
The label-free nature of surface plasmon resonance techniques (SPR) enables a fast, specific, and sensitive analysis of molecular interactions. However, detection of highly diluted concentrations and small molecules is still challenging. It is shown here that in contrast to continuous gold films, gold nanohole arrays can significantly improve the performance of SPR devices in angle-dependent measurement mode, as a signal amplification arises from localized surface plasmons at the nanostructures. This leads consequently to an increased sensing capability of molecules bound to the nanohole array surface. Furthermore, a reduced graphene oxide (rGO) sensor surface was layered over the nanohole array. Reduced graphene oxide is a 2D nanomaterial consisting of sp2-hybridized carbon atoms and is an attractive receptor surface for SPR as it omits any bulk phase and therefore allows fast response times. In fact, it was found that nanohole arrays demonstrated a higher shift in the resonance angle of 250–380% compared to a continuous gold film. At the same time the nanohole array structure as characterized by its diameter-to-periodicity ratio had minimal influence on the binding capacity of the sensor surface. As a simple and environmentally highly relevant model, binding of the plasticizer diethyl phthalate (DEP) via π-stacking was monitored on the rGO gold nanohole array realizing a limit of detection of as low as 20 nM. The concentration-dependent signal change was studied with the best performing rGO-modified nanohole arrays. Compared to continuous gold films a diameter-to-periodicity ratio (D/P) of 0.43 lead to a 12-fold signal enhancement. Finally, the effect of environmental waters on the sensor was evaluated using samples from sea, lake and river waters spiked with analytically relevant amounts of DEP during which significant changes in the SPR signal are observed. It is expected that this concept can be successfully transferred to enhance the sensitivity in SPR sensors.
Diese Abhandlung beschreibt das Konzept eines mikroeletromechanischen Systems (MEMS), das im Messverfahren der cantilever enhanced photoacoustic spectroscopy (CEPAS) Verwendung finden soll.
Es wird die Herstellung eines einseitig eingespannten Biegebalkens aus Silizium mittels deep reactiv ion etching (DRIE) beschrieben. Des Weiteren wird die Resonanzfrequenz dieses Cantilevers mit Hilfe Laservibrometertechnik untersucht. Die resultierenden resonanten Schwingungen 0.Ordnung werden mit den Ergebnissen einer vereinfachten theoretischen Näherung verglichen. Die Messergebnisse stehen in gutem Zusammenhang mit den theoretischen Werten. Solche Cantilever, die aus silicon on insula tor (SOI) Wafer angefertigt wurden, weisen bei einer Zielfrequenz ein mittlere Abweichung von Δf = 118±26Hz (bzw.Δf =0,76±0,17%) auf.
Purpose:
of this paper is experimental investigation of damping properties of unidirectionally and fabric reinforced plastics by the free decay method.
Design/methodology/approach:
For the evaluation of the presumed effect experimental structural dynamic investigations comparing unidirectionally and fabric reinforced plastics are carried out. In detail the free decay behaviour of flat beamlike specimens under fixed-free boundary conditions and relatively constant and reproducible displacement excitation is investigated. Findings: The vibrating structure has been measured by a laser scanning vibrometer PSV 400 from POLYTEC. In both cases evaluation of the results yields enhanced damping properties of the specimens with fabric reinforcement compared to the unidirectionally reinforced specimens. The results justify the presumed acting of a mesomechanic kinematic.
Research limitations/implications:
The results show that in either case the material damping in terms of the logarithmic decrement of the fabric reinforced material is higher than the material damping in of the unidirectionally reinforced material. Additionally, when the fabric reinforced specimens are addressed, in each case the plain weave reinforced specimens exhibited higher values of the material damping as the twill weave 2/2 reinforced ones.
Originality/value:
Ondulations in fabrics as a textile semi-finished product are caused by the alternating crossing of warp and fill yarns. In the mesoscopic scale the acting of a mesomechanic kinematic is presumed to enhance the damping properties under cyclic elastic deformation. For the evaluation of the presumed effect experimental structural dynamic investigations comparing unidirectionally and fabric reinforced plastics are carried out.
Development of a miniaturized photoacoustic multigas sensing system for trace gas measurement
(2014)
Ultrasound measurement technology has advancedin previous decades due to positive developments in computing power and lower cost for the necessary hardware. Correlation-based processing can be advantageous for high-accuracy measurements, especially in noisy environments. Higher computational load makes correlation less attractive for industrialapplications, though, favouring traditional processing techniques. A platform for comparing various processing techniques hasbeen developed. It was found that both zero-crossing detectionas well as correlation can achieve very high accuracy over a hightemperature range but that correlation-based processing can lead to a significant precision bias depending on system bandwidth.
Development of a miniaturized photoacoustic multigas sensing system for trace gas measurement
(2013)
A digital dual-phase lock-in amplifier that is capable to run on a low-cost, low-power platform comprising a 16-bit fixed-point digital signal processor was developed. This is achieved by a set of optimised digital filters including an exponential averager to adjust the time constant of the overall filter. The reference frequency is generated using a direct digital synthesis source utilising angle decomposition with a resolution of 1 Hz. The digital lock-in algorithm is described and the performance of the algorithm is analysed. The experimental results show that the developed lock-in amplifier achieves similar performance to a commercially available lock-in amplifier.