A Review of Gas Measurement Set-Ups.

Measurements of the properties of gas-sensitive materials are a subject of constant research, including continuous developments and improvements of measurement methods and, consequently, measurement set-ups. Preparation of the test set-up is a key aspect of research, and it has a significant impact on the tested sensor. This paper aims to review the current state of the art in the field of gas-sensing measurement and provide overall conclusions of how the different set-ups impact the obtained results.

Developing GLAD Parameters to Control the Deposition of Nanostructured Thin Film.

In this paper, we describe the device developed to control the deposition parameters to manage the glancing angle deposition (GLAD) process of metal-oxide thin films for gas-sensing applications. The GLAD technique is based on a set of parameters such as the tilt, rotation, and substrate temperature. All parameters are crucial to control the deposition of nanostructured thin films. Therefore, the developed GLAD controller enables the control of all parameters by the scientist during the deposition. Additionally, commercially available vacuum components were used, including a three-axis manipulator. High-precision readings were tested, where the relative errors calculated using the parameters provided by the manufacturer were 1.5% and 1.9% for left and right directions, respectively. However, thanks to the formula developed by our team, the values were decreased to 0.8% and 0.69%, respectively.

Review of the algorithms used in exhaled breath analysis for the detection of diabetes.

Currently, intensive work is underway on the development of truly noninvasive medical diagnostic systems, including respiratory analysers based on the detection of biomarkers of several diseases including diabetes. In terms of diabetes, acetone is considered as a one of the potential biomarker, although is not the single one. Therefore, the selective detection is crucial. Most often, the analysers of exhaled breath are based on the utilization of several commercially available gas sensors or on specially designed and manufactured gas sensors to obtain the highest selectivity and sensitivity to diabetes biomarkers present in the exhaled air. An important part of each system are the algorithms that are trained to detect diabetes based on data obtained from sensor matrices. The prepared review of the literature showed that there are many limitations in the development of the versatile breath analyser, such as high metabolic variability between patients, but the results obtained by researchers using the algorithms described in this paper are very promising and most of them achieve over 90% accuracy in the detection of diabetes in exhaled air. This paper summarizes the results using various measurement systems, feature extraction and feature selection methods as well as algorithms such as support vector machines,k-nearest neighbours and various variations of neural networks for the detection of diabetes in patient samples and simulated artificial breath samples.

The Heterostructures of CuO and SnOx for NO2 Detection.

Controlling environmental pollution is a burning problem for all countries more than ever. Currently, due to the increasing industrialization, the number of days when the limits of air pollutants are over the threshold levels exceeds 80-85% of the year. Therefore, cheap and effective sensors are always welcome. One idea is to combine such solutions with cars and provide real-time information about the current pollution level. However, the environmental conditions are demanding, and thus the developed sensors need to be characterized by the high 3S parameters: sensitivity, stability and selectivity. In this paper, we present the results on the heterostructure of CuO/SnOx and SnOx/CuO as a possible approach for selective NO2 detection. The developed gas sensors exhibited lower operating temperature and high response in the wide range of NO2 and in a wide range of relative humidity changes. Material characterizations and impedance spectroscopy measurements were also conducted to analyze the chemical and electrical behavior.

Artificial Breath Classification Using XGBoost Algorithm for Diabetes Detection.

Exhaled breath analysis has become more and more popular as a supplementary tool for medical diagnosis. However, the number of variables that have to be taken into account forces researchers to develop novel algorithms for proper data interpretation. This paper presents a system for analyzing exhaled air with the use of various sensors. Breath simulations with acetone as a diabetes biomarker were performed using the proposed e-nose system. The XGBoost algorithm for diabetes detection based on artificial breath analysis is presented. The results have shown that the designed system based on the XGBoost algorithm is highly selective for acetone, even at low concentrations. Moreover, in comparison with other commonly used algorithms, it was shown that XGBoost exhibits the highest performance and recall.

Nitrogen Dioxide Sensing Using Multilayer Structure of Reduced Graphene Oxide and α-Fe2O3.

Multilayers consisting of graphene oxide (GO) and α-Fe2O3 thin layers were deposited on the ceramic substrates by the spray LbL (layer by layer) coating technique. Graphene oxide was prepared from graphite using the modified Hummers method. Obtained GO flakes reached up to 6 nanometers in thickness and 10 micrometers in lateral size. Iron oxide Fe2O3 was obtained by the wet chemical method from FeCl3 and NH4OH solution. Manufactured samples were deposited as 3 LbL (GO and Fe2O3 layers deposited sequentially) and 6 LbL structures with GO as a bottom layer. Electrical measurements show the decrease of multilayer resistance after the introduction of the oxidizing NO2 gas to the ambient air atmosphere. The concentration of NO2 was changed from 1 ppm to 20 ppm. The samples changed their resistance even at temperatures close to room temperature, however, the sensitivity increased with temperature. Fe2O3 is known as an n-type semiconductor, but the rGO/Fe2O3 hybrid structure behaved similarly to rGO, which is p-type. Both chemisorbed O2 and NO2 act as electron traps decreasing the concentration of electrons and increasing the effective multilayer conductivity. An explanation of the observed variations of multilayer structure resistance also the possibility of heterojunctions formation was taken into account.

SnO2/TiO2 Thin Film n-n Heterostructures of Improved Sensitivity to NO2.

Thin-film n-n nanoheterostructures of SnO2/TiO2, highly sensitive to NO2, were obtained in a two-step process: (i) magnetron sputtering, MS followed by (ii) Langmuir-Blodgett, L-B, technique. Thick (200 nm) SnO2 base layers were deposited by MS and subsequently overcoated with a thin and discontinuous TiO2 film by means of L-B. Rutile nanopowder spread over the ethanol/chloroform/water formed a suspension, which was used as a source in L-B method. The morphology, crystallographic and electronic properties of the prepared sensors were studied by scanning electron microscopy, SEM, X-ray diffraction, XRD in glancing incidence geometry, GID, X-ray photoemission spectroscopy, XPS, and uv-vis-nir spectrophotometry, respectively. It was found that amorphous SnO2 films responded to relatively low concentrations of NO2 of about 200 ppb. A change of more than two orders of magnitude in the electrical resistivity upon exposure to NO2 was further enhanced in SnO2/TiO2 n-n nanoheterostructures. The best sensor responses RNO2/R0 were obtained at the lowest operating temperatures of about 120 °C, which is typical for nanomaterials. Response (recovery) times to 400 ppb NO2 were determined as a function of the operating temperature and indicated a significant decrease from 62 (42) s at 123 °C to 12 (19) s at 385 °C A much smaller sensitivity to H2 was observed, which might be advantageous for selective detection of nitrogen oxides. The influence of humidity on the NO2 response was demonstrated to be significantly below 150 °C and systematically decreased upon increase in the operating temperature up to 400 °C.

CuO-Ga2O3 Thin Films as a Gas-Sensitive Material for Acetone Detection.

The p-n heterostructures of CuO-Ga2O3 obtained by magnetron sputtering technology in a fully reactive mode (deposition in pure oxygen) were tested under exposure to low acetone concentrations. After deposition, the films were annealed at previously confirmed conditions (400 °C/4 h/synthetic air) and further investigated by utilization of X-ray diffraction (XRD), X-ray reflectivity (XRR), energy-dispersive X-ray spectroscopy (EDS). The gas-sensing behavior was tested in the air/acetone atmosphere in the range of 0.1-1.25 ppm, as well as at various relative humidity (RH) levels (10-85%). The highest responses were obtained for samples based on the CuO-Ga2O3 (4% at. Ga).

Tin Dioxide Thin Film with UV-enhanced Acetone Detection in Microwave Frequency Range.

In this paper, the UV illumination effect for microwave gas sensors based on the tin dioxide was verified. A UV LED with emission wavelength close to the absorption edge of the SnO2 gas-sensing layer was selected as the UV source. The developed gas sensors were tested under exposure to acetone in the 0-200 ppm range at room temperature. The sensor's complex reflection coefficient corresponding to target gas concentration was measured with the use of a five-port reflectometer system exhibiting enhanced uncertainty distribution, which allows for the detection of low gas concentration. The UV illumination significantly emphasizes the sensors' response in terms of both magnitude and phase for low gas concentrations, in contrast to previously reported results, in which only the reflection coefficient's phase was affected. The highest responses were obtained for modulated UV illumination.

Metal Oxide Thin Films Prepared by Magnetron Sputtering Technology for Volatile Organic Compound Detection in the Microwave Frequency Range.

Metal oxide thin films such as copper oxide, titanium dioxide, and tin dioxide deposited by magnetron sputtering technology were verified as a gas-sensitive layer in microwave-based gas sensors operated at 2.4 GHz. The developed gas sensors were tested at room temperature (23 °C) and 50% relative humidity (RH) under exposure to 0⁻200 ppm of selected volatile organic compounds (acetone, ethanol, and methanol) that are of high interest in industry and biomedical applications. The highest responses to acetone were obtained for CuO-based gas sensors, to ethanol for SnO2-based gas sensors, while for methanol detection both dioxides, SnO2 and TiO2, exhibited good sensitivity.

Effectiveness of Sensors Contact Metallization (Ti, Au, and Ru) and Biofunctionalization for Escherichia coli Detection.

In designing a bacteria biosensor, various issues must be addressed: the specificity of bacteria recognition, the immobilization of biomolecules that act as the bacteria receptor, and the selectivity of sensor surface. The aim of this paper was to examine how the biofunctionalized surface of Ti, Au, and Ru metals reacts in contact with strains of Escherichia coli (E. coli). The focus on metal surfaces results from their future use as electrodes in high frequency biosensors, e.g., resonant circuits or transmission-line sections. First, the surfaces of different metals were chemically functionalized with 3-aminopropyltriethoxysilane (APTES) and glutaraldehyde or with 3-glycidylooxypropyltrimethoxysilane (GPTMS) followed by N-(5-amino-1-carboxypentyl) iminodiacetic acid (AB-NTA) and NiCl2. Secondly, the lipopolysaccharide binding protein (LBP), polyclonal anti-Escherichia coli antibody and bacteriophage protein gp37 were tested as bacteria receptors. The selectivity and specificity have been confirmed by the Enzyme-Linked Immunosorbent Assay (ELISA) and visualized by scanning electron microscopy at low landing energies. We noticed that LBP, polyclonal antibody, and gp37 were successfully immobilized on all studied metals and recognized the E. coli bacteria selectively. However, for the antibody, the highest reactivity was observed when Ti surface was modified, whereas the bacteria binding was comparable between LBP and gp37 on the functionalized Ru surfaces, independent from modification. Thus, all surfaces were biocompatible within the scope of biosensor functionality, with titanium functionalization showing the best performance.

Sensors for Enhanced Detection of Acetone as a Potential Tool for Noninvasive Diabetes Monitoring.

Measurement of blood-borne volatile organic compounds (VOCs) occurring in human exhaled breath as a result of metabolic changes or pathological disorders is a promising tool for noninvasive medical diagnosis, such as exhaled acetone measurements in terms of diabetes monitoring. The conventional methods for exhaled breath analysis are based on spectrometry techniques, however, the development of gas sensors has made them more and more attractive from a medical point of view. This review focuses on the latest achievements in gas sensors for exhaled acetone detection. Several different methods and techniques are presented and discussed as well.

Comparative study of post-growth annealing of Cu(hfac)2, Co2(CO)8 and Me2Au(acac) metal precursors deposited by FEBID.

Non-noble metals, such as Cu and Co, as well as noble metals, such as Au, can be used in a number modern technological applications, which include advanced scanning-probe systems, magnetic memory and storage, ferroelectric tunnel junction memristors, metal interconnects for high performance integrated circuits in microelectronics and nano-optics applications, especially in the areas of plasmonics and metamaterials. Focused-electron-beam-induced deposition (FEBID) is a maskless direct-write tool capable of defining 3-dimensional metal deposits at nanometre scale for above applications. However, codeposition of organic ligands when using organometallic precursors is a typical problem that limits FEBID of pure metal nanostructures. In this work, we present a comparative study using a post-growth annealing protocol at 100, 200, and 300 °C under high vacuum on deposits obtained from Co2(CO)8, Cu(II)(hfac)2, and Me2Au(acac) to study improvements on composition and electrical conductivity. Although the as-deposited material was similar for all precursors, metal grains embedded in a carbonaceous matrix, the post-growth annealing results differed. Cu-containing deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit for temperatures above 100 °C, due to the migration of Cu atoms from the carbonaceous matrix containing carbon, oxygen, and fluorine atoms. The average size of the Cu crystals doubles between 100 and 300 °C of annealing temperature, while the composition remains constant. In contrast, for Co-containing deposits oxygen release was observed upon annealing, while the carbon content remained approximately constant; the cobalt atoms coalesced to form a metallic film. The as-deposited Au-containing material shows subnanometric grains that coalesce at 100 °C, maintaining the same average size at annealing temperatures up to 300 °C. Raman analysis suggests that the amorphous carbonaceous matrix of the as-written Co, Cu and Au deposits turned into nanocrystalline graphite with comparable crystal sizes of 12-14 nm at 300 °C annealing temperature. However, we observed a more effective formation of graphite clusters in Co- than in Cu- and Au-containing deposits. The graphitisation has a minor influence on the electrical conductivity improvements of Co-C deposits, which is attributed to the high as-deposited Co content and the related metal grain percolation. On the contrary, electrical conductivity improvements by factors of 30 and 12 for, respectively, Cu-C and Au-C deposits with low metal content are mainly attributed to the graphitisation. This relatively simple vacuum-based post-growth annealing protocol may be useful for other precursors as it proved to be efficient in reliably tuning the electrical properties of as-deposited FEBID materials. Finally, a H2-assisted gold purification protocol is demonstrated at temperatures around 300 °C by fully removing the carbon matrix and drastically reducing the electrical resistance of the deposit.

A broadband capacitive sensing method for label-free bacterial LPS detection.

In this paper, the authors present a new type of highly sensitive label-free microwave sensor in a form of interdigital capacitor coated with T4 bacteriophage gp37 adhesin. The adhesin binds Escherichia coli B (E. coli B) by precise recognizing its bacterial host lipopolysaccharide (LPS). The C-terminal part of the adhesin consists of the receptor-binding amino acid residues which are involved in a specific interaction with two terminal glucose residues of the bacterial LPS. The change of the sensors' capacitance and conductance as a subject to LPS presence is an indicator of the detection. The measurements in the frequency range of 0-3GHz utilizing vector network analyzer have been carried out at different concentrations to verify experimentally the proposed method. The measured capacitance change between the reference and the biofunctionalized sensor equals 15% in the entire frequency range and the measured conductance change exceeds 19%. The changes of both parameters can be used as good indicators of the LPS detection. The selectivity has been confirmed by the ELISA experiments and tested by sensor measurements with lipopolysaccharide (LPS) from E. coli B, E. coli 056, E. coli 0111, Pseudomonas aeruginosa NBRC 13743 and Hafnia alvei 1185.

Gas-Sensing Performance of M-Doped CuO-Based Thin Films Working at Different Temperatures upon Exposure to Propane.

Cupric oxide (CuO) thin films are promising materials in gas sensor applications. The CuO-based gas sensors behaved as p-type semiconductors and can be used as part of an e-nose or smart sensor array for breath analysis. The authors present the investigation results on M-doped CuO-based (M = Ag, Au, Cr, Pd, Pt, Sb, Si) sensors working at various temperatures upon exposure to a low concentration of C3H8, which can be found in exhaled human breath, and it can be considered as a one of the biomarkers of several diseases. The films have been deposited in magnetron sputtering technology on low temperature cofired ceramics substrates. The results of the gas sensors' response are also presented and discussed. The Cr:CuO-based structure, annealed at 400 °C for 4 h in air, showed the highest sensor response, of the order of 2.7 at an operation temperature of 250 °C. The response and recovery time(s) were 10 s and 24 s, respectively. The results show that the addition of M-dopants in the cupric oxide films effectively act as catalysts in propane sensors and improve the gas sensing properties. The films' phase composition, microstructure and surface topography have been assessed by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) methods.

A Negative Correlation Between Blood Glucose and Acetone Measured in Healthy and Type 1 Diabetes Mellitus Patient Breath.

BACKGROUND: Exhaled acetone analysis has long been recognized as a supplementary tool for diagnosis and monitoring diabetes, especially type 1 diabetes. It is essential, therefore to determine the relationship between exhaled acetone concentration and glucose in blood. Usually, a direct linear correlation between this both compounds has been expected. However, in some cases we can observe a reverse correlation. When blood glucose was increasing, breath acetone declined. METHODS: The breath analysis as a supplementary tool for diagnosing and monitoring diabetes makes sense only in case of utilization of portable analyzers. This need has created a market for gas sensors. However, commercially available acetone gas sensors are developed for measuring samples at several tens part per million. The exhaled acetone concentration was measured using commercial acetone gas sensor (TGS 822, 823 Figaro, Arlington Heights, IL, USA Inc) with micropreconcentrator in low temperature cofired ceramics. The reference analyzer-mass spectrometry (HPR-20 QIC, Hiden Analytical, Warrington, UK) was used. RESULTS: Twenty-two healthy volunteers with no history of any respiratory disease participated in the research, as did 31 patients diagnosed with type 1 diabetes. Respectively, 3 healthy volunteer and 5 type 1 diabetes mellitus subjects with reverse trend were selected. The linear fitting coefficient various from 0.1139 to 0.9573. Therefore, it is necessary to determine the correlation between blood glucose concentrations and under different conditions, for example, insulin levels, as well as correlate the results with clinical tests, for example, Hb1Ac. CONCLUSIONS: It is well known that the concentration of acetone is strongly influenced by diet, insulin treatment, and so on. Therefore, much more complex analysis with long-term measurements are required. Thus, presented results should be regarded as tentative, and validation studies with the analysis of clinical test and in a large number of patients, including control groups, need to be carried out.

Micropreconcentrator in LTCC Technology with Mass Spectrometry for the Detection of Acetone in Healthy and Type-1 Diabetes Mellitus Patient Breath.

Breath analysis has long been recognized as a potentially attractive method for the diagnosis of several diseases. The main advantage over other diagnostic methods such as blood or urine analysis is that breath analysis is fully non-invasive, comfortable for patients and breath samples can be easily obtained. One possible future application of breath analysis may be the diagnosing and monitoring of diabetes. It is, therefore, essential, to firstly determine a relationship between exhaled biomarker concentration and glucose in blood as well as to compare the results with the results obtained from non-diabetic subjects. Concentrations of molecules which are biomarkers of diseases' states, or early indicators of disease should be well documented, i.e., the variations of abnormal concentrations of breath biomarkers with age, gender and ethnic issues need to be verified. Furthermore, based on performed measurements it is rather obvious that analysis of exhaled acetone as a single biomarker of diabetes is unrealistic. In this paper, the author presents results of his research conducted on samples of breath gas from eleven healthy volunteers (HV) and fourteen type- 1 diabetic patients (T1DM) which were collected in 1-l SKC breath bags. The exhaled acetone concentration was measured using mass spectrometry (HPR-20 QIC, Hiden Analytical, Warrington, UK) coupled with a micropreconcentrator in LTCC (Low Temperature Cofired Ceramic). However, as according to recent studies the level of acetone varies to a significant extent for each blood glucose concentration of single individuals, a direct and absolute relationship between blood glucose and acetone has not been proved. Nevertheless, basing on the research results acetone in diabetic breath was found to be higher than 1.11 ppmv, while its average concentration in normal breath was lower than 0.83 ppmv.