A new generation of hollow waveguide (HWG) gas cells of unprecedented compact dimensions facilitating low sample volumes suitable for broad- and narrow-band mid-infrared (MIR; 2.5-20 μm) sensing applications is reported: the substrate-integrated hollow waveguide (iHWG). iHWGs are layered structures providing light guiding channels integrated into a solid-state substrate material, which are competitive if not superior in performance to conventional leaky-mode fiber optic silica HWGs having similar optical pathlengths. In particular, the provided flexibility in device and optical design and the wide variety of manufacturing strategies, substrate materials, access to the optical channel, and optical coating options highlight the advantages of iHWGs in terms of robustness, compactness, and cost-effectiveness. Finally, the unmatched modularity of this novel waveguide approach facilitates tailoring iHWGs to almost any kind of gas sensor technology providing adaptability to the specific demands of a wide range of sensing scenarios. Device fabrication is demonstrated for the example of a yin-yang-shaped gold-coated iHWG fabricated within an aluminum substrate with a footprint of only 75 mm × 50 mm × 12 mm (L × W × H), yet providing a nominal optical absorption path length of more than 22 cm. The analytical utility of this device for advanced MIR gas sensing applications is demonstrated for the gaseous constituents butane, carbon dioxide, cyclopropane, isobutylene, and methane.

With the availability of broadly tunable external cavity quantum cascade lasers (EC-QCLs), particularly bright mid-infrared (MIR; 3-20 μm) light sources are available offering high spectral brightness along with an analytically relevant spectral tuning range of >2 μm. Accurate isotope ratio determination of (12)CO2 and (13)CO2 in exhaled breath is of critical importance in the field of breath analysis, which may be addressed via measurements in the MIR spectral regime. Here, we combine for the first time an EC-QCL tunable across the (12)CO2/(13)CO2 spectral band with a miniaturized hollow waveguide gas cell for quantitatively determining the (12)CO2/(13)CO2 ratio within the exhaled breath of mice. Due to partially overlapping spectral features, these studies are augmented by appropriate multivariate data evaluation and calibration techniques based on partial least-squares regression along with optimized data preprocessing. Highly accurate determinations of the isotope ratio within breath samples collected from a mouse intensive care unit validated via hyphenated gas chromatography-mass spectrometry confirm the viability of IR-HWG-EC-QCL sensing techniques for isotope-selective exhaled breath analysis.

Volatile sulfur compounds (VSCs) are among the most prevalent emitted pollutants in urban and rural atmospheres. Mainly because of the versatility of sulfur regarding its oxidation state (2- to 6+), VSCs are present in a wide variety of redox-environments, concentration levels, and molar ratios. Among the VSCs, hydrogen sulfide and sulfur dioxide are considered most relevant and have simultaneously been detected within naturally and anthropogenically caused emission events (e.g., volcano emissions, food production and industries, coal pyrolysis, and various biological activities). Next to their presence as pollutants, changes within their molar ratio may also indicate natural anomalies. Prior to analysis, H2S- and SO2-containing samples are usually preconcentrated via solid sorbents and are then detected by gas chromatographic techniques. However, such analytical strategies may be of limited selectivity, and the dimensions and operation modalities of the involved instruments prevent routine field usage. In this contribution, we therefore describe an innovative portable mid-infrared chemical sensor for simultaneously determining and quantifying gaseous H2S and SO2 via coupling a substrate-integrated hollow waveguides (iHWG) serving as a highly miniaturized mid-infrared photon conduit and gas cell with a custom-made preconcentration tube and an in-line UV-converter device. Both species were collected onto a solid sorbent within the preconcentrator and then released by thermal desorption into the UV-device. Hydrogen sulfide is detected by UV-assisted quantitative conversion of the rather weak IR-absorber H2S into SO2, which provides a significantly more pronounced and distinctively detectable rovibrational signature. Modulation of the UV-device system (i.e., UV-lamp on/off) enables discriminating between SO2 generated from H2S conversion and abundant SO2 signals. After optimization of the operational parameters, calibrations in the range of 0.75-10 ppmv with a limit of detection (LOD) at 77 ppbv for SO2 and 207 ppbv for H2S were established after 20 min of sampling time at 200 mL min(-1). Taking advantage of the device flexibility in terms of sampling time, flow-rate, and iHWG design facilitates tailoring the developed Preconcentrator-UV-device-iHWG device toward a wide variety of application scenarios ranging from environmental/atmospheric monitoring to industrial process monitoring and clinical diagnostics.

A fully integrated electromechanical resonator is described that is based on high mobility piezoelectric semiconductors for actuation and detection of nanoscale motion. We employ the two-dimensional electron gas present at an AlGaN/GaN interface and the piezoelectric properties of this heterostructure to demonstrate a resonant high-electron-mobility transistor enabling the detection of strain variation. In this device, we take advantage of the polarization field divergence originated by mechanical flexural modes for generating piezoelectric doping. This enables a modulation of carrier density which results in a large current flow and thus constitutes a motion detector with intrinsic amplification.

Selected volatile organic compounds (VOCs) in breath may be considered biomarkers if they are indicative of distinct diseases or disease states. Given the inherent molecular selectivity of vibrational spectroscopy, infrared sensing technologies appear ideally suitable for the determination of endogenous VOCs in breath. The aim of this study was to determine that mid-infrared (MIR; 3-20 µm) gas phase sensing is capable of determining isoprene in exhaled breath as an exemplary medically relevant VOC by hyphenating novel substrate-integrated hollow waveguides (iHWG) with a likewise miniaturized preconcentration system. A compact preconcentrator column for sampling isoprene from exhaled breath was coupled to an iHWG serving simultaneously as highly miniaturized gas cell and light conduit in combination with a compact Fourier transform infrared spectrometer. A gas mixing system enabled extensive system calibration using isoprene standards. After system optimization, a calibration function obtaining a limit of quantification of 106 ppb was achieved. According to the literature, the obtained sensitivity is sufficient for quantifying middle to high isoprene concentrations occurring in exhaled breath. Finally, a volunteer breath sample was analysed proving comparable values of isoprene in a real-world scenario. Despite its fundamental utility, the proposed methodology contains some limitations in terms of sensitivity and temporal resolution in comparison with the readily available measurement techniques that should be addressed during future optimization of the system. Nonetheless, this study presents the first determination of endogenous VOCs in breath via advanced hollow waveguide MIR sensor technology, clearly demonstrating its potential for the analysis of volatile biomarkers in exhaled breath.

A miniaturised gas analyser is described and evaluated based on the use of a substrate-integrated hollow waveguide (iHWG) coupled to a microsized near-infrared spectrophotometer comprising a linear variable filter and an array of InGaAs detectors. This gas sensing system was applied to analyse surrogate samples of natural fuel gas containing methane, ethane, propane and butane, quantified by using multivariate regression models based on partial least square (PLS) algorithms and Savitzky-Golay 1(st) derivative data preprocessing. The external validation of the obtained models reveals root mean square errors of prediction of 0.37, 0.36, 0.67 and 0.37% (v/v), for methane, ethane, propane and butane, respectively. The developed sensing system provides particularly rapid response times upon composition changes of the gaseous sample (approximately 2 s) due the minute volume of the iHWG-based measurement cell. The sensing system developed in this study is fully portable with a hand-held sized analyser footprint, and thus ideally suited for field analysis. Last but not least, the obtained results corroborate the potential of NIR-iHWG analysers for monitoring the quality of natural gas and petrochemical gaseous products.

Hydrogen sulfide is a highly corrosive, harmful, and toxic gas produced under anaerobic conditions within industrial processes or in natural environments, and plays an important role in the sulfur cycle. According to the U.S. Occupational Safety and Health Administration (OSHA), the permissible exposure limit (during 8 hours) is 10 ppm. Concentrations of 20 ppm are the threshold for critical health issues. In workplace environments with human subjects frequently exposed to H2S, e.g., during petroleum extraction and refining, real-time monitoring of exposure levels is mandatory. Sensors based on electrochemical measurement principles, semiconducting metal-oxides, taking advantage of their optical properties, have been described for H2S monitoring. However, extended response times, limited selectivity, and bulkiness of the instrumentation are common disadvantages of the sensing techniques reported to date. Here, we describe for the first time usage of a new generation of compact gas cells, i.e., so-called substrate-integrated hollow waveguides (iHWGs), combined with a compact Fourier transform infrared (FTIR) spectrometer for advanced gas sensing of H2S. The principle of detection is based on the immediate UV-assisted conversion of the rather weak IR-absorber H2S into much more pronounced and distinctively responding SO2. A calibration was established in the range of 10-100 ppm with a limit of detection (LOD) at 3 ppm, which is suitable for occupational health monitoring purposes. The developed sensing scheme provides an analytical response time of less than 60 seconds. Considering the substantial potential for miniaturization using e.g., a dedicated quantum cascade laser (QCL) in lieu of the FTIR spectrometer, the developed sensing approach may be evolved into a hand-held instrument, which may be tailored to a variety of applications ranging from environmental monitoring to workplace safety surveillance, process analysis and clinical diagnostics, e.g., breath analysis.

Mouse sepsis models are used to gain insight into the complex processes involved with patients suffering from glucose metabolism disorders. Measuring the expiratory release of (13)CO(2) after administering stable labeled (13)C(6)-glucose enables assessment of the in vivo integrity and functionality of key metabolic processes. In the present study, we demonstrate that Fourier transform infrared spectroscopy operating in the mid-infrared spectral regime (2-20 μm) combined with hollow waveguide gas sensing modules simultaneously serving as a miniaturized gas cell and as a waveguide are capable of quantitatively monitoring (13)CO(2) enrichment levels in low volume mouse breath samples.