Ultra-broadband spectroscopy using a 2-11.5 µm IDFG-based supercontinuum source.

Supercontinuum sources based on intrapulse difference frequency generation (IDFG) from mode-locked lasers open new opportunities in mid-infrared gas spectroscopy. These sources provide high power and ultra-broadband spectral coverage in the molecular fingerprint region with very low relative intensity noise. Here, we demonstrate the performance of such a light source in combination with a multipass cell and a custom-built Fourier transform spectrometer (FTS) for multispecies trace gas detection. The light source provides a low-noise, ultra-broad spectrum from 2-11.5 µm with ∼3 W output power, outperforming existing mid-infrared supercontinuum sources in terms of noise, spectral coverage, and output power. This translates to an excellent match for spectroscopic applications, establishing (sub-)ppb sensitivity for molecular hydrocarbons (e.g., CH4, C2H4), oxides (e.g., SO2, NOx), and small organic molecules (e.g., acetone, ethyl acetate) over the spectral range of the supercontinuum source with a measurement time varying from seconds to minutes. We demonstrate a practical application by measuring the off-gas composition of a bioreactor containing an acidic ammonia-oxidizing culture with the simultaneous detection of multiple nitrogen oxides (NO, NO2, N2O, etc.). As the different species absorb various parts of the spectrum, these results highlight the functionality of this spectroscopic system for biological and environmental applications.

Fourier transform and grating-based spectroscopy with a mid-infrared supercontinuum source for trace gas detection in fruit quality monitoring.

We present a multi-species trace gas sensor based on a fast, compact home-built Fourier transform spectrometer (FTS) combined with a broadband mid-infrared supercontinuum (SC) source. The spectrometer covers the spectral bandwidth of the SC source (2 - 4 µm) and provides a best spectral resolution of 1 GHz in 6 seconds. It has a detection sensitivity of a few hundred of ppbv Hz-1/2 for different gas species. We study the performance of the developed spectrometer in terms of precision, linearity, long-term stability, and multi-species detection. We use the spectrometer for measuring fruit-produced volatiles under different atmospheric conditions and compare the performance with a previously developed scanning grating-based spectrometer.

Sensitive multi-species trace gas sensor based on a high repetition rate mid-infrared supercontinuum source.

We present a multi-species trace gas sensor based on a high-repetition-rate mid-infrared supercontinuum source, in combination with a 30 m multipass absorption cell, and a scanning grating spectrometer. The output of the spectrometer is demodulated by a digital lock-in amplifier, referenced to the repetition rate of the supercontinuum source. This improved the detection sensitivity of the system by a factor 5, as compared to direct baseband operation. The spectrometer provides a spectral coverage of 950 cm-1 (between 2.85-3.90 µm) with a resolution of 2.5 cm-1 in 100 ms. It can achieve noise equivalent detection limits in the order of 100 ppbv Hz-1/2 for various hydrocarbons, alcohols, and aldehydes.

Broadband Time-Resolved Absorption and Dispersion Spectroscopy of Methane and Ethane in a Plasma Using a Mid-Infrared Dual-Comb Spectrometer.

Conventional mechanical Fourier Transform Spectrometers (FTS) can simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz (0.18 nm at a wavelength of 3333 nm), a temporal resolution of 20 µs, a total wavelength coverage over 300 cm-1 and a total measurement time of ~70 s. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring the fast dynamics of chemical reactions over a broad wavelength range, which can be interesting for chemical kinetic research, particularly for the combustion and plasma analysis community.

Mid-infrared supercontinuum-based upconversion detection for trace gas sensing.

Recent advancements of mid-infrared (MIR) supercontinuum light sources have opened up new possibilities in laser-based trace gas sensing. While the supercontinuum sources inherently support wide spectral coverage, the detection of broadband absorption signals with high speed and low cost is traditionally limited by the MIR detector arrays. In this work, we demonstrate that this limitation can be circumvented by upconverting the MIR signal into the near-infrared (NIR) region, where cost-effective silicon-based detector arrays can be utilized to measure broadband absorption. We also show that, by combining a MIR supercontinuum source with a MIR-to-NIR upconverter and an astigmatic multipass cell, fast detection (~20 ms) of ethane with sub-ppmv sensitivity can be achieved at room temperature. For multi-species detection, a least-square global fitting method is presented, showing a promising potential for applications such as environmental monitoring and biomedical research.

A Broadband Mid-Infrared Trace Gas Sensor Using Supercontinuum Light Source: Applications for Real-Time Quality Control for Fruit Storage.

We present a fully integrated and transportable multi-species trace gas sensor based on a mid-infrared (MIR) supercontinuum light source. The high brightness (surpassing synchrotron) and ultra-broad spectral bandwidth (2-4 µm) of this light source allows simultaneous detection of multiple broadband absorbing gas species. High sensitivity in the sub-ppmv level has been achieved by utilizing an astigmatic multipass cell. A grating-based spectrometer at a scanning rate of 20 Hz is developed employing a balanced detection scheme. A multi-component global fitting algorithm is implemented into a central LabVIEW program to perform real-time data analysis. The obtained concentration values are validated by the standard gas chromatography mass spectrometry (GC-MS) method. Field application of the sensor for quality control of stored fruits at a small scale is demonstrated, involving the detection of ethylene, ethanol, ethyl acetate, acetaldehyde, methanol, acetone, and water simultaneously. The sensor also shows promising potentials for other applications, such as environmental monitoring and biomedical research.

Laser spectroscopy for breath analysis: towards clinical implementation.

Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.

Intensity enhancement in off-axis integrated cavity output spectroscopy.

In the field of laser-based absorption spectroscopy, off-axis integrated cavity output spectroscopy is considered to be a sensitive and robust method, employing a simple optical design. However, one of the major drawbacks of non-mode-matched cavities combined with highly reflective mirrors (>99.98%) is its low output intensity. Here, we systematically investigate the increase in cavity output intensity, using a third re-injection mirror before the absorption cavity. The presented design not only enables high transmission power but also retains a long effective path length. To investigate the intensity enhancement, we used a CO2 absorption line in the near-IR wavelength region at 6240.10 cm-1. In agreement with our simulation model, we achieved an intensity enhancement factor of 38. We achieved a noise equivalent absorption sensitivity to 1.6×10-8 cm-1 Hz-1/2, which is no longer limited by the detectivity of the detector.

Comprehensive three-dimensional ray tracing model for three-mirror cavity-enhanced spectroscopy.

A 3D ray tracing model is used to simulate optical reinjection in a nonresonant optical cavity, for off-axis integrated cavity output spectroscopy. The optical cavities are optimized for maximum intensity enhancement factors via a grid search and a genetic algorithm. Intensity enhancement factors up to 1400 are found for short cavities (3 cm) and up to 101 for long cavities (50 cm). The model predicts that short absorption cells can be used, having a long effective path length and a high throughput power. This opens new opportunities in the field of ultrasensitive absorption spectroscopy and allows the design of compact optical gas sensors.

Sensitive Spectroscopy of Acetone Using a Widely Tunable External-Cavity Quantum Cascade Laser.

We employed a single-mode, widely tunable (~300 cm−1) external-cavity quantum cascade laser operating around 8 µm for broadband direct absorption spectroscopy and wavelength modulation spectroscopy where a modulation frequency of 50 kHz was employed with high modulation amplitudes of up to 10 GHz. Using a compact multipass cell, we measured the entire molecular absorption band of acetone at ~7.4 µm with a spectral resolution of ~1 cm−1. In addition, to demonstrate the high modulation dynamic range of the laser, we performed direct absorption (DAS) and second harmonic wavelength modulation spectroscopy (WMS-2f) of the Q-branch peak of acetone molecular absorption band (HWHM ~10 GHz) near 1365 cm−1. With WMS-2f, a minimum detection limit of 15 ppbv in less than 10 s is achieved, which yields a noise equivalent absorption sensitivity of 1.9 × 10−8 cm−1 Hz−1/2.

Functionalizing a Tapered Microcavity as a Gas Cell for On-Chip Mid-Infrared Absorption Spectroscopy.

Increasing demand for field instruments designed to measure gas composition has strongly promoted the development of robust, miniaturized and low-cost handheld absorption spectrometers in the mid-infrared. Efforts thus far have focused on miniaturizing individual components. However, the optical absorption path that the light beam travels through the sample defines the length of the gas cell and has so far limited miniaturization. Here, we present a functionally integrated linear variable optical filter and gas cell, where the sample to be measured is fed through the resonator cavity of the filter. By using multiple reflections from the mirrors on each side of the cavity, the optical absorption path is elongated from the physical m m -level to the effective m m -level. The device is batch-fabricated at the wafer level in a CMOS-compatible approach. The optical performance is analyzed using the Fizeau interferometer model and demonstrated with actual gas measurements.

Comprehensive Data Scientific Procedure for Enhanced Analysis and Interpretation of Real-Time Breath Measurements in In Vivo Aroma-Release Studies.

Real-time measurements of many low-abundance volatile organic compounds (VOCs) in breath and air samples are already feasible due to progress in analytical technologies, such as proton transfer reaction mass spectrometry (PTR-MS). Nevertheless, the information content of real-time measurements is not fully exploited, due to the lack of suitable data handling methods. This study develops a data scientific procedure to enhance data analysis and interpretation of longitudinal, multivariate data sets from real-time, in vivo, aroma-release studies. The developed procedure includes an automated data preprocessing and a multivariate assessment of the test panel performance. A large multifactorial PTR-MS data set is investigated that includes four experimental protocols, two tested food products, four aroma compounds, and eight panelists. Real-time measurements are converted into standardized breath profiles by preprocessing, and 10 kinetic parameters are derived. Next to this, panel performance is evaluated per experimental protocol and food product. Comprehensive information about panel performance, individual panelists, studied products, aroma compounds, and kinetic parameters is extracted, demonstrating the great value of the developed approach.

Broadly, independent-tunable, dual-wavelength mid-infrared ultrafast optical parametric oscillator.

We demonstrate a two-crystal mid-infrared dual-wavelength optical parametric oscillator, synchronously pumped by a high power femtosecond Yb:fiber laser. The singly-resonant ring cavity, containing two periodically poled lithium niobate crystals, is capable of generating two synchronized idler wavelengths, independently tunable over 30 THz in the 2.9 - 4.2 µm wavelength region, due to the cascaded quadratic nonlinear effect. The independent tunability of the two idlers makes the optical parametric oscillator a promising source for ultrafast pulse generation towards the THz wavelength region, based on different frequency generation. In addition, the observed frequency doubled idler within the crystal indicates the possibility to realize a broadband optical self-phase locking between pump, signal, idler and higher order generated parametric lights.

Doppler-broadened mid-infrared noise-immune cavity-enhanced optical heterodyne molecular spectrometry based on an optical parametric oscillator for trace gas detection.

An optical parametric oscillator based Doppler-broadened (Db) noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) system suitable for addressing fundamental vibrational transitions in the 3.2-3.9 µm mid-infrared (MIR) region has been realized. An Allan-Werle analysis provides a detection sensitivity of methane of 1.5×10(-9) cm(-1) with a 20 s integration time, which corresponds to 90 ppt of CH4 if detected at the strongest transition addressed at 40 Torr. This supersedes that of previous Db MIR NICE-OHMS demonstrations and suggests that the technique can be suitable for detection of both the environmentally important (13)CH(4) and CH3D isotopologues. It also opens up for detection of many other molecular species at ppt and sub-ppt concentration levels.

Aboveground and Belowground Herbivores Synergistically Induce Volatile Organic Sulfur Compound Emissions from Shoots but Not from Roots.

Studies on aboveground (AG) plant organs have shown that volatile organic compound (VOC) emissions differ between simultaneous attack by herbivores and single herbivore attack. There is growing evidence that interactive effects of simultaneous herbivory also occur across the root-shoot interface. In our study, Brassica rapa roots were infested with root fly larvae (Delia radicum) and the shoots infested with Pieris brassicae, either singly or simultaneously, to study these root-shoot interactions. As an analytical platform, we used Proton Transfer Reaction Mass Spectrometry (PTR-MS) to investigate VOCs over a 3 day time period. Our set-up allowed us to monitor root and shoot emissions concurrently on the same plant. Focus was placed on the sulfur-containing compounds; methanethiol, dimethylsulfide (DMS), and dimethyldisulfide (DMDS), because these compounds previously have been shown to be biologically active in the interactions of Brassica plants, herbivores, parasitoids, and predators, yet have received relatively little attention. The shoots of plants simultaneously infested with AG and belowground (BG) herbivores emitted higher levels of sulfur-containing compounds than plants with a single herbivore species present. In contrast, the emission of sulfur VOCs from the plant roots increased as a consequence of root herbivory, independent of the presence of an AG herbivore. The onset of root emissions was more rapid after damage than the onset of shoot emissions. The shoots of double infested plants also emitted higher levels of methanol. Thus, interactive effects of root and shoot herbivores exhibit more strongly in the VOC emissions from the shoots than from the roots, implying the involvement of specific signaling interactions.

Real-time monitoring of endogenous lipid peroxidation by exhaled ethylene in patients undergoing cardiac surgery.

Pulmonary and systemic organ injury produced by oxidative stress including lipid peroxidation is a fundamental tenet of ischemia-reperfusion injury, inflammatory response to cardiac surgery, and cardiopulmonary bypass (CPB) but is not routinely measured in a surgically relevant time frame. To initiate a paradigm shift toward noninvasive and real-time monitoring of endogenous lipid peroxidation, we have explored pulmonary excretion and dynamism of exhaled breath ethylene during cardiac surgery to test the hypothesis that surgical technique and ischemia-reperfusion triggers lipid peroxidation. We have employed laser photoacoustic spectroscopy to measure real-time trace concentrations of ethylene from the patient breath and from the CPB machine. Patients undergoing aortic or mitral valve surgery-requiring CPB (n = 15) or off-pump coronary artery bypass surgery (OPCAB) (n = 7) were studied. Skin and tissue incision by diathermy caused striking (> 30-fold) increases in exhaled ethylene resulting in elevated levels until CPB. Gaseous ethylene in the CPB circuit was raised upon the establishment of CPB (> 10-fold) and decreased over time. Reperfusion of myocardium and lungs did not appear to enhance ethylene levels significantly. During OPCAB surgery, we have observed increased ethylene in 16 of 30 documented reperfusion events associated with coronary and aortic anastomoses. Therefore, novel real-time monitoring of endogenous lipid peroxidation in the intraoperative setting provides unparalleled detail of endogenous and surgery-triggered production of ethylene. Diathermy and unprotected regional myocardial ischemia and reperfusion are the most significant contributors to increased ethylene.

Two-crystal mid-infrared optical parametric oscillator for absorption and dispersion dual-comb spectroscopy.

We present a femtosecond optical parametric oscillator (OPO) containing two magnesium-doped periodically poled lithium niobate crystals in a singly resonant ring cavity, pumped by two mode-locked Yb-fiber lasers. As such, the OPO generates two idler combs (up to 220 mW), covering a wavelength range from 2.7 to 4.2 µm, from which a mid-infrared dual-comb Fourier transform spectrometer is constructed. By detecting the heterodyning signal between the two idler beams a full broadband spectrum of a molecular gas can be observed over 250 cm(-1) within 70 µs with a spectral resolution of 15 GHz. The absorption and dispersion spectra of acetylene and methane have been measured around 3000 cm(-1), indicating that this OPO represents an ideal broadband mid-infrared source for fast chemical sensing.

An assessment of the biotechnological use of hemoglobin modulation in cereals.

Non-symbiotic hemoglobin (nsHb) genes are ubiquitous in plants, but their biological functions have mostly been studied in model plant species rather than in crops. nsHb influences cell signaling and metabolism by modulating the levels of nitric oxide (NO). Class 1 nsHb is upregulated under hypoxia and is involved in various biotic and abiotic stress responses. Ectopic overexpression of nsHb in Arabidopsis thaliana accelerates development, whilst targeted overexpression in seeds can increase seed yield. Such observations suggest that manipulating nsHb could be a valid biotechnological target. We studied the effects of overexpression of class 1 nsHb in the monocotyledonous crop plant barley (Hordeum vulgare cv. Golden Promise). nsHb was shown to be involved in NO metabolism in barley, as ectopic overexpression reduced the amount of NO released during hypoxia. Further, as in Arabidopsis, nsHb overexpression compromised basal resistance toward pathogens in barley. However, unlike Arabidopsis, nsHb ectopic overexpression delayed growth and development in barley, and seed specific overexpression reduced seed yield. Thus, nsHb overexpression in barley does not seem to be an efficient strategy for increasing yield in cereal crops. These findings highlight the necessity for using actual crop plants rather than laboratory model plants when assessing the effects of biotechnological approaches to crop improvement.

Dynamic changes of the ethylene biosynthesis in 'Jonagold' apple.

In this study, the short-term and dynamic changes of the ethylene biosynthesis of Jonagold apple during and after application of controlled atmosphere (CA) storage conditions were quantified using a systems biology approach. Rapid responses to imposed temperature and atmospheric conditions were captured by continuous online photoacoustic ethylene measurements. Discrete destructive sampling was done to understand observed changes of ethylene biosynthesis at the transcriptional, translational and metabolic level. Application of the ethylene inhibitor 1-methylcyclopropene (1-MCP) allowed for the discrimination between ethylene-mediated changes and ethylene-independent changes related to the imposed conditions. Online ethylene measurements showed fast and slower responses during and after application of CA conditions. The changes in 1-aminocyclopropane-1-carboxylate synthase (ACS) activity were most correlated with changes in ACS1 expression and regulated the cold-induced increase in ethylene production during the early chilling phase. Transcription of ACS3 was found ethylene independent and was triggered upon warming of CA-stored apples. Increased expression of ACO1 during shelf life led to a strong increase in 1-aminocyclopropane-1-carboxylate oxidase (ACO) activity, required for the exponential production of ethylene during system 2. Expression of ACO2 and ACO3 was upregulated in 1-MCP-treated fruit showing a negative correlation with ethylene production. ACO activity never became rate limiting.

Tobacco LSU-like protein couples sulphur-deficiency response with ethylene signalling pathway.

Most genes from the plant-specific family encoding Response to Low Sulphur (LSU)-like proteins are strongly induced in sulphur (S)-deficient conditions. The exact role of these proteins remains unclear; however, some data suggest their importance for plants' adjustment to nutrient deficiency and other environmental stresses. This work established that the regulation of ethylene signalling is a part of plants' response to S deficiency and showed the interaction between UP9C, a tobacco LSU family member, and one of the tobacco isoforms of 1-aminocyclopropane-1-carboxylic acid oxidase (ACO2A). Increase in ethylene level induced by S deficiency does not take place in tobacco plants with UP9C expressed in an antisense orientation. Based on transcriptomics data, this work also demonstrated that the majority of tobacco's response to S deficiency is misregulated in plants expressing UP9C-antisense. A link between response to S deficiency, ethylene sensing, and LSU-like proteins was emphasized by changes in expression of the genes encoding ethylene receptors and F-box proteins specific for the ethylene pathway.