A number of atmospheric pollutants and greenhouse gases have strong fundamental vibrational transitions within the spectral range of 7.5-8 µm, which marks the region as particularly important for trace gas sensing. Here, we report the development of a mid-infrared continuouswave (cw) cavity ring-down spectroscopy (CRDS) technique coupled with an external-cavity (EC) mode-hop-free quantum cascade laser (QCL) operating at 7.5 µm. We validated the EC-QCL based high-resolution cw-CRDS system by measuring 12 CH 4 and 13 CH 4 isotopes of methane (CH 4 ) which served as a benchmark molecule. The direct, quantitative and selective measurements of 12 C and 13 C isotopes of CH 4 in ambient air as well as in human breath samples in the levels of parts per billion by volume were made by probing one of the strongest fundamental vibrational transitions of CH 4 arising from the asymmetric bending (ν 4 band) vibrations of the bonds centred at ~1327.244 cm −1 and ~1332.946 cm −1 , respectively. We achieved a noise-equivalent absorption coefficient of 1.86 × 10 −9 cm −1 Hz −1/2 with 100 Hz data acquisition rate for the current cw-CRDS spectrometer. The current high-resolution cw-CRDS system could be further exploited to harness the full advantage of the spectral region covering 7.5-8 µm to monitor several other trace molecular species along with their isotopic compositions.

The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection.

A laser based N2O sensor for atmospheric measurement.

A high-resolution cavity ring-down spectroscopic (CRDS) system based on a continuous wave (cw) mode-hop-free (MHF) external-cavity quantum cascade laser (EC-QCL) operating at λ∼5.2  μm has been developed for ultrasensitive detection of nitric oxide (NO). We report the performance of the high-resolution EC-QCL based cw-CRDS instrument by measuring the rotationally resolved Λ-doublet e and f components of the P(7.5) line in the fundamental band of NO at 1850.169  cm^-1 and 1850.179  cm^-1. A noise-equivalent absorption coefficient of 1.01×10^-9 cm^-1 Hz^-1/2 was achieved based on an empty cavity ring-down time of τ₀=5.6  μs and standard deviation of 0.11% with averaging of six ring-down time determinations. The CRDS sensor demonstrates the advantages of measuring parts per billion NO concentrations in N₂, as well as in human breath samples with ultrahigh sensitivity and specificity. The CRDS system could also be generalized to measure simultaneously many other trace molecular species within the broad tuning range of cw EC-QCL, as well as for studying the rotationally resolved hyperfine structures.

Monitoring three stable isotopes of H2S using a QCL based CRDS technique.