With the aim to capture and subsequent selective trapping of CO2, a nanocomposite has been developed through selective modification of the outer surface of the halloysite nanotubes (HNTs) with an organosilane to make the nanocomposite a novel solid-phase adsorbent to adsorb CO2 from the atmosphere at standard ambient temperature and pressure. The preferential adsorption of three major abundant isotopes of CO2 (12C16O2, 13C16O2, and 12C16O18O) from the ambient air by amine functionalized HNTs has been explored using an optical cavity-enhanced integrated cavity output spectroscopy. CO2 adsorption/desorption cycling measurements demonstrate that the adsorbent can be regenerated at relatively low temperature and thus, recycled repeatedly to capture atmospheric CO2. The amine grafted halloysite shows excellent stability even in oxidative environments and has high efficacy of CO2 capture, introducing a new route to the adsorption of isotope selective atmospheric CO2.

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.

Carbonic anhydrase (CA), a well-characterized metalloenzyme, is associated with oxygen-18 ( 18O)-isotopic fractionations of CO2. To investigate how CA activity links the 18O of breath CO2 to pre-diabetes (PD) and type 2 diabetes (T2D) during metabolism, we studied pre- and post-dose CA activities in erythrocytes with simultaneous monitoring of 18O/ 16O-isotope ratios of breath CO2 and thereafter elucidated potential metabolic pathways underlying CA alteration in the pathogenesis of T2D. Here we show that the post-dose CA activity in both T2D and PD was markedly enhanced, whereas the non-diabetic controls (NDC) exhibited a considerable reduction in post-dose CA activity when compared with their basal CA activities. However, T2D and PD exhibited isotopic enrichments of 18O in breath CO2, while a marked depletion of 18O in CO2 was manifested in NDC. Thus, the isotopic enrichments and depletions of 18O in breath CO2 were well correlated with the changes in CA activities for controls, PD and T2D. Our findings suggest the changes in CA activities in erythrocytes may contribute to the pathogenesis of T2D and the breath C 18O 16O regulated by the CA activity as a potential biomarker for non-invasive assessment of T2D, and thus may open a new method for treating T2D.

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The underlying mechanisms of the triple-oxygen (16O, 17O, and 18O) isotopic content of deuterated (D) isotopologues of water in H–D exchange reactions in the gas phase remain elusive. Herein, we have demonstrated a high-resolution gas-phase spectral analysis of doubly (D2O) and singly (HDO) deuterated isotopologues of water in the region around 7.8 μm using quantum cascade laser-based cavity ring-down spectroscopy. Isotopic fractionations among doubly and singly deuterated species of water, D2 16O, HD16O, HD17O, and HD18O, in the gas phase were carried out by probing the fundamental and hot band transitions in the ν2 (bending) mode of D2O and the fundamental ν2 transitions for the other water isotopes. We subsequently investigated the fractionations of different D-enriched water isotopologues for the H–D exchange reaction using various mixtures of D2O in H2O. We explored the potential role of triple-oxygen isotopic contents through enrichments and depletions of HD16O, HD17O, and HD18O, involved in the H–D reaction. Our first clear, direct, and quantitative experimental evidence reveals a new picture of gas-phase isotopic fractionation chemistry in a mixture of light and heavy water (H2O–D2O).