Dual-comb spectroscopy of ammonia formation in non-thermal plasmas.

Plasma-activated chemical transformations promise the efficient synthesis of salient chemical products. However, the reaction pathways that lead to desirable products are often unknown, and key quantum-state-resolved information regarding the involved molecular species is lacking. Here we use quantum cascade laser dual-comb spectroscopy (QCL-DCS) to probe plasma-activated NH3 generation with rotational and vibrational state resolution, quantifying state-specific number densities via broadband spectral analysis. The measurements reveal unique translational, rotational and vibrational temperatures for NH3 products, indicative of a highly reactive, non-thermal environment. Ultimately, we postulate on the energy transfer mechanisms that explain trends in temperatures and number densities observed for NH3 generated in low-pressure nitrogen-hydrogen (N2-H2) plasmas.

A multiplex inhalation platform to model in situ like aerosol delivery in a breathing lung-on-chip.

Prolonged exposure to environmental respirable toxicants can lead to the development and worsening of severe respiratory diseases such as asthma, chronic obstructive pulmonary disease (COPD) and fibrosis. The limited number of FDA-approved inhaled drugs for these serious lung conditions has led to a shift from in vivo towards the use of alternative in vitro human-relevant models to better predict the toxicity of inhaled particles in preclinical research. While there are several inhalation exposure models for the upper airways, the fragile and dynamic nature of the alveolar microenvironment has limited the development of reproducible exposure models for the distal lung. Here, we present a mechanistic approach using a new generation of exposure systems, the Cloud α AX12. This novel in vitro inhalation tool consists of a cloud-based exposure chamber (VITROCELL) that integrates the breathing AXLung-on-chip system (AlveoliX). The ultrathin and porous membrane of the AX12 plate was used to create a complex multicellular model that enables key physiological culture conditions: the air-liquid interface (ALI) and the three-dimensional cyclic stretch (CS). Human-relevant cellular models were established for a) the distal alveolar-capillary interface using primary cell-derived immortalized alveolar epithelial cells (AXiAECs), macrophages (THP-1) and endothelial (HLMVEC) cells, and b) the upper-airways using Calu3 cells. Primary human alveolar epithelial cells (AXhAEpCs) were used to validate the toxicity results obtained from the immortalized cell lines. To mimic in vivo relevant aerosol exposures with the Cloud α AX12, three different models were established using: a) titanium dioxide (TiO2) and zinc oxide nanoparticles b) polyhexamethylene guanidine a toxic chemical and c) an anti-inflammatory inhaled corticosteroid, fluticasone propionate (FL). Our results suggest an important synergistic effect on the air-blood barrier sensitivity, cytotoxicity and inflammation, when air-liquid interface and cyclic stretch culture conditions are combined. To the best of our knowledge, this is the first time that an in vitro inhalation exposure system for the distal lung has been described with a breathing lung-on-chip technology. The Cloud α AX12 model thus represents a state-of-the-art pre-clinical tool to study inhalation toxicity risks, drug safety and efficacy.

Frequency noise correlation between the offset frequency and the mode spacing in a mid-infrared quantum cascade laser frequency comb.

The generation of frequency combs in the mid-infrared (MIR) spectral range by quantum cascade lasers (QCLs) has the potential for revolutionizing dual-comb multi-heterodyne spectroscopy in the molecular fingerprint region. However, in contrast to frequency combs based on passively mode-locked ultrafast lasers, their operation relies on a completely different mechanism resulting from a four-wave mixing process occurring in the semiconductor gain medium that locks the modes together. As a result, these lasers do not emit pulses and no direct self-referencing of a QCL comb spectrum has been achieved so far. Here, we present a detailed frequency noise characterization of a MIR QCL frequency comb operating at a wavelength of 8 µm with a mode spacing of ∼7.4 GHz. Using a beat measurement with a narrow-linewidth single-mode QCL in combination with a dedicated electrical scheme, we measured the frequency noise properties of an optical mode of the QCL comb, and indirectly of its offset frequency for the first time, without detecting it by the standard approach of nonlinear interferometry applied to ultrafast mode-locked lasers. In addition, we also separately measured the noise of the comb mode spacing extracted electrically from the QCL. We observed a strong anti-correlation between the frequency fluctuations of the offset frequency and mode spacing, leading to optical modes with a linewidth slightly below 1 MHz in the free-running QCL comb (at 1-s integration time), which is narrower than the individual contributions of the offset frequency and mode spacing that are at least 2 MHz each.

High-resolution and gapless dual comb spectroscopy with current-tuned quantum cascade lasers.

We present gapless, high-resolution absorption and dispersion spectra obtained with quantum cascade laser frequency combs covering 55 cm-1. Using phase-sensitive dual comb design, the comb lines are gradually swept over 10 GHz, corresponding to the free spectral range of the laser devices, by applying a current modulation. We show that with interleaving the spectral point spacing is reduced by more than four orders of magnitude over the full spectral span of the frequency comb. The potential of this technique for high-precision gas sensing is illustrated by measuring the low pressure (107 hPa) absorption and dispersion spectra of methane spanning the range of 1170 cm-1 - 1225 cm-1 with a resolution of 0.001 cm-1.

Single-Shot Sub-microsecond Mid-infrared Spectroscopy on Protein Reactions with Quantum Cascade Laser Frequency Combs.

The kinetic analysis of irreversible protein reactions requires an analytical technique that provides access to time-dependent infrared spectra in a single shot. Here, we present a spectrometer based on dual-frequency-comb spectroscopy using mid-infrared frequency combs generated by quantum cascade lasers. Attenuation of the intensity of the combs by molecular vibrational resonances results in absorption spectra covering 55 cm-1 in the fingerprint region. The setup has a native resolution of 0.3 cm-1, noise levels in the µOD range, and achieves sub-microsecond time resolution. We demonstrate the simultaneous recording of both spectra and transients of the photoactivated proton pump bacteriorhodopsin. More importantly, a single shot, i.e., a single visible light excitation, is sufficient to extract spectral and kinetic characteristics of several intermediates in the bacteriorhodopsin photocycle. This development paves the way for the noninvasive analysis of enzymatic conversions with high time resolution, broad spectral coverage, and minimal sample consumption.

Rf-modulation of mid-infrared distributed feedback quantum cascade lasers.

We present the electrical and optical characterization and theoretical modeling of the transient behavior of regular 4.5-µm single-mode emitting distributed feedback (DFB) quantum cascade lasers (QCLs). Low residual capacitance together with a high-frequency optimized three-terminal coplanar waveguide configuration leads to modulation frequencies up to 23.5 GHz (optical) and 26.5 GHz (electrical), respectively. A maximum 3-dB cut-off value of 6.6 GHz in a microwave rectification scheme is obtained, with a significant increase in electrical modulation bandwidth when increasing the DC-current for the entire current range of the devices. Optical measurements by means of FTIR-spectroscopy and a heterodyne beating experiment reveal the presence of a resonance peak, due to coupling of the lasing DFB- with its neighboring below-threshold Fabry-Pérot-(FP-)mode, when modulating around the cavity roundtrip frequency. This resonance is modeled by a 2-mode Maxwell-Bloch formalism. It enhances only one sideband and consequently leads to the first experimental observation of the single-sideband regime in such kind of devices.

Simultaneous measurement of NO and NO(2) by dual-wavelength quantum cascade laser spectroscopy.

The concept of a multi-wavelength quantum cascade laser emitting at two or more spectrally well-separated wavelengths is highly appealing for applied spectroscopy, as it allows detecting several species with compact and cost-efficient optical setups. Here we present a practical realization of such a dual-wavelength setup, which is based on a room-temperature quantum cascade laser emitting single-mode at 1600 cm-1 and 1900 cm-1 and is thus well-suited for simultaneous NO and NO2 detection. Operated in a time-division multiplexed mode, our spectrometer reaches detection limits of 0.5 and 1.5 ppb for NO2 and NO, respectively. The performance of the system is validated against the well-established chemiluminescence detection while measuring the NOx emissions on an automotive test-bench, as well as upon monitoring the pollution at a suburban site.

Dual-comb spectroscopy based on quantum-cascade-laser frequency combs.

Dual-comb spectroscopy performed in the mid-infrared-where molecules have their strongest rotovibrational absorption lines-offers the promise of high spectral resolution broadband spectroscopy with very short acquisition times (µs) and no moving parts. Recently, we demonstrated frequency comb operation of a quantum-cascade-laser. We now use that device in a compact, dual-comb spectrometer. The noise properties of the heterodyne beat are close to the shot noise limit. Broadband (15 cm(-1)) high-resolution (80 MHz) absorption spectroscopy of both a GaAs etalon and water vapour is demonstrated, showing the potential of quantum-cascade-laser frequency combs as the basis for a compact, all solid-state, broadband chemical sensor.

Mid-infrared frequency comb based on a quantum cascade laser.

Optical frequency combs act as rulers in the frequency domain and have opened new avenues in many fields such as fundamental time metrology, spectroscopy and frequency synthesis. In particular, spectroscopy by means of optical frequency combs has surpassed the precision and speed of Fourier spectrometers. Such a spectroscopy technique is especially relevant for the mid-infrared range, where the fundamental rotational-vibrational bands of most light molecules are found. Most mid-infrared comb sources are based on down-conversion of near-infrared, mode-locked, ultrafast lasers using nonlinear crystals. Their use in frequency comb spectroscopy applications has resulted in an unequalled combination of spectral coverage, resolution and sensitivity. Another means of comb generation is pumping an ultrahigh-quality factor microresonator with a continuous-wave laser. However, these combs depend on a chain of optical components, which limits their use. Therefore, to widen the spectroscopic applications of such mid-infrared combs, a more direct and compact generation scheme, using electrical injection, is preferable. Here we present a compact, broadband, semiconductor frequency comb generator that operates in the mid-infrared. We demonstrate that the modes of a continuous-wave, free-running, broadband quantum cascade laser are phase-locked. Combining mode proliferation based on four-wave mixing with gain provided by the quantum cascade laser leads to a phase relation similar to that of a frequency-modulated laser. The comb centre carrier wavelength is 7 micrometres. We identify a narrow drive current range with intermode beat linewidths narrower than 10 hertz. We find comb bandwidths of 4.4 per cent with an intermode stability of less than or equal to 200 hertz. The intermode beat can be varied over a frequency range of 65 kilohertz by radio-frequency injection. The large gain bandwidth and independent control over the carrier frequency offset and the mode spacing open the way to broadband, compact, all-solid-state mid-infrared spectrometers.

Room-temperature continuous-wave operation of an external-cavity quantum cascade laser.

Room-temperature, continuous-wave operation of an external-cavity quantum cascade laser (EC-QCL) is reported. Single-mode tuning range of 120 cm(-1) was achieved, from 7.96 to 8.84 microm. The gain chips utilized are based on the bound to continuum design and were fabricated as buried heterostructure lasers. Gap-free tuning (mode hops only on the external-cavity modes) is demonstrated for an antireflection-coated laser, just by grating rotation. The EC-QCL was implemented in a Littrow setup and an average power of 1.5 mW was obtained at 20 degrees C, while a peak power of 20 mW was obtained for a modified Littrow setup with the back extraction of light.