Integrated cavity output spectroscopy measurements of NO levels in breath with a pulsed room-temperature QCL

A cavity-enhanced spectrometer is developed for detection of exhaled nitric oxide in human breath. A thermoelectrically cooled, pulsed, quantum cascade laser, coupled to a high-finesse cavity, is used for trace-gas measurements. The trace-gas analyzer operates at 5.2 microns and utilizes integrated cavity output spectroscopy. Effective optical path lengths of 1.5 km are achieved in a 50-cm-length cell with a sample volume of 60 mL. The instrument is also capable of simultaneously measuringCO2 concentration in exhaled breath. Measurements were performed on human breath samples as well as simulated breath samples. Here we report a detection limit of ≤ 1 ppbv in 4 s for NO in human breath samples.     

Infrared laser-spectroscopic analysis of <Superscript>14</Superscript>NO and <Superscript>15</Superscript>NO in human breath

We report on monitoring of nitric oxide (NO) traces in human breath via infrared cavity leak-out spectroscopy. Using a CO sideband laser near 5 μm wavelength and an optical cavity with two high-reflectivity mirrors (R=99.98%), the minimum detectable absorption is 2×10⁻¹⁰ cm⁻¹ Hz^1/2. This allows for spectroscopic analysis of rare NO isotopologues with unprecedented sensitivity. Application to simultaneous online detection of ¹⁴NO and ¹⁵NO in breath samples collected in the nasal cavity is described for the first time. We achieved a noise-equivalent detection limit of 7 parts per trillion for nasal ¹⁵NO (integration time: 70 s).     

Online monitoring of ethane traces in exhaled breath with a difference frequency generation spectrometer

We report a transportable mid-infrared laser cavity leak-out spectrometer for online detection of trace gases. The laser spectrometer is based on continuous-wave difference-frequency generation in the wavelength region around 3 μm. Sensitive spectroscopic trace gas monitoring was achieved using a high-finesse ring-down cavity. For difference-frequency generation, we use a periodically poled lithium niobate (PPLN) crystal, pumped by a Nd:YAG laser (signal wave) and a diode laser (pump wave) with a tapered amplifier. A maximum power of 280 μW near λ=3.3 μm is achieved using a pump power of 180 mW at 807 nm, a signal power of 890 mW at 1064.46 nm, and a 50-mm-long PPLN crystal. The resulting system proved to be a unique tool with high sensitivity and specificity for rapid and precise breath testing. We demonstrate spectroscopic online monitoring of ethane traces in exhaled human breath with a precision of 270 parts per trillion (1σ) and a time resolution of 1 s. PACS 42.62.Be; 42.60.-v; 07.57.Ty     

Automatically tunable continuous-wave optical parametric oscillator for high-resolution spectroscopy and sensitive trace-gas detection

We present a high-power (2.75 W), broadly tunable (2.75–3.83 μm) continuous-wave optical parametric oscillator based on MgO-doped periodically poled lithium niobate. Automated tuning of the pump laser, etalon and crystal temperature results in a continuous wavelength coverage up to 450 cm^-1 per poling period at <5×10^-4 cm^-1 resolution. The versatility of the optical parametric oscillator as a coherent light source in trace-gas detection is demonstrated with photoacoustic and cavity ring-down spectroscopy. A 17-cm^-1-wide CO₂ spectrum at 2.8 μm and multi-component gas mixtures of methane, ethane and water in human breath were measured using photoacoustics. Methane (at 3.2 μm) and ethane (at 3.3 μm) were detected using cavity ring-down spectroscopy with detection limits of 0.16 and 0.07 parts per billion by volume, respectively. A recording of ¹²CH₄ and ¹³CH₄ isotopes of methane shows the ability to detect both species simultaneously at similar sensitivities. PACS 42.65.Yj; 42.72.Ai; 42.62.Fi     

Parts per trillion sensitivity for ethane in air with an optical parametric oscillator cavity leak-out spectrometer

Spectroscopic detection of ethane in the 3-microm wavelength region was performed by means of a cw optical parametric oscillator and cavity leak-out. We achieved a minimum detectable absorption coefficient of 1.6 x 10(-10) cm 1/square root of Hz, corresponding to an ethane detection limit of 6 parts per trillion/square root of Hz. For 3-min integration time the detection limit was 0.5 parts per trillion. The levels are to our knowledge the best demonstrated so far. These frequency-tuning capabilities facilitated multigas analysis with simultaneous monitoring of ethane, methane, and water vapor in human breath.     

Optical parametric oscillator based off-axis integrated cavity output spectroscopy for rapid chemical sensing

An optical parametric oscillator (OPO), pumped by a fiber-amplified diode laser, is combined with off-axis integrated cavity output spectroscopy (OA-ICOS). The cw OPO (power 1.2 W, tunability 3-4 μm, 5 cm(-1) mode-hop-free tuning) has a tuning speed of 100 THz/s, which is ideal for rapid and sensitive trace gas detection. Combined with OA-ICOS, a detection limit of 50 parts per trillion by volume (1×10(12)) of ethane (C(2)H(6)) in nitrogen was obtained in 0.25s at 2997 cm(-1), corresponding to a noise equivalent absorption sensitivity of 4.8×10(-11) cm(-1) Hz(-1/2). The system demonstrates real-time measurements of methane and water in exhaled human breath.     

Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C₂H₂) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS. Received: 22 October 2001 / Revised version: 16 January 2002 / Published online: 14 March 2002     

Near-infrared cavity enhanced absorption spectroscopy of hot water and OH in an oven and in flames

A compact diode laser operating around 1.5 μm was used to measure cavity enhanced absorption spectra of hot water molecules and OH radicals in radiative environments under atmospheric conditions. Spectra of air were measured in an oven at temperatures ranging from 300 K to 1500 K. These spectra contained rovibrational lines from water and OH. The water spectra were compared to simulations from the HITRAN and HITEMP databases. Furthermore, spectra were recorded in the flame of a flat methane/air burner and in an oxyacetylene flame produced by a welding torch. The results show that cavity enhanced absorption spectroscopy provides a sensitive method for rapid monitoring of species in radiative environments. Received: 22 February 2001 / Revised version: 23 April 2001 / Published online: 7 June 2001     

Selected optoelectronic sensors in medical applications

Optoelectronic technology plays an important role in medical diagnosis. In the paper a review of some optoelectronic sensors for invasive and non-invasive human health test is presented. The main attention is paid on their basic operation principle and medical usefulness. The paper presents also own research related to developing of tools for human breath analysis. Breath sample unit and three gaseous biomarkers analyzer employing laser absorption spectroscopy designed for clinical diagnostics were described. The analyzer is equipped with sensors for CO, CH₄ and NO detection. The sensors operate using multi-pass spectroscopy with wavelength modulation method (MUPASS-WMS) and cavity enhanced spectroscopy (CEAS).     

Ultra-sensitive mid-infrared cavity leak-out spectroscopy using a cw optical parametric oscillator

We report a portable, all-solid-state, mid-infrared spectrometer for trace-gas analysis. The light source is a continuous-wave optical parametric oscillator based on PPLN and pumped by a Nd:YAG laser at 1064 nm. The generated single-frequency idler output covers the wavelength region between 2.35 and 3.75 μm. With its narrow line width, this light source is suitable for precise trace-gas analysis with very high sensitivity. Using cavity leak-out spectroscopy we achieved a minimum detectable absorption coefficient of 1.2×10^-9 /cm (integration time: 16 s), corresponding, for example, to a detection limit of 300 parts per trillion ethane. This sensitivity and the compact design make this trace-gas analyzer a promising tool for various in situ environmental and medical applications. Received: 19 September 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733-474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

High-precision pulsed photoacoustic spectroscopy in NO2-N2

A method for high-precision pulsed photoacoustic spectroscopy applied to a simple system for detection of NO₂ traces in nitrogen is presented. The acoustic signal from a closed cell containing NO₂/N₂ samples irradiated by a pulsed visible laser is analyzed in the frequency domain. A signal-processing method to obtain a high-resolution Fourier spectrum of the signal was developed. An accurate fitting of the resonance peaks with Lorentzian profiles gives high-precision determination of the amplitude and width of the resonance peaks. The resonance maximum is proportional to the absorbed energy; therefore, the choice of the laser wavelength, linewidth and frequency stability are critical for a precise calibration due to the fine structure of the NO₂ optical spectrum. The method also allows high-accuracy measurement of the Q of the acoustic cavity. The dependence of Q on the buffer gas pressure is characteristic of an acoustic cavity where energy losses near the walls predominate. Consequently, an important enhancement of sensitivity takes place at high N₂ pressure. Received: 1 June 2001 / Revised version: 27 July 2001 / Published online: 7 November 2001     

Ultrasensitive laser spectroscopy for breath analysis

At present there are many reasons for seeking new methods and technologies that aim to develop new and more perfect sensors for different chemical compounds. However, the main reasons are safety ensuring and health care. In the paper, recent advances in the human breath analysis by the use of different techniques are presented. We have selected non-invasive ones ensuring detection of pathogenic changes at a molecular level. The presence of certain molecules in the human breath is used as an indicator of a specific disease. Thus, the analysis of the human breath is very useful for health monitoring. We have shown some examples of diseases’ biomarkers and various methods capable of detecting them. Described methods have been divided into non-optical and optical methods. The former ones are the following: gas chromatography, flame ionization detection, mass spectrometry, ion mobility spectrometry, proton transfer reaction mass spectrometry, selected ion flow tube mass spectrometry. In recent twenty years, the optical methods have become more popular, especially the laser techniques. They have a great potential for detection and monitoring of the components in the gas phase. These methods are characterized by high sensitivity and good selectivity. The spectroscopic sensors provide the opportunity to detect specific gases and to measure their concentration either in a sampling place or a remote one. Multipass spectroscopy, cavity ring-down spectroscopy, and photo-acoustic spectroscopy were characterised in the paper as well.     

Quantitative gas measurements using a versatile OPO-based cavity ringdown spectrometer and the comparison with spectroscopic databases

A versatile OPO-based cavity ringdown spectrometer is reported for quantitative and sensitive gas measurement down to nmol/mol levels. The system is based on cavity ringdown spectroscopy (CRDS) in combination with a continuous wave optical parametric oscillator tunable from 2693 to 3505 nm. Using a single set of CRDS mirrors, spectra were recorded of methane, ethane, benzene, propane, water, acetone and formaldehyde. Gas mixtures were gravimetrically prepared in cylinders or via dynamic generation using diffusion tubes (formaldehyde). Results were compared with data from the Hitran, PNNL and NIST databases. Good agreement was found with PNNL and NIST data for most molecules while agreement with Hitran was less for ethane and formaldehyde.     

Tuning and stability of a continuous-wave mid-infrared high-power single resonant optical parametric oscillator

A 2.2-W continuous-wave, continuously tunable, single-frequency OPO has been developed in the 3.0–3.8 μm wavelength range for the detection of molecular trace gasses. The oscillation threshold, output power and stability of the single resonant OPO were improved by optimizing pump beam waist and OPO cavity length. Both air-spaced and solid etalons were tested to frequency stabilize and tune the OPO, from which the solid etalon gave a better performance. Temperature oscillations in the PPLN crystal caused oscillations in the idler wavelength of less than 200 MHz over 300 s; the short-term stability was less than 3 MHz over 1 s. The high laser power, in combination with photoacoustic spectroscopy, achieved a detection limit of 10 parts-per-trillion for ethane in nitrogen. Received: 9 April 2002 / Revised version: 14 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax:+31-24/3653311, E-Mail: maartenh@sci.kun.nl     

基于光腔衰荡光谱的便携式呼气异戊二烯分析仪性能评估

呼气异戊二烯是一种内源性代谢产物,其含量与人体血液中的胆固醇水平存在关联。但人体呼气影响因素众多,寻找其与胆固醇水平诊断参数的定量相关性,需要对选取的特定人群进行有效的呼吸气体分析（实时、在线、高灵敏度、高选择性、高精度的大量呼气数据获取）。光腔衰荡光谱（CRDS）是一种具有极高灵敏度、稳定性和选择性的光谱技术。采用目前市场在售的单波长紧凑型半导体紫外激光器,搭建了一套基于CRDS的呼气异戊二烯分析仪,该分析仪主要由激光系统、真空腔体、光电探测模块以及数据采集模块构成。线性拟合的结果显示所获得的衰荡信号接近单指数衰减（R2=0.998 39）,符合朗伯-比尔定律。探究了不同信号平均次数对衰荡信号稳定性的影响,综合考虑衰荡信号的稳定性和分析仪的响应时间,采用128次作为实验过程中的信号平均次数。对呼气异戊二烯分析仪的性能进行了测试,为了表征分析仪的稳定性,持续测量了分析仪16 min的真空衰荡时间。使用氮气、空气和呼吸样本,测量了呼气异戊二烯分析仪的重复性和响应速度。为了测试分析仪的线性度,测量了不同粒子数密度的异戊二烯标准气体（10×10-9,30×10-9,50×10-9,100×10-9,200×10-9）的衰荡时间。最后分析了在224 nm测量异戊二烯存在的光谱干扰问题（NO,N₂O和丙酮）。实验表明：分析仪具有高的灵敏度（检测极限为0.49×10-9）、良好的重复性、稳定性（0.48%）、近实时的响应速度（1秒测量一个数据）和良好的线性度（R2=0.993 13）,将检测极限提高至现有水平的1/1 000。研究证明基于CRDS的便携式呼气异戊二烯分析仪可实现对人体呼气异戊二烯的有效分析。     

Controlled two-pulse generation in Q-switch mode from a single laser using Q-modulator with frustrated total internal reflection

In this work a cavity design for double-pulse generation in Q-switched mode from a single laser is proposed, based on the construction of a second laser channel using a FTIR (frustrated total internal reflection) Q-modulator. A time interval between the two pulses from 500 ns to 120 μs is obtained in a Nd:YAG laser. A comparison with other methods and cavity designs for double-pulse generation is presented. The case when this technique is applied on a tunable laser with metastable upper laser level (Cr:LiCAF, Cr:LiSAF, Alexandrite, Co:MgF₂ or other) is also considered. Even though the method presented in the paper does not rely only on the cavity configuration proposed, some advantages can be obtained – both polarization and wavelength-independent tuning without polarization and wavelength restrictions in combination with the possibility of different wavelengths and polarizations in each pulse. Moreover, by using an active medium generating wavelengths around and up to 3 μm, the Pockels-cell-Q-switch optical transmission problems can be avoided. Received: 9 May 2001 / Revised version: 2 August 2001 / Published online: 15 October 2001     

Oxygen measurements at high pressures with vertical cavity surface-emitting lasers

Measurements of oxygen concentration at high pressures (to 10.9 bar) were made using diode-laser absorption of oxygen A-band transitions near 760 nm. The wide current-tuning frequency range (>30 cm^-1) of vertical cavity surface-emitting lasers (VCSELs) was exploited to enable the first scanned-wavelength demonstration of diode-laser absorption at high pressures; this strategy is more robust than fixed-wavelength strategies, particularly in hostile environments. The wide tuning range and rapid frequency response of the current tuning were further exploited to demonstrate wavelength-modulation absorption spectroscopy in a high-pressure environment. The minimum detectable absorbance demonstrated, ∼1×10^-4, corresponds to ∼800 ppm-m oxygen detectivity at room temperature and is limited by etalon noise. The rapid- and wide-frequency tunability of VCSELs should significantly expand the application domain of absorption-based sensors limited in the past by the small current-tuning frequency range (typically <2 cm^-1) of conventional edge-emitting diode lasers. Received: 26 July 2000 / Revised version: 2 January 2001 / Published online: 20 April 2001     

Electrical and optical characterization of thrombin-induced permeability of cultured endothelial cell monolayers on semiconductor electrode arrays

Impedance spectroscopy and phase-contrast microscopy are combined to monitor the electrical and morphological properties of human umbilical vein endothelial cell monolayers. The cells were cultured on optically transparent indium-tin-oxide (ITO) semiconductor electrode arrays coated with collagen IV, and the effect of the inflammatory mediator thrombin on monolayer permeability was monitored in real time. ITO electrodes provide several advantages for these kinds of experiments, because they are optically transparent, polarizable and highly sensitive due to the absence of insulating oxide layers. A qualitative correlation between the thrombin-induced gap formation and the electrical parameters of the cell layer is established. Received: 8 August 2000 / Accepted: 2 March 2001 / Published online: 20 June 2001     

Portable difference-frequency laser-based cavity leak-out spectrometer for trace-gas analysis

We report a portable mid-infrared spectrometer for trace-gas analysis which is based on an all-solid-state difference-frequency-generation laser. The spectrometer provides in situ absorption path lengths of more than 3 km by means of the cavity leak-out method, a cw variant of the cavity ring-down technique. The design, performance, and application of this spectrometer are presented. The light source utilizes difference-frequency generation in a periodically poled lithium niobate (PPLN) crystal pumped by two single-frequency solid-state lasers. A maximum power of 27 μW in the wavelength region near 3.3 μm is achieved using a pump power of 20 mW at 808 nm, a signal power of 660 mW at 1064 nm, and a 50-mm-long PPLN crystal. This corresponds to a conversion efficiency of 0.42 mW/(W² cm). We demonstrate that this portable laser system is suitable as a light source in a cavity leak-out spectrometer. We achieved a minimum detectable absorption coefficient of 1×10^-8/cm (integration time: 2 s), corresponding, for example, to a detection limit of 1 part per billion ethane. This compact trace-gas analyzer with high sensitivity and specificity is promising for various environmental and medical applications. Received: 8 April 2002 / Revised version: 28 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de     

Importance of pre-ionisation for the non-chain discharge-pumped HF laser

The importance of pre-ionisation for the non-chain discharge-pumped HF laser is studied through experiments on an X-ray photo-triggered laser using mixtures of Ne, SF₆, and ethane. The discharge dynamic in Ne/SF₆ mixtures or pure SF₆, as well as the stabilisation effect induced by C₂H₆ and consequences for the laser performance, are investigated for pre-ionisation electron density values, n_eo, ranging from 10⁶ cm^-3 up to 10⁹ cm^-3, as well as for the so-called discharge self-breakdown mode. Without ethane, the minimum n_eo value which is needed to complete 100% homogeneous charge deposition in the plasma is a very sharply increasing function of the SF₆ pressure. This hinders performance optimisation when the molecule used to react with F-atoms, for instance H₂, has no effect on the discharge dynamic. The minimum ethane partial pressure that is needed to stabilise the discharge depends on n_eo, the pumping pulse duration, the deposited electric charge, and the SF₆ pressure. Discharges in Ne/SF₆ can be much more efficiently stabilised by addition of a small amount of ethane than by an increase of n_eo. A pre-ionisation density as low as 10⁶ cm^-3 is sufficient to achieve the maximum laser energy value, but total suppression of the pre-ionisation has a detrimental effect on the active medium homogeneity. Received: 30 May 2000 / Revised version: 9 October 2000 / Published online: 9 February 2001