Methane leak detection by tunable laser spectroscopy and mid-infrared imaging.

Tunable laser spectroscopy (TLS) combined with mid-infrared imaging is a powerful tool for a sensitive and quantitative visualization of gas leaks. This work deals with standoff methane leak detection within 2 m by an interband cascade laser (3270 nm wavelength) and an infrared camera. The concept demonstrates visualization of methane leakage rates down to 2 ml/min by images and sequences at frame rates up to 125 Hz. The gas plume and leak can be localized and quantified within a single image by direct absorption spectroscopy (DAS). The HITRAN database allows a calibration-free, pixelwise determination of the concentration in ppm*m. The active optical imaging concept showed pixelwise sensitivities around 1 ppm*m.

Gas Leak Detection by Dilution of Atmospheric Oxygen.

Gas leak detection is an important issue in infrastructure monitoring and industrial production. In this context, infrared (IR) absorption spectroscopy is a major measurement method. It can be applied in an extractive or remote detection scheme. Tunable laser spectroscopy (TLS) instruments are able to detect CH4 leaks with column densities below 10 ppm·m from a distance of 30 m in less than a second. However, leak detection of non-IR absorbing gases such as N2 is not possible in this manner. Due to the fact that any leaking gas displaces or dilutes the surrounding background gas, an indirect detection is still possible. It is shown by sensitive TLS measurements of the ambient background concentration of O2 that N2 leaks can be localized with extractive and standoff methods for distances below 1 m. Minimum leak rates of 0.1 mbar·L/s were determined. Flow simulations confirm that the leakage gas typically effuses in a narrow jet. The sensitivity is mainly determined by ambient flow conditions. Compared to TLS detection of CH4 at 1651 nm, the indirect method using O2 at 761 nm is experimentally found to be less sensitive by a factor of 100. However, the well-established TLS of O2 may become a universal tool for rapid leakage screening of vessels that contain unknown or inexpensive gases, such as N2.

Self-gated mid-infrared short pulse upconversion detection for gas sensing.

Pulsed nonlinear-optical upconversion is used for mid-infrared signal detection. A setup for both mid-infrared generation and upconversion based on a single pump laser enables sensitive light detection and is utilized for gas spectroscopy. With the demonstrated pulsed setup, quantum efficiencies above 80 % for the upconversion of a Gaussian beam signal and 25 % for the upconversion of backscattered radiation are achieved and in agreement with theoretical predictions. Combined with efficient background suppression due to spectral and temporal gating, this results in highly sensitive detection of the infrared signals. As a demonstration of application, the presented system is used for methane sensing in an open path geometry, highlighting the potential for stand-off leak detection with a concentration resolution better than 1.5 ppm·m.

Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

Laser spectroscopy is a powerful tool for analyzing small molecules, i.e. in the gas phase. In the mid-infrared spectral region quantum cascade lasers (QCLs) have been established as the most frequently used laser radiation source. Spectroscopy of larger molecules in the gas phase, of complex mixtures, and analysis in the liquid phase requires a broader tuning range and is thus still the domain of Fourier transform infrared (FTIR) spectroscopy. However, the development of tunable external cavity (EC) QCLs is starting to change this situation. The main advantage of QCLs is their high spectral emission power that is enhanced by a factor of 10(4) compared with thermal light sources. Obviously, transmission measurements with EC-QCLs in strongly absorbing samples are feasible, which can hardly be measured by FTIR due to detector noise limitations. We show that the high power of EC-QCLs facilitates spectroscopy beyond simple absorption measurements. Starting from QCL experiments with liquid samples, we show results of fiber evanescent field analysis (FEFA) to detect pesticides in drinking water. FEFA is a special case of attenuated total reflection spectroscopy. Furthermore, powerful CW EC-QCLs enable fast vibrational circular dichroism (VCD) spectroscopy of chiral molecules in the liquid phase - a technique which is very time consuming with standard FTIR equipment. We present results obtained for the chiral compound 1,1'-bi-2-naphthol (BINOL). Finally, powerful CW EC-QCLs enable the application of laser photothermal emission spectroscopy (LPTES). We demonstrate this for a narrowband and broadband absorber in the gas phase. All three techniques have great potential for MIR process analytical applications.

Ultrafast protein conformational alterations in bacteriorhodopsin and its locked analogue BR5.12.

Bacteriorhodopsin, reconstituted with a sterically "locked" retinal chromophore, BR5.12, has frequently been used to elucidate elementary photoinduced processes in the native pigment bacteriorhodopsin. In this work, the vibrational response of BR5.12 to photoexcitation is investigated by means of femtosecond time-resolved mid-infrared and UV-vis spectroscopy. The electronically excited state of BR5.12 decays with a time constant of 18 ps. Neither in the UV-vis nor in the mid-IR spectral region are indications found for chromophore photoproducts, besides the full recovery of the electronic ground state. However, vibrational bands are observed at around 1660 and 1550 cm(-1) in the protein amide I and amide II band regions, respectively. They are formed within a few picoseconds or even instantaneously. Thus, they appear faster than the S1 decay and persist for at least 130 ps, i.e., for much longer than the S1 lifetime. These findings strongly suggest that the observed bands must be assigned to protein vibrations and that they are not caused by a photoinduced temperature rise. Thus, for the first time, ultrafast protein vibrational changes are detected in BR5.12, that are not associated with isomerization. Possibly they can be related to the enhanced chemical reactivity of photoactivated BR5.12 reported in the literature. In wild-type bacteriorhodopsin, bands with very similar spectral and kinetic characteristics are observed, suggesting that they might originate from a similar mechanism which is not isomerization. A plausible mechanism is a polarization induced protein conformational change, as discussed in the literature.

Femtosecond infrared spectroscopy of bacteriorhodopsin chromophore isomerization.

The vibrational dynamics of the retinal chromophore all-trans-to-13-cis photoisomerization in bacteriorhodopsin has been studied with mid-infrared absorption spectroscopy at high time resolution (about 200 femtoseconds). After photoexcitation of light-adapted bacteriorhodopsin, the transient infrared absorption was probed in a broad spectral region, including vibrations with dominant C-C, C=C, and C=NH stretching mode amplitude. All photoproduct modes, especially those around 1190 reciprocal-centimeters that are indicative for a 13-cis configuration of the chromophore, rise with a time constant of approximately 0.5 picosecond. The results presented give direct vibrational-spectroscopic evidence for the isomerization taking place within 0.5 picosecond, as has been suggested by previous optical femtosecond time-resolved experiments but questioned recently by picosecond time-resolved vibrational spectroscopy experiments.

Ultrafast dynamics of phytochrome from the cyanobacterium synechocystis, reconstituted with phycocyanobilin and phycoerythrobilin.

Femtosecond time-resolved transient absorption spectroscopy was employed to characterize for the first time the primary photoisomerization dynamics of a bacterial phytochrome system in the two thermally stable states of the photocycle. The 85-kDa phytochrome Cph1 from the cyanobacterium Synechocystis PCC 6803 expressed in Escherichia coli was reconstituted with phycocyanobilin (Cph1-PCB) and phycoerythrobilin (Cph1-PEB). The red-light-absorbing form Pr of Cph1-PCB shows an approximately 150 fs relaxation in the S(1) state after photoexcitation at 650 nm. The subsequent Z-E isomerization between rings C and D of the linear tetrapyrrole-chromophore is best described by a distribution of rate constants with the first moment at (16 ps)(-1). Excitation at 615 nm leads to a slightly broadened distribution. The reverse E-Z isomerization, starting from the far-red-absorbing form Pfr, is characterized by two shorter time constants of 0.54 and 3.2 ps. In the case of Cph1-PEB, double-bond isomerization does not take place, and the excited-state lifetime extends into the nanosecond regime. Besides a stimulated emission rise time between 40 and 150 fs, no fast relaxation processes are observed. This suggests that the chromophore-protein interaction along rings A, B, and C does not contribute much to the picosecond dynamics observed in Cph1-PCB but rather the region around ring D near the isomerizing C(15) [double bond] C(16) double bond. The primary reaction dynamics of Cph1-PCB at ambient temperature is found to exhibit very similar features as those described for plant type A phytochrome, i.e., a relatively slow Pr, and a fast Pfr, photoreaction. This suggests that the initial reactions were established already before evolution of plant phytochromes began.