Spectroscopic tests of a 2.3 microm tunable diode laser

A 2.3 microm near-room temperature tunable diode laser was tested for applications in high-resolution laboratory spectroscopy. It was mounted using a simple adaptor in a spectrometer usually used with lead-salt diode lasers, and was found to be electrically and optically compatible with the system. Good output power (several milliwatts) was observed, and a tuning range of 4460-4150 cm(-1) was achieved for laser temperatures of 210-310 K. Some spectra of N(2)O and NH(3) were recorded in the 4300-4430 cm(-1) region. However, the laser was not generally useful due to noisy and unstable output and high sensitivity to optical feedback.     

Tunable single-frequency diode laser at wavelength λ=1.65 μm for methane concentration measurements

This paper deals with the development of a novel single-frequency tunable diode laser with fiber-optic output for gas-analysis applications. The approach we propose is a convenient, simple and cheap solution for spectroscopy of single absorption lines of any gases having absorption bands in the optical fiber transparency window (0.7 microm/1.7 microm). The presence of fiber-optic output is an additional advantage for remote sensing applications. The laser operation is demonstrated as applied to R7 line of 2 nu(3) methane absorption band at lambda = 1.645 microm. The mode-hop-free tuning range of 35 GHz (1.2 cm(-1)) has been achieved.     

Line profile study with tunable diode laser spectrometers

In this paper, we present the different theoretical line profiles, which can be used to describe a shape of molecular transitions in dilute gases: the Voigt, Galatry, Rautian and speed dependence models. We discuss their limitations and their advantages, and present for illustration different comparisons of model results with experimental data obtained with several diode laser spectrometers suitable for precise line shape measurements.     

Preliminary results of heterodyne detection with quantum-cascade lasers in the 9 μm region

In this paper, we describe recent results in mid-infrared heterodyne detection using quantum-cascade (QC) lasers as local oscillator (LO). In the 9 μm range, the heterodyne detection technique was first developed with CO₂ lasers and then with Pb-salt diode lasers. Quantum-cascade lasers are promising high quality tunable mid-infrared sources. We developed a quantum-cascade laser based heterodyne spectrometer. Atmospheric absorption spectra of ozone are presented.     

Near-infrared tunable diode laser spectrometer for the remote sensing of vehicle emissions

A near-infrared diode laser-based spectrometer has been designed and built for the remote sensing of vehicle emissions. It detects carbon monoxide and carbon dioxide absorptions around 1580 nm and can provide the ratio CO/CO(2) for vehicle exhaust studies. The system is battery powered and is designed to sit unobtrusively at the side of the road. The optics and electronics of the system is described and preliminary results are presented from field trials. Extensions to the spectrometer in terms of sensitivity by detection of the more intense first overtone of carbon monoxide around 2320 nm are described, in addition to further work on other species of interest.     

DFB laser diodes in the wavelength range from 760 nm to 2.5 μm

We present a novel device technology to produce DFB laser diodes which are suitable for tunable diode laser spectroscopy. The new technological approach employs lateral metal distributed feedback (DFB) gratings in close proximity to the laser ridge which results in single mode emission with high spectral purity and output powers as required for most spectroscopic applications. Over the entire wavelength range from the visible (760 nm) up to the near-infrared (2.5 microm) single mode emission can be obtained for devices based on different semiconductor systems such as GaAs, InP and GaSb. Typical side mode suppression ratios are better than 35 dB for cw-room temperature operation and narrow linewidths ensure high spectroscopic resolution.     

Infrared diode laser probing of methane in excimer laser photolysis of pyruvic acid

The photodissociation of pyruvic acid at 193 nm has been studied and one of the photoproducts, methane, was detected using an infrared diode laser absorption probe technique. Using second-derivative absorption spectroscopy at 1346.326 cm^-1[R ^(-)(7) transition in v₄ band], the progress of the reaction was monitored. The quantum yield of formation of methane = 0.09 ± 0.01 and was further corroborated by a simple measurement of pressure changes following the photolysis. The secondary photolysis of the photoproduct acetaldehyde via the established route was found to be negligible. This result may help to account for the energetics of the photodissociation process by a 6.4 eV excimer laser photon. The possibility of using this technique to examine the nascent methane molecule in real-time domain to gain better insight of the dissociation dynamics is also indicated.     

Characterization of a 10.3-μm pulsed DFB quantum cascade laser

We have measured the output parameters of a 10.3-μm pulsed distributed-feedback (DFB) quantum cascade (QC) laser manufactured by Alpes Lasers and intended for high-sensitivity detection of ammonia and ethylene. The laser beam was collimated with an AR-coated aspheric ZnSe lens with focal length of 11.6 mm and clear aperture of 16.5 mm. Near- and far-field distributions of the laser emission were recorded with an infrared imaging camera. The fast-and slow-axis laser beam divergences were measured to be 1.2 and 1.4 mrad (FWHM), respectively. The divergence was found to be increasing with injection current. An air-spaced Fabry–Perot interferometer with free spectral range of 0.05 cm⁻¹ was used to measure the frequency tuning rates of the laser. The laser was tuned by either heat sink temperature, injection current or pulse repetition rate with rates of −8 × 10⁻² cm⁻¹ K⁻¹, −7 × 10⁻² cm⁻¹ A⁻¹ and −9 × 10⁻⁴ cm⁻¹ kHz⁻¹, respectively. The laser frequency decreased linearly with a rate of 10⁻² cm⁻¹ ns⁻¹ (300 MHz ns⁻¹) for laser pulses varied from 10 to 50 ns, and the frequency chirp rate was found to decrease for longer laser pulses.     

Microstructural characterization of self-supported 1.6 μm Pd/Ag membranes

The microstructures of self-supported 1.6 μm thick Pd/23 wt% Ag membranes grown by magnetron sputtering and tested for hydrogen permeability under water–gas shift reaction conditions at different temperatures have been studied. The highest hydrogen permeation was observed through the membrane tested at the highest temperature. X-ray diffraction, transmission electron microscopy, scanning electron microscopy and secondary ion mass spectroscopy were used to characterize the membranes. The grain structure is highly textured and the surface topology is roughened as a function of testing temperature. Hydrogen was trapped in the membranes, localized at and near the feed surface, and the level increased with temperature. The Ag composition at some positions on the feed side of the membrane tested at the highest temperature was reduced to around 5 wt%, probably due to the presence of impurities in the feed gas. This dealloying was associated with the presence of Fe impurity and is probably the cause of small satellite peaks in the X-ray diffractograms.     

Element selective detection of molecular species applying chromatographic techniques and diode laser atomic absorption spectrometry

Tunable diode laser atomic absorption spectroscopy (DLAAS) combined with separation techniques and atomization in plasmas and flames is presented as a powerful method for analysis of molecular species. The analytical figures of merit of the technique are demonstrated by the measurement of Cr(VI) and Mn compounds, as well as molecular species including halogen atoms, hydrogen, carbon and sulfur.     

Micro-interferometric backscatter detection using a diode laser

Micro-interferometric backscatter detection (MIBD) is performed with a simple, folded optical train based on the interaction of a diode laser beam and a fused silica capillary tube allowing for refractive index (RI) determinations and detection of optically active molecules in small volumes. Side illumination of the capillary by a laser produces a 360° fan of scattered light that contains two sets of high contrast interference fringes. These light and dark spots are viewed on a flat plane in the direct backscatter configuration. Signal interrogation for polarimetry is based on quantifying the relative intensities (depth of modulation (DOM)) of adjacent high frequency (HF) interference fringes for polarimetry and relative fringe position for RI detection. Positional changes of the interference pattern extrema (fringes) allow for the determination of Δn at the 10⁻⁷ level or 5.3 pmol or 0.48 ng of solute. The MIBD-RI detection volume is just 5.0 nl. DOM changes allow for optical activity detection limits of 5.7 × 10⁻⁵° (mandelic acid, []²³ = −153°, and D-glucose, []²⁵ = +52.5°), and a 2σ detection limit of 7.5 × 10⁻⁴ M (D-glucose) and 1.14 × 10⁻³ M (R-mandelic acid). The probe volume of MIBD-polarimetry was 38 nl, and within the probed volume at the limit of detection, about 28.7 pmol of mandelic acid or about 43.7 pmol of D-glucose is present. Furthermore, DOM (polarimetry signal) is unchanged when a non-optically active solute is interrogated by the MIBD-polarimeter. Finally, an optical model was derived and used to evaluate the advantages and pitfalls of using diode laser for MIBD.     

Temperature dependence of the resolution of diastereomeric isoprenoids in capillary GC. Experiments with 50 μm, 100 μm,and 250 μm i.d. Columns

The resolution of the diastereoisomers of norpristane, pristane, and phytane was studied as a function of the column internal diameter and/or the residence time of the compounds in the column. Increasing the residence time in the column by operating the column at a lower temperature program rate enhances the resolution more than reducing the internal diameter of the column. Practical experience with ultra narrow bore columns is also presented.     

Application of laser photoacoustic spectroscopy for the detection of water vapor near 1.38 μm

Laser photoacoustic (PA) spectroscopy is applied for the determination of the trace content of water vapor using a differential Helmholtz resonant (DHR) cell and a narrow bandwidth diode laser operating near 1380 nm. The PA spectroscopy revealed a rich absorption spectra in this wavelength region and the observed result was compared with the HITRAN database. A multipass optical system was also developed by adopting one aluminum-coated flat mirror with a small uncoated spot for the laser introduction to the detection chamber and one aluminum-coated concave mirror. The multipass optical system enabled the enhancement of the PA signal up to eight times when compared to the single pass case. The calibration curve was plotted by measuring PA signals for various pressures of the water vapor. The sensitivity of the PA detection system is estimated as 7.3×10¹² molecules cm⁻³ with a signal-to-noise ratio (SNR) of 1.     

Infrared laser magnetic resonance spectroscopy of OD at 118.8, 96.5 and 215.4μ m

Zeeman spectral data are presented for the ²Π_3/2: J = _7/2 → J= _9/2,²Π_3/2: J= _7/2→²Π_1/2:J= _5/2 and²Π_3/2 J= _3/2→ J = _5/2 transitions in OD. Data for the ²Π_3/2. J=3/2→ J= 5/2 and ²Π_3/2 J= _5/2 → ²Π_l/2 : J= _3/2 transitions in OH, taken under similar conditions, are included.     

β‐Peptide Conjugates: Syntheses and CD and NMR Investigations of β/α‐Chimeric Peptides,of a DPA‐β‐Decapeptide,and of a PEGylated β‐Heptapeptide

β³‐Peptides consisting of six, seven, and ten homologated proteinogenic amino acid residues have been attached to an α‐heptapeptide (all d‐ amino acid residues; 4 ), to a hexaethylene glycol chain (PEGylation; 5c ), and to dipicolinic acid (DPA derivative 6 ), respectively. The conjugation of the β‐peptides with the second component was carried out through the N‐termini in all three cases. According to NMR analysis (CD₃OH solutions), the (M)‐3₁₄‐helical structure of the β‐peptidic segments was unscathed in all three chimeric compounds (Figs. 2, 4, and 5). The α‐peptidic section of the α/β‐peptide was unstructured, and so was the oligoethylene glycol chain in the PEGylated compound. Thus, neither does the appendage influence the β‐peptidic secondary structure, nor does the latter cause any order in the attached oligomers to be observed by this method of analysis. A similar conclusion may be drawn from CD spectra (Figs. 1, 3, and 5). These results bode well for the development of delivery systems involving β‐peptides.     

Sensitive photoacoustic overtone spectroscopy of acetylene with a multipass photoacoustic cell and a colour centre laser at 1.5 μm

Sensitive Doppler-limited overtone spectra of acetylene in the spectral region 6300–6400 cm⁻¹ have been recorded using a single mode NaCl---OH⁻ colour centre laser and a radial resonant photoacoustic multipass cell. We observed some very weak bands which have not been recorded up to now. By comparing our signal strength with direct absorption measurements of some stronger bands, we were able to calculate a minimum detectable absorption coefficient _min ≈ 10⁻⁹ cm⁻¹.     

Fast separation of flavonoids by supercritical fluid chromatography using a column packed with a sub‐2 μm particle stationary phase

The purpose of this study was to compare the effects of different chromatographic columns for the separation of seven flavonoids. Four different stationary phases are available, including bridged ethyl hybrid, BEH and the same hybrid phase modified with 2‐ethylpyridine, CSH fluorophenyl, and HSS C₁₈ SB. The analytes included calycosin, genistein, medicarpin, calycosin‐7‐O‐β‐d ‐glucoside, formononetin, formononetin‐7‐O‐β‐d ‐glucoside, and liquiritigenin. The CSH fluorophenyl column was determined to be the most suitable and provided the fastest separation within 17 min using gradient elution with carbon dioxide as the mobile phase and methanol as the co‐solvent. Good peak shapes were obtained, and the values of the peak asymmetry were close to 1.0 for all of the flavonoids. The resolution was more than 1.41 for all of the separated peaks. Baseline separation on the optimal columns was achieved by changing the co‐solvent type and adjusting the temperature and pressure. Quantitative performance was evaluated under optimized conditions, and method validation was accomplished. The validation parameters, such as linearity, sensitivity, precision, and accuracy, were satisfactory. Good repeatability of both peak area (relative standard deviation <1.02%) and retention time (relative standard deviation <0.88%) was observed. The optimized chromatographic methods were successfully used for the determination of seven flavonoids in Radix astragali . The sensitivity was sufficient for the analysis of real samples.     

An investigation of microbore reverse-phase columns containing 3 μm packing materials

A procedure for packing 15 cm × 1 mm id reverse-phase microbore columns with 3 μm silicas obtained from different manufacturers is described. The speed of analysis and detection limits are compared to those obtained with a 50 cm × 1 mm id column packed with 10 μm ODS. The effect of detector time constant on the system, and flow rates on column efficiency are also examined.     

Comparison of electrothermal atomization diode laser Zeeman- and wavelength-modulated atomic absorption and coherent forward scattering spectrometry

Atomic absorption and coherent forward scattering spectrometry by using a near-infrared diode laser with and without Zeeman and wavelength modulation were carried out with graphite furnace electrothermal atomization. Analytical curves and limits of detection were compared. The magnetic field was modulated with 50 Hz, and the wavelength of the diode laser with 10 kHz. Coherent forward scattering was measured with crossed and slightly uncrossed polarizers. The results show that the detection limits of atomic absorption spectrometry are roughly the same as those of coherent forward scattering spectrometry with crossed polarizers. According to the theory with bright flicker noise limited laser sources the detection limits and linear ranges obtained with coherent forward scattering spectrometry with slightly uncrossed polarizers are significantly better than those obtained with crossed polarizers and with atomic absorption spectrometry. This is due to the fact that employing approaches of polarization spectroscopy reduce laser intensity fluctuations to their signal carried fractions.