(2+1) laser-induced fluorescence of spin-polarized hydrogen atoms

We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments.     

Analytical interference effects on laser-induced fluorescence of ethylene by selected molecular species

The interference of numerous compounds on the laser-induced fluorescence of ethylene at 10.6-mm was studied. The compounds studied were methane, propane, hexane, heptane, propylene, 1-butene, acetylene, benzene, cyclohexane, acetone, chloroform, carbon tetrachloride, methanol, ethanol, sulfur dioxide, nitrogen dioxide, nitric oxide, carbon dioxide, water, argon, helium, nitrogen, and air. Only some of these, in low concentrations, interfered at atmospheric pressure, but most interfered in evacuated systems. Compounds which absorbed the excitation 10.6μm radiation enhanced the fluorescence signals of ethylene, while non-absorbing compounds generally did not interfere. The quenching efficiencies of helium, argon, nitrogen, and methane on excited ethylene molecules were determined, and compared to values calculated from published data; good agreement was found except for methane. Quenching experiments with higher concentrations of added compounds were also performed.     

Anomalous saturation curves in laser-induced fluorescence

This is partly a tutorial and partly a review paper (with a few original additions) on saturation curves (SC) which describe the dependence of fluorescence intensity on laser intensity in atomic spectroscopy. The interest in SCs stems from applications in analytical chemistry, plasma diagnostics, physical and chemical kinetics, etc., as well as from their fundamental implications. After a brief introduction, some general facts and basic assumptions regarding atom-laser interactions are critically examined (Section 2.1) and the concepts of the “ideal” SC and saturation parameter are defined (Section 2.2). In the following Sections 3–7 various effects are discussed that can distort the SC and shift the (apparent) saturation parameter. The effects of a spatially, a temporally and a spectrally inhomogeneous laser beam, of laser-enhanced chemical reactions and ionization processes, of an optically thick atomic vapour and of various non-steady-state processes are successively reviewed. Atom trapping and polarization effects on the SCs measured recently with an atomic Na beam in vacuo are reported and discussed in some detail. Also, some new observations at high resolution on the spectrum of pulsed and cw multimode dye lasers are reported. In Section 8 some general conclusions are drawn and warnings given, and the possible extension of the concept of SC to multiphoton and multistep excitation processes, as well as to optogalvanic spectroscopy, is suggested.     

Europium speciation by time-resolved laser-induced fluorescence

Time-resolved laser-induced fluorescence has been used to investigate Eu complexes formed with a few main ligands encountered in natural waters: hydroxide, carbonate and humic substances. By varying pH and concentrations of ligands at fixed europium concentration and ionic strength, it was possible, together with free europium Eu³⁺, to identify spectrally and temporally carbonate complexes, namely Eu(CO₃)⁺, Eu(CO₃)₂⁻ and Eu(CO₃)₃³⁻ and humate complexes EuHA. For hydroxide complexes, no differences were found in terms of fluorescence spectra and lifetimes. A spectral interpretation is described by using deconvolution for all systems.     

一种便携式激光诱导荧光检测器的研制

基于共聚焦检测原理,自组装了一台便携式激光诱导光检测器,用于微型液相流动系统。精巧的目视观察校准装置使光学校准非常容易。以亚甲基蓝试剂作为检测物质对该系统性能进行了评价,在检测池直径0.25mm时,检测下限为0.2nmol/L,线性范围为10^3,性能达到了文献报道的水平。     

Reactions of CFBr studied by laser-induced fluorescence

Laser-induced fluorescence has been used to study reactions of CFBr radicals in a discharge-flow system. Arrhenius expressions of (1.9 ± 0.6) ξ 10^?12 exp(?762± 92/T) and (1.4 ± 0.3) ξ 10^?12 exp(?533 ± 62/T) cm³ molecule ^?1s^?1 for their reactions with Cl₂ and Br₂ respectively. Upper limits were obtained for the rate of reaction of CFBr with O₂ and F₂CCFBr.     

The laser-induced fluorescence spectrum of chromyl fluoride (chromium dioxidedifluoride) in a seeded molecular beam

We habe obtained part of the laser-induced fluorescence spectrum of chromyl fluoride in a free jet expansion at an instrumental resolution of better than 0.001 cm^?1. This spectrum (together with that of the dispersed fluorescence) allows the identification of the (0,0) band or the absorption spectrum and of several progressions in the lowest bending frequency.     

Analysis of aminophospholipid molecular species by methyl-beta-cyclodextrin modified micellar electrokinetic capillary chromatography with laser-induced fluorescence detection

Micellar electrokinetic capillary chromatography (MEKC) with laser-induced fluorescence detection is used for the analysis of three classes of aminophospholipids: phosphatidylethanolamine (PE), phosphatidylserine (PS), and lysophosphatidylethanolamine (LPE) molecular species. 3-(2-Furoyl) quinoline-2-carboxaldehyde (FQ), a fluorogenic dye, was employed for labeling of these phospholipids. The FQ-labeled lipid species were then separated by sodium deoxycholate MEKC modified with methyl-beta-cyclodextrin. Baseline resolution of each class of phospholipids was achieved within 7 min. The migration time in each class increased with the carbon number of their side aliphatic chain. Separation efficiencies of approximately 3x10(5) plates were observed for most of these species. Concentration detection limits (3 sigma) were from 10(-9) to 10(-10) M for PE and LPE species and from 10(-8) to 10(-9) M for PS species. The relative standard deviations for migration time and peak area were less than 0.9% and 4.5%, respectively, for seven PE species. This method was applied to the separation of PE isolated from HT29 human colon cancer cells and roughly 30 PE species were resolved.     

VUV photon induced fluorescence study of SF5CF3

The interaction of SF(5)CF(3) with vacuum-UV radiation has been investigated by photon induced fluorescence spectroscopy. Total fluorescence yield and dispersed fluorescence spectra of SF(5)CF(3) were recorded in the 200-1000 nm fluorescence window. In all cases, the fluorescence spectra resemble those of CF(3)X (X = H, F, Cl, and Br) molecules. At photon energies below 20 eV, the emission is attributed to the excited CF(3) and CF(2) fragments. The threshold for the CF(3) emission is 10.2 +/- 0.2 eV, giving an upper limit estimate for the SF(5)-CF(3) bond dissociation energy of 3.9 +/- 0.3 eV. The excitation functions of the CF(3) and CF(2) emissions were measured in the photon energy range 13.6-27.0 eV. The resonant structures observed in SF(5)CF(3) are attributed to electronic transitions from valence to Rydberg orbitals, following similar assignments in CF(3)X molecules. The photoabsorption spectrum of SF(5)CF(3) shows features at the same energies, indicating a strong contribution from Rydberg excitations.     

Determination of the fluorescence properties of polynuclear aromatic hydrocarbons in the vapor phase and adsorbed on solid supports by laser-induced molecular fluorescence

The fluorescence properties (lifetimes and spectra) of anthracene and fluoranthene were found to be independent of temperature in the ranges 80–110°C and 60–95°C, respectively, in vacuum and in helium, nitrogen, and air atmospheres. The fluorescence lifetimes and spectra were also measured for these two compounds individually adsorbed on silica, alumina, magnetite, or hematite. In all cases, the emission profiles for the adsorbed aromatic hydrocarbon were red-shifted with respect to the gas-phase spectra. The fluorescence lifetimes for both anthracene and fluoranthene increased for the different supports in the order alumina < silica < magnetite < hematite.     

Resonance fluorescence spectroscopy in laser-induced cavitation bubbles

Laser-induced breakdown spectroscopy (LIBS) in liquids using a double-pulse Q-switched Nd:YAG laser system has provided reliable results that give trace detection limits in water. Resonant laser excitation has been added to enhance detection sensitivity. A primary laser pulse (at 532 nm), transmitted via an optical fiber, induces a cavitation bubble and shockwave at a target immersed in a 10 mg l⁻¹–100 mg l⁻¹ indium (In) water suspension. The low-pressure rear of the shockwave induces bubble expansion and a resulting reduction in cavity pressure as it extends away from the target. Shortly before the maximum diameter is expected, a secondary laser pulse (also at 532 nm) is fed into the bubble in order to reduce quenching processes. The plasma field generated is then resonantly excited by a fiber-guided dye laser beam to increase detection selectivity. The resulting resonance fluorescence emission is optically detected and processed by an intensified optical multichannel analyzer system.      

Ar+ laser-induced fluorescence in NO2

The assignment of the resonant fluorescence induced by the AR⁺ laser lines in ¹⁴N¹⁶O₂ is reported for the first time with the 4727 and 4765 Å laser lines and is further developed with the 4579 and 4965 Å laser lines.     

Capillary electrophoresis with wavelength-resolved laser-induced fluorescence detection

Capillary electrophoresis (CE) enables rapid separations with high separation efficiency and compatibility with small sample volumes. Laser-induced fluorescence detection can result in extremely low limits of detection in CE. Single-channel fluorescence detection, however, furnishes little qualitative information about a species being detected, except for its CE migration time. Use of multidimensional information often enables unambiguous identification of analytes. Combination of CE with information-rich wavelength-resolved fluorescence detection is analogous with ultraviolet-visible diode-array detection and furnishes both qualitative and quantitative chemical information about target species. This review discusses recent advances in wavelength-resolved laser-induced fluorescence detection coupled with CE, with an emphasis on instrument design.     

Near-infrared laser-induced fluorescence detection in capillary electrophoresis

As capillary electrophoresis continues to focus on miniaturization, either through reducing column dimensions or situating entire electrophoresis systems on planar chips, advances in detection become necessary to meet the challenges posed by these electrophoresis platforms. The challenges result from the fact that miniaturization requires smaller load volumes, demanding highly sensitive detection. In addition, many times multiple targets must be analyzed simultaneously (multiplexed applications), further complicating detection. Near-infrared (NIR) fluorescence offers an attractive alternative to visible fluorescence for critical applications in capillary electrophoresis due to the impressive limits of detection that can be generated, in part resulting from the low background levels that are observed in the NIR. Advances in instrumentation and fluorogenic labels appropriate for NIR monitoring have led to a growing number of examples of the use of NIR fluorescence in capillary electrophoresis. In this review, we will cover instrumental components used to construct ultrasensitive NIR fluorescence detectors, including light sources and photon transducers. In addition, we will discuss various types of labeling dyes appropriate for NIR fluorescence and finally, we will present several applications that have used NIR fluorescence in capillary electrophoresis, especially for DNA sequencing and fragment analysis.     

In-column fiber-optic laser-induced fluorescence detection for CE

A highly sensitive in-column fiber-optic LIF detector for CE has been constructed and evaluated. In this detection system, a 457-nm diode-pumped solid-state blue laser was used as the excitation light source and an optical fiber (40 mum od) was used to transmit the excitation light. One end of the optical fiber was inserted into the separation capillary and was in situ positioned at the detection window. The other end of the fiber was protruded from the capillary to capture the excitation light beam from the blue laser. Fluorescence emission was collected by a 40 x microscope objective, focused on a spatial filter, and passed through a yellow color filter before reaching the photomultiplier tube. The present CE-fluorescence detection is a simple and compact optical system. It reduces the laser scattering effect from the capillary and fiber as compared to the conventional LIF detection for CE. Its utility was successfully demonstrated by the separation and determination of D-penicillamine labeled with naphthalene-2,3-dicarboxaldehyde. The detection limit was 0.8 nM (S/N = 3). The present detection scheme has been proven to be attractive for sensitive fluorescence detection for CE.     

Analysis of heavy metals in soils using laser-induced breakdown spectrometry combined with laser-induced fluorescence

The investigation of a hyphenated technique combining laser-induced breakdown spectrometry (LIBS) with laser-induced fluorescence (LIF) for the analysis of heavy metals in soils is described. In order to evaluate the applicability of the technique for fast in-situ analytical purposes, measurements were performed at atmospheric pressure. The plasma radiation was detected using a Paschen–Runge spectrometer equipped with photomultipliers for the simultaneous analysis of 22 different elements. The photomultiplier signals were processed by a fast gateable multichannel integrator. Calibration curves were recorded using a set of spiked soil samples. Limits of detection were derived from these curves for As (3.3 μg/g), Cd (6 μg/g), Cr (2.5 μg/g), Cu (3.3 μg/g), Hg (84 μg/g), Ni (6.8 μg/g), Pb (17 μg/g), Tl (48 μg/g) and Zn (98 μg/g) using the LIBS signals. LIBS-LIF measurements were performed for Cd and Tl. The excitation wavelength as well as the detected fluorescence wavelength for Cd was 228.8 nm. Alternatively, Tl was excited at 276.8 nm, where the observed fluorescence wavelength was 351.9 nm. The calibration curves based on the LIF signals showed significantly improved limits of detection of 0.3 and 0.5 μg/g for Cd and Tl, respectively.     

Two-photon laser-induced fluorescence in oxygen and nitrogen atoms

Two-photon absorption is used to populate the 3p ³P state of O and the 2s²2p²3p⁴D^o state of N in a flow discharge. Exciting photons are produced by anti-Stokes Raman frequency conversion of tunable UV laser radiation; the resulting near IR fluorescence from the excited state yielded lifetimes, quenching rates, and relative two-photon transition probabilities.     

Solid-state UV laser-induced fluorescence detection in capillary electrophoresis

Two solid-state UV lasers were applied to the laser-induced fluorescence (LIF) detection of various groups of compounds after separation by capillary electrophoresis. These lasers are thermoelectric-cooled, highly compact, and inexpensive. Such lasers provide few mW of quasi-continuous wave (CW) power which are sufficient and stable for LIF detection. Native fluorescence detection of tryptophan-containing proteins and peptides and related indoles was achieved at the nM level with the laser operating at 266 nm. Detection of fluorescamine-labeled amino acids and peptides was also possible at the nM level with the laser operating at 355 nm. Amino acids at a concentration as low as 10 ng/mL could be labeled with fluorescamine. Solid-state UV-LIF detection of the tryptic digest of cytochrome c after fluorescamine derivatization was demonstrated.