ABSTRACT
Recording absorption spectra via transmittance through frozen matrixes is a challenging task. The main reason is the difficulty in overcoming the strong scattering light reaching the detector. This is particularly true when thick samples are necessary for recording absorption spectra of weak oscillators. In the case of strongly fluorescent compounds, additional errors in absorbance measurements arise from the emission reaching the detector, which might have an intensity comparable to that of the transmitted light. This article presents a fundamentally different approach to low-temperature absorption measurements as the sought for information is the intensity of laser excitation returning from the frozen sample to the ICCD. Laser excitation is collected with the aid of a cryogenic fiber optic probe. The feasibility of our approach is demonstrated with single-site and multiple-site Shpol'skii systems. The 4.2 K absorption spectra show excellent agreement with their literature counterparts recorded via transmittance with closed-cycle cryogenators. Fluorescence quantum yields measured at room temperature compare well to experimental data acquired in our laboratory via classical methodology. Similar agreement is observed between 77 K fluorescence quantum yields and previously reported data acquired with classical methodology. We then extend our approach to generate original data on fluorescence quantum yields at 4.2 K.
ABSTRACT
We present a single instrument with the capability to collect multidimensional data formats in both the fluorescence and the phosphorescence time domains. We also demonstrate the ability to perform luminescence measurements in highly scattering media by comparing the precision of measurements in Shpol'skii solvents to those obtained in "snowlike" matrixes and solid samples. For decades, conventional low-temperature methodology has been restricted to optically transparent media. This restriction has limited its application to organic solvents that freeze into a glass. We remove this limitation with the use of cryogenic fiber-optic probes.
ABSTRACT
The potential of solid-liquid extraction fluorescence line narrowing spectroscopy is evaluated for screening polycyclic aromatic hydrocarbons in aqueous samples. Octadecyl silica membranes are used with the dual purpose of sample preconcentration and solid substrate for spectroscopic measurements. 4.2 K fluorescence line narrowed spectra are directly recorded from the membrane with the aid of a fiber-optic probe. The experimental procedure is free from organic solvents and takes less than 5 min per sample. With 10 mL of water sample, the limits of detection are at the parts-per-billion level. Qualitative analysis is based on wavelength time matrices, which provide a unique format for compound identification based on spectral and lifetime data. The selectivity of this approach is demonstrated with the unambiguous determination of naphthalene in a heavily contaminated water sample.
Subject(s)
Membranes, Artificial , Polycyclic Aromatic Hydrocarbons/analysis , Polycyclic Aromatic Hydrocarbons/chemistry , Spectrometry, Fluorescence/methods , Ultrafiltration/methods , Feasibility Studies , Phase Transition , Reproducibility of Results , Sensitivity and SpecificityABSTRACT
Laser-excited time-resolved Shpol'skii spectrometry at liquid helium temperature (4.2 K) is presented for the analysis of polycyclic aromatic hydrocarbons in high-performance liquid chromatography fractions. Fluorescence measurements are rapidly done with the aid of a fiber-optic probe, pulsed tunable dye laser, spectrograph, and intensified charge-coupled device. Analyte identification and peak-purity checking are made through wavelength-time matrix formats, which give simultaneous access to spectral and lifetime information. Sample preparation is rapid and simple. It involves liquid-liquid extraction or solid-liquid extraction of chromatographic fractions at the tip of the fiber-optic probe. The potential of both approaches is demonstrated with the semi-quantitative analysis of priority pollutants in heavily contaminated water samples.
ABSTRACT
Fluorescence measurements are easily made with the aid of a cryogenic fiber optic probe. Emission wavelength time matrixes, excitation emission matrixes, and time-resolved excitation emission matrixes are rapidly collected with a pulsed tunable dye laser, a spectrograph, and an intensified charged-coupled device. Compound identification is based on spectral and lifetime information. The potential of this approach for supporting high-performance liquid chromatography analysis and for the direct determination of benzo[a]pyrene without previous separation is demonstrated.
Subject(s)
Environmental Pollutants/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Chromatography, High Pressure Liquid , Environmental Monitoring/methods , Fiber Optic Technology , Lasers , Optical Fibers , Spectrometry, FluorescenceABSTRACT
A new procedure is presented for the analysis of polycyclic aromatic hydrocarbons by solid-liquid extraction (SLE) and laser-excited time-resolved Shpol'skii spectrometry (LETRSS). Microliters of Shpol'skii solvent are spiked on the surface of the extraction membrane and LETRSS is directly performed on the organic layer above the surface of the solid substrate. Fluorescence measurements are easily performed with a fiber-optic cell specifically designed for cryogenic measurements at 77 and 4.2 K. In comparison to the SLE-LETRSS procedure previously reported (Environ. Sci. Technol. 35 (2001) 2566), the spiking procedure eliminates the eluting step, reduces solvent consumption and improves limits of detection for at least one order of magnitude.
