Phosphorescence spectra and detection limits of nitrated polynuclear aromatic hydrocarbons

Phosphoresence excitation and emission spectra and detection limits for 22 nitrated polynuclear aromatic hydrocarbons at 77 K are reported. Detection limits are lower than 10 ng ml^?1 in several cases. The spectral properties of 1-nitropyrene (a frequently used reference substance) permit is selective determination in the presence of other nitroaromatics.     

Liquid chromatographic method with fluorescence detection for the determination of polycyclic aromatic hydrocarbons in environmental samples

A method for the determination of some polynuclear aromatic hydrocarbons (PAHs) in water samples and air filters is presented. Samples were extracted with light petroleum-diethyl ether (85 + 15) and the extracts were concentrated before analysis. Reversed-phase liquid chromatography with fluorescence detection was applied to separate and determine the PAHs. Recoveries of individual PAHs from spiked water samples were 0.16–0.27 ng ml^?1. Detection limits in the picogram range were obtained for each compound.     

Analyse quantitative des hydrocarbures aromatiques polynucleaires par spectrofluorimetrie shpol'skii a 10 k: utilisation de la raie de mercure excitatrice diffusee par la matrice comme intensite lumineuse de reference

(Quantitative analysis by Shpol'skii spectrofluorimetry of polynuclear aromatic hydrocarbons at 10 K with the mercury excitation line scattered by the matrix used as a standard intensity.)High-resolution Shpol'skii spectrometry in a matrix is particularly suitable for the determination of trace polynuclear aromatic hydrocarbons in complex mixtures. In the usual technique, the method of standard additions is backed up by internal calibration, which is tedious. A direct calibration technique is proposed in which the mercury excitation line, scattered by the polycrystalline matrix, serves as the standard intensity. Detection limits vary from 0.3 ng ml^?1 for benzo(a)pyrene to 48 ng ml^?1 for pyrene, with linear response over about 2 orders of magnitude. The dynamics and a statistical analysis of the confidence interval for the results are discussed.     

Laser fluorimetry of polynuclear aromatic hydrocarbons based on time-resolved fluorescence detection

Three polynuclear aromatic hydrocarbons are quantified from the pre-exponential factor of the fluorescence decay curve, instead of the integrated fluorescence intensity. The slopes of the calibration plots are independent of the oxygen concentration in the solvent as predicted. Deaeration of sample solutions gives lower detection limits (around 10^?10 M); the extent of improvement depends on the fluorescence lifetime.     

The Combination of Laser-Induced Fluorescence and Intensified Linear Diode Array Detection in Column Liquid Chromatography

Abstract

The frequency-doubled 514-nm argon-ion laser line providing excitation at 257 nm is combined with an intensified linear diode array (ILDA) detector to enable on-the-fly identification by laser-induced fluorescence (LIF) in conventional-size column liquid chromatography (LC). The potential of this detection system is demonstrated for the analysis of a standard mixture of polynuclear aromatic hydrocarbons (PAHs). Detection limits are at the 1.5 μg 1^?1 level (15 pg injected); the identitication limits are about one order of magnitude higher.     

Laser-Induced fluorescence detection in conventional-size liquid chromatography with a frequency-doubled argon-ion laser

Laser-induced fluorescence (LIF) detection in conventional-size column liquid chromatography is achieved at 257 nm with a frequency-doubled argon-ion laser. Short-wavelength excitation offers two important advantages: firstly, a wide variety of analytes can be excited, and secondly, the Raman scatter of the eluent does not interfere with the fluorescence of the analytes. A standard mixture of polynuclear aromatic hydrocarbons was studied, both with LIF detection and with a commercially available sensitive conventional fluorescence detector. The improvement in the detection limits ranges from about a factory of 4 to 30; the LIF detection limits are typically at the 50 ng l^?1 level, which corresponds to an injected amount of 0.5 pg.     

Quantitation and identification of polynuclear aromatic hydrocarbons by liquid chromatography and multiwavelength absorption spectrometry

This paper describes the combined use of liquid chromatographic separation with multiwavelength absorption detection for the quantitation and identification of polynuclear aromatic hydrocarbons. Quantiative results are presented for three- and four-component mixtures with complete and partial separation. Qualitative data are presented for a twelve-component synthetic mixture and for extracts from a filter used to collect particulate emissions from a biomass-gasifier system. It is shown that multiwavelength data-processing methods commonly applied to absorption spectra can be applied with significant advantage to second-derivative spectra. Results indicate that significant improvements can be achieved by the use of different wavelength ranges for different components in mixtures. Detection limits for single-component samples varied between 3 and 11 μg l^?1 for eleven hydrocarbons and the scatter about calibration plots for mixtures was in the range of 0.05 to 0.4 μg ml^?1. The identities of all twelve components in the synthetic mixture were confirmed and nineteen components were identified in the sample from the biomass gasifier filter.     

Laser-excited fluorescence line-narrowing: an analytical study

The limits of detection obtained by fluorescence line-narrowing spectroscopy for 6 polynuclear aromatic hydrocarbons are compared with those obtained by low-temperature and room-temperature fluorescence, and the merits of the technique are discussed.     

Analysis of organic pollutants in water at trace levels using fully automated solid-phase extraction coupled to high-performance liquid chromatography

Summary A method has been developed for the determination of trace levels of 32 pesticides, 19 explosives and 16 polycyclic aromatic hydrocarbons (PAH) in water in three individual steps. Solid-phase enrichment (SPE) is coupled to high-performance liquid chromatography (HPLC) with a fully automated system. The organic pollutants are enriched on reusable cartridges packed with adsorbent materials: pesticides and explosives on a mixed bed of divinylbenzene-ethylvinylbenzene copolymers (LiChrolut EN^?) and perfluorinated polyethylene (PolyF^?), and polycyclic aromatic hydrocarbons on C₁₈-modified silica (Zorbax^? ODS1). Thermally assisted desorption (TAD) has been shown to increase the recovery of analytes significantly. As all enriched analytes are transferred to the detector, only fifty millilitres of sample is needed for each single on-line analysis, compared with at least a litre for conventional methods. The separation of the enriched organic analytes is performed on specialized HPLC columns based on reversed-phase materials. The limits of detection of the system employed were found to be below 100 ng L⁻¹. Use of fluorescence detection for the polycyclic aromatic hydrocarbons resulted in limits of detection in the upper pg L⁻¹ range. Thek values, number of theoretical plates, the recovery rates and the limits of detection of this method for fast screening of organic pollutants from three fifty-millilitre aqueous samples are described. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Luminescence analysis of complex organic materials based on resolved line spectra produced by selective laser excitation

Selective methods of obtaining the resolved line spectra of the solutions of complex molecules, along with the peculiarities of these spectra, are considered. At sufficiently low temperatures (4.2 K), broad-band absorption and luminescence spectra of the solutions of organic compounds are often broadened, mainly inhomogeneously. Excitation of the luminescence by tunable lasers can eliminate this broadening. The spectra obtained consist of dozens of narrow (Δv ≈ 1 cm^-1) vibrational lines. Some examples of selective excitation for the spectrofluorimetric analysis of complex organic materials are given: identification (at the 10^-11 g ml^-1 level) and determination of individual polynuclear hydrocarbons in certain materials without preliminary separation is demonstrated by the determination of benzopyrene and perylene in gasoline and the detection of perylene in a solid paraffin.     

Functionalized semiconductor nanocrystals for ultrasensitive detection of peptides

Semiconductor CdS nanoparticle have been prepared and modified with thiovanic acid. The functionalized nanoparticles are water-soluble. They were used as the fluorescence probes in the ultrasensitive detection of peptides. This method is based on the fluorescence enhancement of functionalized nano-CdS in the presence of peptide with mercapto groups (GN-9) and the fluorescence quenching of functionalized nano-CdS in the presence of peptide (GA-8 and MT-25). Excitation and emission wavelengths were 360 and 530 nm, respectively. Under optimum conditions, the calibration graphs are linear over the range of 0.15-3.5, 0.2-4.0, and 0.2-3.8 μg ml⁻¹ for GN-9, GA-8 and MT-25, respectively. The corresponding detection limits were 0.010 μg ml⁻¹ for GN-9, 0.018 μg ml⁻¹ for GA-8 and 0.022 μg ml⁻¹ for MT-25, respectively. This method has been proved to be a simple, rapid and sensitive method.     

1,2-Diamino-4,5-ethylenedioxybenzene as a highly sensitive fluorogenic reagent for aromatic aldehydes

1,2-Diamino-4,5-ethylenedioxybenzene is shown to be a highly sensitive reagent for aromatic aldehydes, especially for benzaldehydes having a hydroxy group. The reagent reacts selectively with aromatic aldehydes at pH 3.0 (phosphate buffer) within 30 min at 60°C; the products fluoresce most intensely at pH 11. In the manual method, the lower limits of detection vary from 6 pmol ml^?1 to 7 nmol ml^?2. The fluorescent derivatives of aromatic aldehydes can be separated by reversed-phase high-performance liquid chromatography. The fluorescent product from 4-hydroxybenzaldehyde is shown to be 2-(4-hydroxyphenyl)-5,6-ethylenedioxybenzimidazole.     

Direct determination of selected polynuclear aromatic hydrocarbons in a coal liquefaction product by synchronous luminescence techniques

Synchronous fluorescence and the room-temperature phosphorescence methods were used to determine selected polynuclar aromatic hydrocarbons in a coal liquid (solvent-refined coal) product without a preseparation step. The procedure identified and quantified ten polynuclear aromatic compounds including anthracene, 2,3-benzofluorene, benzo[a]pyrene, benzo[e]pyrene, carbazole, dibenzothiophene, fluoranthene, fluorene, perylene and pyrene. Standard deviations for repeated determinations ranged from 10–30% for concentrations in the range of 0.1–6 mg g^-1. The data obtained by these methods agree with results by other methods within the estimated experimental uncertainty.     

Determination of Fe, Cu and Zn in sugar-cane spirits commercialized in Southeastern Brazil by TXRF

Total reflection X-ray fluorescence (TXRF) was used to determine simultaneously the concentration of Cu, Fe and Zn in seven sugar-cane spirit samples (“aguardente”), a processed alcoholic beverage made from the fermentation and distillation of sugar-cane juice. The limits of detection ranged from 35 to 8 ng^.ml^-1 for V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As and Se. Excluding Fe, Cu and Zn, the concentrations were below their limits. Two samples showed Cu concentrations higher than the value allowed by Brazilian legislation (5 μg^.ml^-1), and concerning Fe and Zn, no sample were above the limits permitted by WHO for drinking water (2 and 3 μg^.ml^-1, respectively). This revised version was published online in August 2006 with corrections to the Cover Date.     

Atomiser, source, inductively coupled plasmas, in atomic fluorescence spectrometry (ASIA). Some recent work

The dual-plasma atomic fluorescence/atomic emission spectrometer (ASIA spectrometer) is described and the detection limits for several elements in both the fluorescence and the emission mode are presented and compared directly. The detection limits for the non-refractory elements are, in general, better in fluorescence than emission While for the refractory elements the converse is true, but all are in the ng ml⁻¹ range. Growth curves for a refractory and a non-refractory element are presented and evaluated.     

Polarographic determination of isoniazide, N-acetylisoniazide and isonicotinic acid by superimposed sinusoidal tension]

The a.c. polarographic determination of isoniazid (INH), N-acetylisoniazid (AcINH) and isonicotinic acid (INA) is described. Under the optimal conditions of pH, ionic strength and electrical parameters, the limits of detection are 0.5 μg ml^-1 for AcINH, 0.2 μg ml^-1 for INH, and 0.03 μg ml^-1 for INA.     

Evaluation of multi-element analysis of blood serum by energy-dispersive x-ray spectrometry

Conventional energy-dispersive x-ray fluorescence is applied in the analysis of blood serum to give the concentrations of 7–10 elements simultaneously with minimal manipulation of the samples. Simple spotting onto a Mylar carrier of 250 μl of serum, doped with two internal standards, was chosen as the sample preparation step. Some 200 serum samples, analyzed in replicate (n = 2–6), were used to evaluate this procedure. The detection limits are 4 μg ml^-1 for K and Ca, 0.5–0.2 μg ml^-1 for Fe, Cu, Pb and Zn, and less than 0.1 μg ml^-1 for Se, Rb and Sr. Well above these limits, the standard deviation is around 10%. Comparison with the results of other measurements on the same samples indicates an accuracy of that order. The simplicity and high throughput, and the possibility of automating the x.r.f. measurements, make the proposed procedure suitable for screening large numbers of sera.     

Ionen-chromatographische Bestimmung yon Chloracetat und Dichloracetat in Niederschlagswasserproben

Summary Chlorinated hydrocarbons are released to the atmosphere by anthropogenic activities. To some extent they are decomposed in the troposphere by chemical reactions. Chlorinated acyl chlorides were found as degradation products in laboratory studies. Chloroacetate and dichloroacetate are supposed to be formed by hydrolysis of the intermediately produced chlorinated acyl chlorides. A multidimensional ion-chromatographic method was developed to separate traces of chloroacetate and dichloroacetate from the more than thousandfold excess of matrix ions. The limits of detection are 0.25 ng ml^–1 chloroacetate and 0.4 ng ml^–1 dichloroacetate. This technique is applied to the analysis of chloroacetate and dichloroacetate in precipitation samples. Mean concentrations of 1.5 ng ml^–1 chloroacetate and 1.6 ng ml^–1 dichloroacetate were found.     

Fluorimetric assay of ergotamine

Studies on the fluorescence properties of ergotamine in water at various pH values, and in several organic solvents are described. An assay procedure for ergotamine, based on its intense fluorescence in ethanol, is presented. Extraction of ergotamine into benzene from basic aqueous solution is followed by transfer of the extract to ethanol for fluorescence determination. The plot of fluorescence intensity vs. concentration is linear up to 5 μg ml^?1, and the assay has a limit of detection of 0.002 μg ml^?1. Reproducibility data at the 2.5-μg ml^?1 level are given.     

Determination of nucleic acids based on the fluorescence quenching of Hoechst 33258 at pH 4.5

It was found the strong fluorescence emitted by the bis-benzimidazole derivative Hoechst 33258 at 490 nm could be efficiently quenched in pH 4.5 buffer when nucleic acids were added. Analysis of fluorescence intensity showed that the procedure was a static quenching dominated one, which was also demonstrated by the electron absorption spectra and lifetime of the excited state. The binding constant and numbers of binding sites were obtained from the Scatchard plot. The decreased fluorescence intensity was in proportion to the concentration of nucleic acids in the range 40-1800 ng ml⁻¹ for dsDNA and 26-1700 ng ml⁻¹ for ssDNA. The limits of detection were 12 and 8 ng ml⁻¹, respectively. The sensitivity of the method was about 3.4 times higher for dsDNA detection and 5.4 times higher for ssDNA detection compared with the widely used fluorescence enhancement method using the same dye. Application results to synthetic samples showed simplicity, rapidity and satisfactory reproducibility of the presented method. Measurement of real samples extracted from leaves of Crassula argentea and E. coli genome also gave satisfactory results, which were in good agreement with those obtained using spectrophotometric method.