Hydrocarbons fluorescence analysis

In thTs communication, we will illustrate the application of the Video Fluorometer to simultaneous analysis of polycyclic aromatic hydrocarbons and warfarin and its metabolite 7-OH warfarin. We hope to convince the reader of the utility of "higher-order" strategies in fluorescence analysis made practicable by imaging detector based instrumentation. 

There continues to be extensive interest in latexes and micellar systems. The structure of acrylic latex particles has been investigated by non-radiative energy transfer by labelling the co-monomers with fluorescent acceptor-donor systems. Phase separations could also be measured in this way. Excimer fluorescence has been used to measure the critical micelle temperature in diblock copolymers of polystyrene with ethylene-propylene and the results agree well with dynamic light scattering measurements. Fluorescence anisotropy has been used to measure adsorption isotherms of labelled polymers to silica as well as segmental relaxation processes in solutions of acrylic polymers. In the latter case unusual interactions were indicated between the polymers and chlorinated hydrocarbon solvents. Fluorescence analysis of hydrophobically modifled cellulose have shown the operation of slow dynamic processes while fluorescence... 

Carbonized coal products have a unique fingerprint by both GC and fluorescence analyses. Both these fingerprints confirm that sediments from the Elizabeth River are contaminated with carbonized coal products and allow for the detection of carbonized coal hydrocarbons, even in the presence of petroleum-derived hydrocarbons. Fluorescence allows for the rapid analysis of more samples and shows the contamination within the Elizabeth River to be widespread. Carbonized coal products in the sediments may constitute a chronic long-term source of PNA s to the water column. 

Farrington, J.W., S.G. Wakeham, J.B Livramenta, B.W. Tripp, and J.M. Teal. 1986. Aromatic hydrocarbons in New York Bight polychaetes ultraviolet fluorescence analysis and gas chromatography / gas chromatography-mass spectrometry analysis. Environ. Sci. Technol. 20 69-72. 

Nevertheless, this type of analysis, usually done by chromatography, is not always justified when taking into account the operator s time. Other quicker analyses are used such as FIA (Fluorescent Indicator Analysis) (see paragraph 3.3.5), which give approximate but usually acceptable proportions of saturated, olefinic, and aromatic hydrocarbons. Another way to characterize the aromatic content is to use the solvent s aniline point the lowest temperature at which equal volumes of the solvent and pure aniline are miscible. 

The analysis of cigarette smoke for 16 different polyaromatic hydrocarbons is described in this experiment. Separations are carried out using a polymeric bonded silica column with a mobile phase of 50% v/v water, 40% v/v acetonitrile, and 10% v/v tetrahydrofuran. A notable feature of this experiment is the evaluation of two means of detection. The ability to improve sensitivity by selecting the optimum excitation and emission wavelengths when using a fluorescence detector is demonstrated. A comparison of fluorescence detection with absorbance detection shows that better detection limits are obtained when using fluorescence. 

Principal component analysis has been used in combination with spectroscopy in other types of multicomponent analyses. For example, compatible and incompatible blends of polyphenzlene oxides and polystyrene were distinguished using Fourier-transform-infrared spectra (59). Raman spectra of sulfuric acid/water mixtures were used in conjunction with principal component analysis to identify different ions, compositions, and hydrates (60). The identity and number of species present in binary and tertiary mixtures of polycycHc aromatic hydrocarbons were deterrnined using fluorescence spectra (61). 

In LIF detection systems, excitation power may be increased up to six orders of magnitude compared to CF detection. Most LC-LIF detection concerns under-ivatised polynuclear aromatic hydrocarbons (PAHs) and fluorescing dyes (e.g. polymethines). Because only a limited number of analytes possess native fluorescence, derivatisation of the analyte before detection is normally required in trace analysis of organic solutes by means of LIF detection. LIF detection in HPLC was reviewed... 

Rachel, K., Asuncionpunzalan, E. and London, E. (1995) Anchoring of tryptophan and tyrosine analogs at the hydrocarbon polar boundary in model membrane-vesicles - paralax analysis of fluorescence quenching induced by nitroxide-labelled phospholipids. Biochemistry 34,15475-15479. 

A second approach with respect to anisotropic flavin (photo-)chemistry has been described by Trissl 18°) and Frehland and Trissl61). These authors anchored flavins in artificial lipid bilayers by means of C18-hydrocarbon chains at various positions of the chromophore. From fluorescence polarization analysis and model calculations they conclude, that the rotational relaxation time of the chromophore within the membrane is small compared to the fluorescence lifetime (about 2 ns74)). They further obtain the surprising result that the chromophore is localized within the water/lipid interface, with a tilt angle of about 30° (long axis of the chromophore against the normal of the membrane), irrespective of the position where the hydrocarbon chain is bound to the flavin nucleus. They estimate an upper limit of the microviscosity of the membrane of 1 Poise. 

The difficulties in the use of fluorescence for quantitative measurement of hydrocarbons are much like those for the ultraviolet absorption methods. Each compound has its own excitation and emission maxima, with the fluorescence quantum yields varying sometimes by an order of magnitude. Thus the amount of hydrocarbon reported by an analysis will depend upon the emission and excitation wavelengths chosen, and upon the compound selected as the standard. 

Naphthalene-2,3-dicarboxaldehyde Nicotinamide adenine dinucleotide N-Acetylneuraminic acid 4-Fluoro-7-nitrobenzoxadiazole Naphthalene-2,3-dicarboxaldehyde Nondestructive readout Near infrared Near infrared fluorescence Nuclear magnetic resonance 2-Nitrophenyl oxalate 1,1 -Oxalyldiimidazole Polycyclic aromatic hydrocarbon Principal component analysis Photosensitized chemiluminescence Pentachlorophenyl oxalate Polymerase chain reaction... 

When an analyte is fluorescent, direct fluorometric detection is possible by means of a spectrofluorometer operating at appropriate excitation and observation wavelengths. This is the case for aromatic hydrocarbons (e.g. in crude oils), proteins (e.g. in blood serum, in cow milk), some drugs (e.g. morphine), chlorophylls, etc. Numerous fields of applications have been reported analysis of air and water pollutants, oils, foods, drugs monitoring of industrial processes monitoring of species of clinical relevance criminology etc. 

Although many hydrocarbons exhibit fluorescence, often they are colourless and the fluorescence is only just into the blue, e.g. the linear terphenyl and quaterphenyl. Polycyclic ring systems such as terrylene and rubicene are used in analytical methods and OLEDs but a large number are ruled out of commercial use because of their potential to act as carcinogens. However, as mentioned in section 3.5.1.3, pery-lene is a useful fluorophore in a variety of outlets and pyrene is another polycyclic compound of interest. One derivative of pyrene (3.27) is a yellow-green fluorescent dye used in textile applications (Cl Solvent Green 7) and in analysis and sensors (see section 3.5.6.4). 

Jager, J., Detection and Characterization of Nitro Derivatives of Some Polycyclic Aromatic Hydrocarbons by Fluorescence Quenching after Thin-Layer Chromatography Application to Air Pollution Analysis, J. Chromatogr., 152, 575-578 (1978). 

To investigate further the chemical characteristics of potential alternative emulsifiers, the water-soluble fractions (WSFs) of each emulsifier were measured [61]. The samples were analyzed for total recovered hydrocarbons (TRH) in the C10-C36 region and PAHs [3, 62]. The chemical analysis of the emulsifier WSFs did not detect PAHs. Consequently, in the future, use of low-fluorescence emulsifiers in the reformulated Syndrill 80 20 (Mod) will allow the measurement of biliary fluorescence as a biomarker of exposure in field-caught fish attracted to cutting piles, with any detected fluorescence eliminating the drilling mud Syndrill 80 20 (Mod) as a source of fluorescent metabolites in the biliary secretions. 

HPLC analysis of polycyclic aromatic hydrocarbons (PAH) in drinking water is one of the current and classical applications of fluorescence. In this case, the detector contains a fluorescence flow cell placed after the chromatographic column. This mode of detection is specifically adapted to obtain threshold measurements imposed by legislation. The same process allows the measurement of aflatoxins (Fig. 12.11) and many other organic compounds (such as adrenaline, quinine, steroids and vitamins). 

The name lepidopterene refers to the hydrocarbon 113 (L) whose butterflylike molecular shape was first revealed by X-ray diffraction analysis [129,130]. The structured electronic absorption spectra of lepidopterenes around 270 nm closely resemble that of 9,10-dihydroanthracene (see Figure 31). However, in terms of excited state properties, lepidopterenes have very little in common with 9,10-dihydroanthracene, which in solution fluoresces with a quantum yield of 0.16. By contrast, photoexcitation of lepidopterenes leads mainly to intramolecular exciplexes of 7i-chromophorically substituted anthracenes in an adiabatic process, for which both the molecular topology... 

---