We present for the first time experimental evidence of fluorescence lifetime enhancement of organic chromophores attached to metal nanospheres via radiative decay engineering. The hybrid system (HS) was a modified "diconjugated" molecular probe, 4-acetamido-4'-maleimidylstilbene-2,2'-dithiol (AMDT), covalently bound to the surface of 5-nm-diameter Au nanospheres by its two sulfur atoms, at a distance d < 1 nm and with its molecular axis parallel to the surface of the nanoparticle surface. We measured a fluorescence lifetime increase of a factor of 2 at room temperature (tau(AMDT) = (4.32 +/- 0.10) ns and tau(HS) = (8.73 +/- 0.23) ns) and a factor of 3.4 at 4.2 K (tau(AMDT) = (2.64 +/- 0.07) ns and tau(HS) = (7.96 +/- 0.14) ns). We also found that the fluorescence quantum yield of this hybrid system is not reduced, proof of a weak energy transfer between the molecular probe and the nanoparticle. These results demonstrate that a molecular dipole oriented parallel to the metal surface tends to be reduced by the coupling with its image.

Dibenzo[a,l]pyrene is considered the most potent carcinogen of all polycyclic aromatic hydrocarbons ever tested. Its four isomers, which include dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, dibenzo[a,i]pyrene, and dibenzo[e,l]pyrene, are also carcinogenic and, therefore, a potential threat to humans. The method presented here provides a direct way for their determination in water samples. The entire procedure--from water extraction to LETRSS analysis--takes less than 15 min/sample and it consumes only 100 microL of organic solvent. This fact makes our approach environmentally friendly and cost-effective. Unambiguous isomer determination is accomplished via multidimensional data formats, namely, wavelength time matrixes, excitation-emission matrixes, and time-resolved excitation-emission matrixes. The analytical figures of merit demonstrate precise and accurate analysis at the sub-parts-per-billion level. Limits of detection are at the parts-per-trillion level. The potential of this approach for real-world analysis is illustrated with a heavily contaminated water samples.

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.

We present a unique method for the unambiguous determination of dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, dibenzo[a,i]pyrene, and dibenzo[e,l]pyrene in high-performance liquid chromatography (HPLC) fractions. Chemical analysis is performed via laser-excited time-resolved Shpol'skii spectroscopy with the aid of a cryogenic fiber-optic probe, pulsed tunable dye laser, spectrograph, and intensified charge-coupled device. Unambiguous identification is accomplished via wavelength time matrix formats, which give simultaneous access to spectral and lifetime information. Prior to spectroscopic analysis, HPLC fractions are pre-treated with liquid-liquid extraction or solid-liquid extraction at the tip of the fiber-optic probe. Solid-liquid extraction gives the best limits of detection, which vary from 40 pg mL(-1) (dibenzo[a,l]pyrene) to 0.2 ng mL(-1)(dibenzo[e,l]pyrene).

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