Highly fluorescent silver nanoparticles (AgFNP) have been prepared by a facile photochemical method, yielding these materials in just a few minutes and with excellent long-term stability. The method makes use of photogenerated ketyl radicals that reduce Ag(+) from silver trifluoroacetate in the presence of amines. While as functional materials these AgFNP can be described as of nanometer dimensions, we believe that the luminescence arises from particle-supported small metal clusters (predominantly Ag(2)). The materials have been characterized by electron microscopy, fluorescence and absorption spectroscopy, fluorescence lifetime studies, and (19)F NMR spectroscopy. Exploratory work shows that the fluorescence from AgFNP can be efficiently quenched by paramagnetic quenchers, and these studies have been combined with electron paramagnetic resonance work.

The photolysis of an alkoxyamine triad comprised of the 1-phenylethyl moiety, 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) and 2-methyl-3-hydroxy quinoline leads to energy transfer from the quinoline moiety (antenna) and cleavage of the C-O alkoxyamine bond, suggesting its possible applications in low temperature living free radical polymerization.

A novel approach employing a prefluorescent paramagnetic sensor has been employed to determine the absolute kinetics for end-cap cleavage in TEMPO-capped polystyrene obtained by "living" free radical polymerization. This new methodology takes advantage of the suppression of coumarin fluorescence when this chromophore is tethered to a paramagnetic nitroxide. This coumarin-nitroxide is an excellent free radical trap for carbon-centered radicals; upon radical trapping, the resulting diamagnetic alkoxyamine is strongly fluorescent. Thus, fluorescence buildup is a direct measure of free radical formation and can be employed to quantify their formation or to study their kinetics. Studies of the temperature dependence of the process can be employed to determine activation parameters and bond dissociation energies. This simple technique can be employed to study the dynamics in the actual polymer systems, overcoming the frequent need to resort to model compounds.

The photochemical and photophysical properties of 4-(3-hydroxy-2-methyl-4-quinolinoyloxy)-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (QT) have been studied as a prefluorescent probe to monitor free radical processes in polymer films. This methodology takes advantage of the efficient intramolecular quenching of the fluorescence of quinoline by the paramagnetic nitroxide, which is disabled when TEMPO reacts with carbon-centered radicals. The fluorescence intensity-time profile observed in the thermal decomposition of 2,2′-azobis(isobutyronitrile) (AIBN) in poly(methyl methacrylate) (PMMA) films showed initial increments in the fluorescence with time, according to the trapping of carbon-centered radicals by QT in the polymer films. Comparison of data under nitrogen and oxygen saturation conditions suggests that oxygen trapping of the carbon-centered radicals at 90 °C is about 20 times faster than reaction with nitroxides. The activation energy for AIBN decomposition in PMMA was measured as 34.1 kcal/mol. Analysis of the fluorescence lifetime distribution establishes the involvement of both static and dynamic fluorescence quenching of the diamagnetic reaction product by AIBN.

The photostability of the widely used UVB sunscreen agents 2'-ethylhexyl-2-cyano-3-phenylcinnamate (1), 2-hydroxy-4-methoxybenzophenone (2), octyl salicilate (3), and 2'-ethylhexyl-4-methoxycinnamate (4) has been investigated under UVA irradiation in the absence and presence of TiO2, an inorganic filter commonly employed in combination with organic filters in sunscreen preparations. In the absence of TiO2, 1-3 are photostable and 4 undergoes the expected E-Z isomerization; the presence of TiO2 caused mineralization of the organic filters and, surprisingly, the process is noticeably faster in the presence of surfactant than in sunscreen and water suspensions. The results indicate that in water suspension, mineralization is likely to occur on or near the TiO2 particle surface; when the organic sunscreens are segregated in the micelle core, reactive radicals, produced during TiO2-promoted degradation of the micellar system, may participate in sunscreen degradation. In addition, a pre-fluorescent probe for carbon-centered radical detection, 4-(3-hydroxy-2-methyl-4-quinolineoxy)-2,2,6,6-tetramethylpiperidine-1-oxyl free radical or QT (5), was employed to demonstrate that carbon-centered radicals are evolved during micelle degradation and may participate in the mineralization of sunscreens.

As applications for semiconductor nanoparticle quantum dots (QDs) continue to expand in fields such as biology, imaging, and sensors, 1 it is paramount to have a fundamental understanding of their chemical and electronic interactions. Thiol-stabilized QDs have received considerable attention because they suffer from fewer fluctuations in their properties, and in certain cases their photoluminescence quantum yields show an improvement over trioctylphosphine oxide (TOPO)-capped QDs. 2,3 Further, from the perspective of QDs biological applications, the interaction of RS-H and RS-SR bonds with the surface is of the utmost importance.As part of our study of the interaction of (TOPO)-capped CdSe QDs with free radicals, 4-6 we have found that binding of disulfide biradical C2 to the QD surface provides a unique perspective of the mechanism by which disulfide binding evolves on the surface. By probing the system with fluorescence and EPR spectroscopies, we have found that the disulfide linkage is useful for the attachment of species to the surface of CdSe QDs leading to robust, strong chemical bonds to the particle surface and reporting on the dynamics of surface binding and S-S dissociation.

Benzyl radicals derived from photodecomposition of dibenzyl ketone have been monitored in NaY zeolite using the pre-fluorescent probe 4-(3-hydroxy-2-methyl-4-quinolinoyloxy)-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (QT). The steady-state and time-resolved fluorescence show a strong interaction of QT within the zeolite cavities. Furthermore, the increase in the fluorescence with the irradiation time reveals the efficient trapping of benzyl radicals by QT under vacuum. Dispersion of the zeolite composites in liquid polymers results in an improvement in the fluorescence measurement and faster kinetics in comparison with the solid samples. These results are interpreted in terms of partial refractive index matching as a consequence of polymer reptation into the zeolite cavities. Analysis of the fluorescence lifetime distribution shows the presence of different fluorescence ensembles with different fluorescence quantum yields, depending on the microenvironment within the zeolite particle. Pre-fluorescent probes offer a novel and useful methodology for studying radical processes in zeolites.

2,4,6-Triphenylpyrylium (TP(+)), an electron acceptor, has been included inside the channels of two ordered mesoporous titania (mpTiO(2)). MpTiO(2) contain anatase nanoparticles (3-5 nm) templated by cetyltrimethylammonium and differ by the presence or absence of silica domains as binders of the structure. UV irradiation of TP-mpTiO(2) gives rise to a strong EPR signal. This behaviour was not observed for related materials in which TP(+) was included inside the channels of MCM-41 or the cavities of zeolite Y. Also, transient spectroscopy shows remarkable differences between TP(+) included in mpTiO(2) (charge separation) and in porous silicates (triplet excited state). Based on EPR and laser flash spectroscopic evidence, the occurrence of photo-induced electron transfer from TiO(2) as the donor to TP(+) as the acceptor leading to a long-lived (minutes at room temperature) charge separated state is proposed.