We report on the preparation, characterization, and photophysical study of new fluorescent core/shell nanoparticles fabricated by electrostatic layer-by-layer assembly. On the basis of gold cores with a diameter of 13 nm, these nanocolloids possess different fluorescently labeled polymer corona layers at various distances from the surface of the core metal using nonfluorescent polyelectrolytes as spacer layers. UV-visible spectroscopy and transmission electron microscopy confirm that the particle suspensions of fluorescently labeled core/shell nanoparticles are stable at all stages of their construction. Photophysical investigations reveal strongly distance-dependent fluorescence quenching in these particle systems. The contribution of the metal core to this quenching can be assesed precisely after the gentle dissolution of the gold cores by potassium cyanide. The photophysical measurements reveal clearly that the gold nanoparticles decrease the transition probability for radiative transitions.

Four different luminescent lanthanide complexes have been studied with respect to multiphoton excitation using near-infrared femtosecond pulses. The method for measuring action cross sections of two-photon excited fluorescence in solution relative to a known standard is reviewed. Two refractive index-related corrections are necessary in this method: one for the multiphoton excitation process, the other for the collection of the emitted light. It has been found that (2,4,6-trimethoxyphenyl)dipicolinic acid and Michler's ketone are reasonable sensitisers of two-photon excited lanthanide luminescence in solution, whereas dipicolinic acid and carbostyril-124 do not give rise to any detectable two-photon excited lanthanide luminescence using modest excitation powers (<20 mW focused at the sample) in the 700-1000 nm range.

The insertion of fluorescently labeled thiols into the protecting self-assembled monolayer on the surface of gold nanoparticles through place exchange reactions and the effects of this insertion on the photophysical properties of the fluorophores are investigated. Analysis of solution-phase fluorescence data using a dynamic equilibrium model yields the equilibrium constant for the place exchange equilibrium, as well as the relative fluorescence brightness of the fluorophores on the particle surface. In all cases we find a significant quenching of the fluorescence, and potential reasons for this quenching are discussed. In the case of these relatively small particles (4.5 nm diameter), the quenching appears to be mainly related to enhanced nonradiative deactivation pathways. The place exchange equilibrium constant reveals a reduced affinity of the fluorescently labeled thiols for insertion into the nonfluorescent alkylthiol monolayer (K(eq) approximately 0.2) compared to unlabeled alkylthiols.