Excess electrons in nanocrystalline TiO2 were studied in bare and dopairtine-capped TiO2 nanoparticles by electron-beam pulse radiolysis. Reaction of hydrated electrons with dopamine-capped TiO2 nanoparticles was found to be at the diffusion-controlled limit, k = 1 x 10(11) M-1 s(-1), while the reaction with 1-hydroxy-1-methylethyl radicals, (CH3)(2)(C) over dot OH, was 2 orders of magnitude slower, k = 4 x 10(8) M-1 s(-1). The reactions result in injection of electrons into the conduction band of TiO2 nanoparticles. Optical absorption spectra of injected excess electrons in dopamine-capped nanoparticles display monotonic featureless wavelength dependence up to 1800 nm. In contrast, bare particles have shown two preferential optical transitions with energies in the visible region (lambda(max) = 670 nm and lambda(max) = 900 nm). Flat band potential of dopamine-capped TiO2 nanoparticles was shifted by 100 mV to more negative values. The strong coupling of dopamine to surface Ti atoms was also found to improve the separation of photogenerated charges. This was demonstrated by the enhanced efficiency of photogenerated electrons in reducing silver cations to metallic silver in systems linked via a dopamine bridge, compared to the same systems linked through carboxyl groups.