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Fabrication of precisely tailored layers of conductive polymers in thin film assemblies is an attractive extension of the layer-by-layer technique. This approach provides tools for fabricating thin films with customized optical and electrical properties. In this paper, we study inorganic layer-by-layer assembled films prepared using polyphosphate and cerium(IV). It is shown that these multilayers can oxidize certain monomers from the adjacent aqueous solution to produce conducting polymer layers. We studied the thermodynamic factors that allow the aforementioned autopolymerization. A five bilayer polyphosphate/cerium(IV) film was shown to possess high oxidative power in acidic solutions. It was found that the polymerization of pyrrole, aniline and 3,4-ethylenedioxythiophene in contact with the redox active multilayer is thermodynamically favored. The rate of polymer formation and the thickness of the conducting film could be controlled by the concentration of the monomer in solution and the number of cerium/polyphosphate bilayers in the oxidative film. The oxidative polymerization of pyrrole was unambiguously recognized on UV-vis spectra with characteristic reduction and oxidation bands. The film formation was not restricted by charge diffusion and the reaction formally followed first-order kinetics. The results suggest that the reaction takes place effectively within the whole pre-existing polypyrrole film and it continues until all oxidant in the film was used. The spectral changes that are characteristic for conducting polypyrrole are shown on spectroelectrochemical analysis of the films indicating that cationic (polaron) and dicationic (bipolaron) species are involved in the redox processes of the film. The functional polymer films formed are found to be electroactive and conducting. Therefore, they fully resemble of conducting polymer films prepared using traditional electropolymerization.

A caroteno-purpurin dyad molecule was studied by steady-state and pump-probe spectroscopies to resolve the excited-state deactivation dynamics of the different energy levels as well as the connecting energy flow pathways and corresponding rate constants. The data were analyzed with a two-step multi-parameter global fitting procedure that makes use of an evolutionary algorithm. We found that following ultrafast excitation of the donor (carotenoid) chromophore to its S2 state, the energy flows via two channels: energy transfer (70%) and internal conversion (30%) with time constants of 54 and 110 fs, respectively. Additionally, some of the initial excitation is found to populate the hot ground state, revealing another limitation to the functional efficiency. At later times, a back transfer occurs from the purpurin to the carotenoid triplet state in nanosecond timescales. Details of the energy flow within the dyad as well as species associated spectra are disentangled for all excited-state and ground-state species for the first time. We also observe oscillations with the most pronounced peak on the Fourier transform spectrum having a frequency of 530 cm(-1). The dyad mimics the dynamics of the natural light-harvesting complex LH2 from Rhodopseudomonas acidophila and is hence a good model system to be used in studies aimed to further explain previous work in which the branching ratio between the competing pathways of energy loss and energy transfer could be manipulated by adaptive femtosecond pulse shaping.

The blood-brain barrier efficiently controls the entry of drug molecules into the brain. We describe a feasible means to achieve carrier-mediated drug transport into the rat brain via the specific, large neutral amino acid transporter (LAT1) by conjugating a model compound to L-tyrosine. A hydrophilic drug, ketoprofen, that is not a substrate for LAT1 was chosen as a model compound. The mechanism and the kinetics of the brain uptake of the prodrug were determined with an in situ rat brain perfusion technique. The brain uptake of the prodrug was found to be concentration-dependent. In addition, a specific LAT1 inhibitor significantly decreased the brain uptake of the prodrug. Therefore, our results reveal for the first time that a drug-substrate conjugate is able to transport drugs into the brain via LAT1.