Polymer vesicles as robust scaffolds for the directed assembly of highly crystalline nanocrystals.

We report the incorporation of various inorganic nanoparticles (NPs) (PbS, LaOF, LaF(3), and TiO(2), each capped by oleic acid, and CdSe/ZnS core/shell QDs capped by trioctylphosphine oxide) into vesicles (d = 70-150 nm) formed by a sample of poly(styrene-b-acrylic acid) (PS(404)-b-PAA(62), where the subscripts refer to the degree of polymerization) in mixtures of tetrahydrofuran (THF), dioxane, and water. The block copolymer formed mixtures of crew-cut micelles and vesicles with some enhancement of the vesicle population when the NPs were present. The vesicle fraction could be isolated by selective sedimentation via centrifugation, followed by redispersion in water. The NPs appeared to be incorporated into the PAA layers on the internal and external walls of the vesicles (strongly favoring the former). NPs on the exterior surface of the vesicles could be removed completely by treating the samples with a solution of ethylenediaminetetraacetate (EDTA) in water. The triangular nanoplatelets of LaF(3) behaved differently. Stacks of these platelets were incorporated into solid colloidal entities, similar in size to the empty vesicles that accompanied them, during the coassembly as water was added to the polymer/LaF(3)/THF/dioxane mixture.

Overcoming kinetic limitations of electron injection in the dye solar cell via coadsorption and FRET.

A new, extremely simple concept for the use of energy transfer as a means to the enhancement of light absorption and current generation in the dye solar cell (DSC) is presented. This model study is based upon a carboxy-functionalized 4-aminonaphthalimide dye (carboxy-fluorol) as donor, and (NBu4)2[Ru(dcbpy)2(NCS)2] (N719) as acceptor chromophores. A set of three different devices is assembled containing either exclusively carboxy-fluorol or N719, or a mixture of both. This set of transparent devices is characterized via IV-measurements under AM1.5G and monochromatic illumination and their light-harvesting and external quantum efficiencies (LHE and EQE, respectively) are determined as well. It is shown that the device containing only the donor chromophore has a marginal power conversion efficiency, thus indicating that carboxy-fluorol is a poor sensitizer for the DSC. Cyclovoltametric measurements show that the poor sensitization ability arises from the kinetic inhibition of electron injection into the TiO2 conduction band. Comparing the spectral properties of the DSCs assembled presently, however, demonstrates that light absorbed by carboxy-fluorol is almost quantitatively contributing to the photocurrent if N719 is present as an additional sensitizer. In this case, N719 acts as a catalyst for the sensitization of TiO2 by carboxy-fluorol in addition to being a photosensitizer. Evaluation of the maximum output power under blue illumination shows that the introduction of an energy-donor moiety via coadsorption, leads to a significant increase in the monochromatic maximum output power. This result demonstrates that energy transfer between coadsorbed chromophores could be useful for the generation of current in dye-sensitized solar cells.

A dyadic sensitizer for dye solar cells with high energy-transfer efficiency in the device.

A new bichromophoric dyad based on an alkyl-functionalized aminonaphthalimide as energy-donor chromophore and [Ru(dcbpy)2(acac)]Cl (dcbpy=4,4'-dicarboxybipyridine, acac=acetylacetonato) as energy acceptor and sensitizing chromophore is synthesized. Efficient quenching of the donor-chromophore emission is observed in solution, presumably due to resonant energy transfer. This dyad is then used as a sensitizer in a dye solar cell. By comparing the spectral properties of transparent dye solar cells sensitized with the dyad and [Ru(dcbpy)2(acac)]Cl, it is possible to demonstrate that photons absorbed by the donor moiety also contribute significantly to the generation of current. Instead of using acceptor luminescence as a probe, enhanced photocurrent generation is employed to estimate the energy-transfer efficiency. Fitting theoretical to experimental external quantum efficiency functions gives a value for the energy-transfer efficiency of 85 %. Evaluation of the maximum output power of dye solar cells sensitized with the dyad and [Ru(dcbpy)2(acac)]Cl showed, under selective illumination at the absorption maximum of the donor chromophore, that the introduction of the energy-donor moiety leads to a significant increase in the monochromatic maximum output power under blue illumination. This result demonstrates the usefulness of energy transfer for the generation of current in dye-sensitized solar cells.

Self-assembled monolayers of dendritic polyglycerol derivatives on gold that resist the adsorption of proteins.

Highly protein-resistant, self-assembled monolayers (SAMs) of dendritic polyglycerols (PGs) on gold can easily be obtained by simple chemical modification of these readily available polymers with a surface-active disulfide linker group. Several disulfide-functionalized PGs were synthesized by N,N'-dicyclohexylcarbodiimide-mediated ester coupling of thioctic acid. Monolayers of the disulfide-functionalized PG derivatives spontaneously form on a semitransparent gold surface and effectively prevent the adsorption of proteins, as demonstrated by surface plasmon resonance (SPR) kinetic measurements. A structure-activity relationship relating the polymer architecture to its ability to effectuate protein resistance has been derived from results of different surface characterization techniques (SPR, attenuated total reflectance infrared (ATR-IR), and contact-angle measurements). Dendritic PGs combine the characteristic structural features of several highly protein-resistant surfaces: a highly flexible aliphatic polyether, hydrophilic surface groups, and a highly branched architecture. PG monolayers are as protein resistant as poly(ethylene glycol) (PEG) SAMs and are significantly better than dextran-coated surfaces, which are currently used as the background for SPR spectroscopy. Due to the higher thermal and oxidative stability of the bulk PG as compared to the PEG and the easy accessibility of these materials, dendritic polyglycerols are novel and promising candidates as surface coatings for biomedical applications.