Kinetically trapped co-continuous polymer morphologies through intraphase gelation of nanoparticles.

We describe an approach to prepare co-continuous microstructured blends of polymers and nanoparticles by formation of a percolating network of particles within one phase of a polymer mixture undergoing spinodal decomposition. Nanorods or nanospheres of CdSe were added to near-critical blends of polystyrene and poly(vinyl methyl ether) quenched to above their lower critical solution temperature. Beyond a critical loading of nanoparticles, phase separation is arrested due to the aggregation of particles into a network (or colloidal gel) within the poly(vinyl methyl ether) phase, yielding a co-continuous spinodal-like structure with a characteristic length scale of several micrometers. The critical concentration of nanorods to achieve kinetic arrest is found to be smaller than for nanospheres, which is in qualitative agreement with the expected dependence of the nanoparticle percolation threshold on aspect ratio. Compared to structural arrest by interfacial jamming, our approach avoids the necessity for neutral wetting of particles by the two phases, providing a general pathway to co-continuous micro- and nanoscopic structures.

Polarization-driven stark shifts in quantum dot luminescence from single CdSe/oligo-PPV nanoparticles.

We demonstrate polarization-induced spectral shifts and associated linearly polarized absorption and emission in single CdSe/oligo-(phenylene vinylene) (CdSe/OPV) nanoparticles. A mechanism for these observations is presented in which charge separation from photoexcited ligands results in a significant Stark distortion of the quantum dot electron/hole wavefunctions. This distortion results in an induced linear polarization and an associated red shift in band-edge photoluminescence. These studies suggest the use of single quantum dots as local charge mobility probes.

PEGylated silicon nanoparticles: synthesis and characterization.

Silicon nanoparticles were prepared and functionalized with alkene-terminated poly(ethylene oxide) to impart amphiphilic solution properties to the particles.

Ruthenium(II) trisbipyridine functionalized gold nanorods. Morphological changes and excited-state interactions.

Gold nanorods synthesized using cetyltrimethylammonium bromide and tetraoctylammonium bromide as stabilizers are functionalized with a thiol derivative of ruthenium(II) trisbipyridyl complex [(Ru(bpy)3(2+)-C5-SH] in dodecanethiol using a place-exchange reaction. The changes in the plasmon absorption bands and transmission electron micrographs indicate significant changes in the gold rod morphology during the place-exchange reaction. The (Ru(bpy)(3)2+-C5-SH in its excited state undergoes quick deactivation when bound to gold nanorods. More than 60% of the emission was quenched when [(Ru(bpy)3(2+)-C5-SH] was bound to gold nanorods. Emission decay analysis indicates that the energy transfer rate constant is greater than 10(10) s(-1).

Harvesting infrared photons with tricarbocyanine dye clusters.

The absorption of 4,5-benzoindotricarbocyanine dye (IR125) in the infrared can be tuned by controlling the type of aggregation in different media. Molecular clusters of this dye formed in a mixed solvent show broad absorption in the 550-950 nm region as compared to the absorption bands of J- and H-type aggregates. The molecular clusters of the carbocyanine dye are electrophoretically deposited as thin film on optically transparent electrodes using a dc electric field. These tricarbocyanine dye cluster films are photoactive in the infrared region and produce cathodic current when employed as photocathode in a photoelectrochemical cell. Transient absorption spectroscopy of the molecular clusters show short-lived singlet state in the picosecond time scale (lifetime 6 ps) and a charge separated state in the nanosecond time scale. Implication of such dye cluster films for harvesting infrared photons in a photoelectrochemical cell is discussed.

Photochemistry of ruthenium trisbipyridine functionalized on gold nanoparticles.

Design of nanohybrid systems possessing several ruthenium trisbipyridine (Ru(bpy)(3)(2+)) chromophores on the surface of gold nanoparticles, by adopting a place exchange reaction, was reported and their photophysical properties were tuned by varying the density of chromophores. The charge shift between the excited and ground-state Ru(bpy)(3)(2+) chromophores was reported for the first time, leading to the formation of Ru(bpy)(3)(+) and Ru(bpy)(3)(3+). Electron-transfer products were not observed on decreasing the concentration of Ru(bpy)(3)(2+) functionalized on Au nanoparticles or in a saturated solution of unbound chromophores. The close proximity of the chromophores on periphery of the gold core may lead to an electron transfer reaction and the products sustained for several nanoseconds before undergoing recombination, probably due to the stabilizing effect of the polar ethylene glycol moieties embedded between the chromophore groups.

Pearls of wisdom: stringing nanoparticles and polymers into new assemblies and materials.

From size considerations alone, polymers and nanoparticles should be natural partners for the preparation of composite materials. However, this prospect is more difficult than first glance would suggest, and clever synthetic, physical, and engineering considerations are required to optimize the merged value of polymers and nanoparticles. In this issue, Jeffrey Pyun and co-workers provide compelling evidence of the value of such composite materials, by stringing together magnetic nanoparticles into "pearl necklace" assemblies. In instructively interdisciplinary fashion, a full complement of polymer chemistry, nanoparticle synthesis, and nanostructural engineering (via solid-phase atomic diffusion) are combined to reveal artistically appealing products with novel properties that hold promise for the future of energy-storage devices and catalytic materials.

Functional Si and CdSe quantum dots: synthesis, conjugate formation, and photoluminescence quenching by surface interactions.

Silicon quantum dots (QDs) were prepared with a corona of di-n-octyl phosphine oxides, by performing hydrosilylation chemistry on the surface of hydrogen-terminated Si QDs. These novel Si QDs proved well-suited to serve as "ligands" for other semiconductor QDs, such as CdSe, by interaction of the phosphine oxide corona with the CdSe surface. A pronounced photoluminescence quenching of CdSe quantum dots was observed upon introduction of the phosphine oxide functionalized Si QDs to a CdSe QD solution. Surface functionalization of the Si QDs proved critically important to observing these effects, as conventional (alkane-covered) Si QD samples gave no evidence of electronic interactions with TOPO-covered CdSe. In a comparative system, phosphine oxide terminated oligo(phenylene vinylene) molecules acting as CdSe QD ligands provide a similar fluorescence quenching, with exciton decay kinetics supporting the formation of an electronically interacting hybrid materials system.

Linear dipole behavior in single CdSe-oligo(phenylene vinylene) nanostructures.

We report on linearly polarized absorption and emission from individual (4.3 nm) CdSe quantum dots whose surfaces are coordinated with monodisperse oligo-phenylene vinylene ligands. Shown previously to suppress quantum dot blinking, we demonstrate here that the electronic interaction of photoexcited ligands with the quantum dot core is manifested as a strong polarization anisotropy in absorption (M = 0.5), as well as distinct linear dipole emission patterns from the quantum dot core. Further, there is a correlation between the quantum dot emission moment and polarization orientation corresponding to the absorption maxima that is manifested as fluctuations in emission moment orientation in the X-Y plane. The observed polarization effects can be switched off by tuning the excitation away from the ligand absorption band. We propose a mechanism based on exciton dissociation from the photoexcited ligand, followed by the pinning of electrons at the quantum dot surface. The resulting Stark interaction is sufficiently strong to break the 2D degeneracy of the emission moment within the dot, and may therefore account for the linear dipole emission character.

Photophysical and theoretical investigations of oligo(p-phenyleneethynylene)s: effect of alkoxy substitution and alkyne-aryl bond rotations.

The unique photophysical, conformational, and electronic properties of two model phenyleneethynylene-based rigid rod molecular systems, possessing dialkoxy substitutions, are reported in comparison with an unsubstituted system. Twisting of the phenyl rings along the carbon-carbon triple bond is almost frictionless in these systems giving rise to planar as well as several twisted ground-state conformations, and this results in broad structureless absorption in the spectral region of 250-450 nm. In the case of 1,4-bis(phenylethynyl)benzene, a broad absorption band was observed due to the HOMO-LUMO transition, whereas dialkoxy-substituted compounds possess two well-separated bands. Dialkoxy substitution in the 2,5-position of the phenyl ring in phenyleneethynylenes alters its central arene pi-orbitals through the resonance interaction with oxygen lone pairs resulting in similar orbital features for HOMO and HOMO-1/HOMO-2. Electronic transition from the low-lying HOMO-1/HOMO-2 orbital to LUMO results in the high-energy band, and the red-shifted band originates from the HOMO-LUMO transition. The first excited-state transition energies at different dihedral angles, calculated by the TDDFT method, indicate that the orthogonal conformation has the highest excitation energy with an energy difference of 15 kcal/mol higher than the low-lying planar conformation. The emission of these compounds originates preferentially from the more relaxed planar conformation resulting in well-defined vibronic features. The fluorescence spectral profile and lifetimes were found to be independent of excitation wavelengths, confirming the existence of a single emitting species.

Singlet and triplet excited-state interactions and photochemical reactivity of phenyleneethynylene oligomers.

The rigid rodlike character of phenyleneethynylenes and their ability to communicate charge/excitation energy over long distances have made them useful as molecular linkers in the light energy harvesting assemblies and molecular electronics devices. These linker molecules themselves possess rich photochemistry as evident from the relatively large yields of the excited singlet (0.5-0.66) and triplet (0.4-0.5) states of two model oligomers, 1,4-bis(phenylethynyl)-2,5-bis(hexyloxy)benzene (OPE-1) and 1,4-bis((4-phenylethynyl)phenylethynyl)-2,5-bis(hexyloxy)benzene (OPE-2). In particular, the long-lived triplet excited state is capable of undergoing deactivation by self-quenching processes such as ground-state quenching and triplet-triplet (T-T) annihilation. The T-T annihilation occurs with a nearly diffusion-controlled rate (approximately 2 x 10(9) M(-1) s(-1)), and ground-state quenching occurs with a rate constant of approximately 6 x 10(7) M(-1) s(-1). The electron transfer from the excited OPE-1 and OPE-2 to benzoquinone as characterized from the transient absorption spectroscopy illustrates the ability of these molecules to shuttle the electrons to acceptor moieties. In addition, pulse radiolysis experiments confirm the spectroscopic fingerprint of the cation radical (or "trapped hole") with absorption bands in the 500-600 nm region.

Selective detection of cysteine and glutathione using gold nanorods.

A unique strategy for the selective detection of micromolar concentrations of cysteine/glutathione in the presence of various other alpha-amino acids through the plasmon coupling of Au nanorods is reported.