Modification of emission photon statistics from single quantum dots using metal/SiO2 core/shell nanostructures.

Emission photon statistics, i.e., single-photon and multi-photon emissions, of isolated QDs is required for tailoring optoelectronic applications. In this article, we demonstrate that the emission photon statistics can be modified by the control of the spectral overlap of the QDs with the localized surface plasmon resonance (LSPR) of the metal nanoparticle (metal NP) and by the distance between the QD and the metal NP. Moreover, the contribution to the modification of the emission photon statistics, which is the excitation and emission enhancements and the quenching generated by the spectral overlap and the distance, is elucidated. By fabricating well-defined SiO2-coated AgNPs and AuNPs (metal/SiO2), the spectral overlap originated from the metal species of Ag and Au and the distance constituted by the thickness of the SiO2 shell are controlled. The probability of single-photon emission of single QD was increased by the enhancement of the excitation rate via adjusting the distance using Ag/SiO2 while the single-photon emission was converted to multi-photon emission by the effect of exciton quenching at a short distance and a small spectral overlap. By contrast, the probability of multi-photon emission was increased by enhancement of the multi-photon emission rate and the quenching via the spectral overlap using Au/SiO2. These results indicated the fundamental finding to control emission photon statistics in single QDs by controlling the spectral overlap and the distance, and understand the interaction of plasmonic nanostructures and single QD systems.

Giant Amplification of Photoswitching by a Few Photons in Fluorescent Photochromic Organic Nanoparticles.

Controlling or switching the optical signal from a large collection of molecules with the minimum of photons represents an extremely attractive concept. Promising fundamental and practical applications may be derived from such a photon-saving principle. With this aim in mind, we have prepared fluorescent photochromic organic nanoparticles (NPs), showing bright red emission, complete ON-OFF contrast with full reversibility, and excellent fatigue resistance. Most interestingly, upon successive UV and visible light irradiation, the NPs exhibit a complete fluorescence quenching and recovery at very low photochromic conversion levels (<5 %), leading to the fluorescence photoswitching of 420±20 molecules for only one converted photochromic molecule. This "giant amplification of fluorescence photoswitching" originates from efficient intermolecular energy-transfer processes within the NPs.

Influence of micro-joints formed between spheres in coupled-resonator optical waveguide.

Light propagation is simulated through coupled-resonator optical waveguides (CROWs) composed of seven transparent polystyrene microspheres, including micro-joints formed between the spheres. In nanojet-induced mode (NIM) light propagation, the micro-joints increased the optical coupling between microspheres drastically, and the light confinement by individual microspheres weakened as the micro-joint diameter increases. These results suggest that we can control NIM light propagation by changing the micro-joint diameter; this amounts to a nanojet throttle valve.

Radical-initiator-Induced solid-state polymerization of butadiyne nanocrystals in water and their dispersion stabilization.

Butadiyne nanocrystals in water are usually polymerized by UV or gamma-ray irradiation to give polydiacetylene (PDA) nanocrystals. In this study, we confirmed that solid-state polymerization of 1,6-di(N-carbazolyl)-2,4-hexadiyne (DCHD) and 5,7-dodecadiyn-1,12-diyl bis[N-(butoxycarbonyl-methyl)carbamate] (4BCMU) could be stimulated by water-soluble radical initiators. The radical initiators used were potassium peroxodisulfate, three kinds of azo-type compounds and a redox initiator. In all cases, the solid-state polymerization was confirmed by color change into blue indicating that PDA modified by the radical residues at the end was formed. However, nanocrystal cohesion occurred especially when the concentration of the initiators was high or the dispersion was kept for a long time. In order to improve the dispersion stability, two kinds of surfactants, i.e., sodium dodecyl sulfate (SDS) or dodecyltrimethylammonium chloride (DTMAC), were added to the DCHD nanocrystal aqueous dispersion. As a result, when anionic SDS was added, the solid-state polymerization of nanocrystals proceeded without coagulation and quantitative conversion was confirmed for all initiators. Cationic DTMAC has no effect on dispersion stabilization. PDA nanocrystal surfaces in water are negatively charged in nature and electric interaction of nanocrystals with the cations results in decrease of surface charge and aggregation of nanocrystals.

Random laser oscillation from an organic fluorescent dye loaded inside a porous zirconia medium.

Porous zirconia medium (PZrM) has been fabricated successfully using polystyrene microparticles (MPs) as templates. The emission spectra of rhodamine B (RhB) [optical amplifying medium] loaded inside PZrM [porous scatterers] were obtained at numerous excitation light intensities. The lasing thresholds (I th) have been determined experimentally from the variations in the intensity of random laser oscillation peaks, which are suitably separated from the measured emission spectra. I th is closely related to the pore sizes of PZrM and the added amount of PZrM powder, and it clearly provided the minimum against the pore size. This fact is explained reasonably by the simulation of scattering efficiency on the basis of the Mie scattering theory. Consequently, PZrM as a porous scatterer is superior to Zr MPs from the viewpoint of random laser oscillation.

Chemical modification utilizing a terminal structure exposed on the specific surface of polymer-metal complex nanocrystals.

It has been difficult to selectively modify the surface of molecular crystals by chemical reactions because they usually have no reaction points on their surfaces. In this paper, focusing on the unique nanocrystal surface of the polymer metal complex (PMC) [{Cu2(µ-Br)2(PPh3)2}(µ-bpy)] n having an exposed reactive terminal chain, we successfully modified the surface of PMC nanocrystals (NCs) through an alkylation reaction. Interestingly, after the alkylation reaction, the luminescence spectrum of PMC NCs blue-shifted, and the luminescence quantum yield increased. PMC NCs with a large specific surface area showed optically peculiar or characteristic properties compared with the corresponding bulk crystals. PMC NCs have high potential as a new class of luminescent materials due to their surface effect.

Layer-by-Layer Growth Control of Metal-Organic Framework Thin Films Assembled on Polymer Films.

We demonstrate growth control of Cu-based metal-organic framework (MOF) (HKUST-1) thin films assembled by the layer-by-layer technique on polymer films. The crystallinity and crystal face of MOF thin films were found to be controlled by reaction sites in polymer films such as hydroxy groups (the (100) crystal face), carbonyl groups (the (111) crystal face), and amide groups (the (100) crystal face). The HKUST-1 film growth amount is highly correlated with the polar component of the surface free energy, indicating that polymer sites, which afford hydrogen and coordination bonding, are important for the initial adsorption of Cu complexes. We also demonstrated a resistive switching device application using an HKUST-1 thin film on the poly(vinyl alcohol) dip-coated film at 40 deposition cycles, which suggests that the HKUST-1 thin film serves as a resistive switching layer with good film formation capability.

Nanostructural characterization and catalytic analysis of hybridized platinum/phthalocyanine nanocomposites.

Organic crystals, such as phthalocyanine nanocrystal, were successfully hybridized with Pt nanoparticles using a nanohybridization technique. The presence of highly dispersed Pt nanoparticles on the surface of phthalocyanine was confirmed by the combination of transmission electron microscopy and three-dimensional electron tomography. Catalytic activities of hybridized samples with different degrees of dispersions were also examined as oxygen reduction reactivity (ORR) with a linear potential sweep method. It was found that oxygen reduction activity increased with increasing Pt dispersion, and reasonably high ORR was observed on Pt-dispersed phthalocyanine nanocrystal even at 2 wt% Pt loading.

Introducing porosity into polyimide nanoparticles.

Novel porous polyimides (PIs) having diameters of several hundred nanometers have been fabricated successfully from precursor poly(amic acid) (PAA) derivatives with poly(acrylic acid) (PAS) as the porogen, using a reprecipitation method and subsequent imidization. The superficial high porosity with deep pores was introduced when using a more compatible combination of PAA and the porogen, i.e., PI (BPDA-PDA) and PAS rather than PI (10FEDA-4FMPD and PAS); the pore sizes ranged from 20 to 100 nm. The resulting porous PI nanoparticles had thermally stabilities (determined from their 5% weight loss temperatures at 400 degrees C) similar to those of corresponding PI nanoparticles lacking porous structures. Microphase separation within the PAA nanoparticles after reprecipitation induced the porous surface structure, the properties of which were influenced by the molecular weight of PAS and the chemical structure of PAA. These unique porous PI nanoparticles have great potential for application as low-k materials in next-generation technologies.

Attempt to visualize terminal structure on a specific facet in polymer-metal complex nanocrystals.

We have successfully visualized the surface terminal structure of polymer-metal complex [{Cu2(µ-Br)2(PPh3)2}(µ-bpy)] n nanocrystals (NCs) using Prussian blue (PB) nanoparticles (NPs). From TEM observation and analysis of the electron beam diffraction pattern, it was found that the (010) plane had grown well, and that the terminal ends of main chains would be located on the (010) plane of the present NCs as a dangling bond. Actually, PB NPs were selectively adsorbed on the (010) plane of [{Cu2(µ-Br)2(PPh3)2}(µ-bpy)] n NCs. This fact clearly means bipyridine ligands having a nitrogen-terminal located on the surface of the (010) plane would coordinate and bind to Fe ions in PB NPs, which would lead to a new class of polymer-metal complex NCs materials.

A promising visible light-driven photocatalytic activity of conjugated polymer nanocrystals.

Conjugated polymers have recently emerged as a new class of photocatalysts. However, many conjugated polymer photocatalysts are not as effective as inorganic materials due to the limited electronic properties of their LUMO and HOMO and low long-term stability caused by the degradation of the conjugated backbone. In the present study, we have demonstrated, for the first time, the superior Visible (Vis) light-driven photocatalytic activity of conjugated polymer nanocrystals (NCs) of polydiacetylene (PDA) derivatives, namely, p-DCHD NCs for the photodegradation of Rhodamine B (RhB) compared with that of the state-of-the-art P25 TiO2 nanoparticles (NPs). In addition, we have revealed the morphological effects of p-DCHD NCs, long-term stability, and the photocatalytic degradation mechanisms. These results will open a new pathway for the further development and understanding of conjugated polymer photocatalysts toward various potential applications.

Facile synthesis and bridgehead-functionalization of bicyclo[3.3.3]pentasiloxanes.

A fascinating but still rare bicyclic siloxane, bicyclo[3.3.3]pentasiloxane, was synthesized by the oxidation of a bicyclic silicon cluster and characterized using a combination of NMR spectroscopy and X-ray diffraction analysis. The bridgehead OSiMe3 groups of the siloxane were selectively and efficiently converted to O-K+ (siloxide) by treating with tBuOK in the presence of 18-crown-6-ether. The resulting siloxides provided various bridgehead-functionalized bicyclo[3.3.3]pentasiloxanes after treatment with electrophiles.

Creation of nano eye-drops and effective drug delivery to the interior of the eye.

Nano eye-drops are a new type of ophthalmic treatment with increased potency and reduced side effects. Compounds in conventional eye-drops barely penetrate into the eye because the cornea, located at the surface of eye, has a strong barrier function for preventing invasion of hydrophilic or large-sized materials from the outside. In this work, we describe the utility of nano eye-drops utilising brinzolamide, a commercially available glaucoma treatment drug, as a target compound. Fabrication of the nanoparticles of brinzolamide prodrug increases the eye penetration rate and results in high drug efficacy, compared with that of commercially available brinzolamide eye-drops formulated as micro-sized structures. In addition, the resulting nano eye-drops were not toxic to the corneal epithelium after repeated administration for 1 week. The nano eye-drops may have applications as a next-generation ophthalmic treatment.

The effect of molecular structure on the anticancer drug release rate from prodrug nanoparticles.

The controlled release of an anticancer agent from drug nanoparticles could be achieved by varying the linker length of dimeric compounds as prodrug. Notably, the cytotoxicity of the cancer cells was closely related to the release rate of drug compounds. This strategy will lead to the establishment of the novel delivery system using drug nanoparticles.

Monodispersed quinacridone nanocrystals prepared by a high-temperature and high-pressure liquid crystallization method.

Monodispersed quinacridone nanocrystals were fabricated by a high-temperature and high-pressure liquid crystallization method, which proved to be an advanced technique for fabricating nanocrystals of pigment compound. The aqueous dispersion liquid of quinacridone nanocrystals was very stable. The nanocrystats had a spherical shape with an average size of 60 nm when water was used as the high-temperature and high-pressure liquid at 260 degrees C and cooling solvent. The crystal structure of the nanocrystals could be controlled by varying the experimental conditions.

Synthesis of photolabile fluorescent polymeric micelles.

A new amphiphilic block copolymers were synthesized with the atom transfer radical polymerization (ATRP) method. Then, the micelle structures were fabricated with a self-assembly method for application in nanocarriers and sensing. The fluorescent intensity was increased by a factor of 4 in the micelle solution due to more stacked pyrene moieties. The core-shell structure of the micelle was confirmed by HR-TEM images. The pyrene moieties were positioned in the core of the micelle, and the surface consisted of hydrophilic PMMA blocks. The ester bond of the polymer backbone was breakable by irradiation with UV light. Therefore, the micelle structure was deformed after UV irradiation, and the excimer peak was drastically reduced as the monomer peak appeared. The deformation of micelle structures was clearly confirmed by FE-SEM and NMR analysis. These photolabile polymeric micelles may be widely useful for photo-stimulative nanocarriers as well as for the design of new functional micelles with many other chromophores.

Direct deposition of two nanomaterials with the same surface charge using a liquid-liquid interface.

Two negatively charged nanoparticles (SDS-coated SWCNT and polydiacetylene nanocrystals) were sequentially adsorbed onto the same water-hexane interface. The absorbed film can be transferred onto a solid substrate. Repeating the adsorption and transfer process enables assembly of the two nanoparticles in a layer-by-layer growth fashion up to three bi-layers.

Nanocrystallization of oligosilanes by a reprecipitation method: easy fabrication of H-aggregates of linear-chain oligosilane molecules.

Nanocrystals of several oligosilanes have been fabricated easily by using a reprecipitation method. The nanocrystals reveal an intense absorption band at the UVB region (280 to 320 nm) and a fluorescence band with large Stokes shift. These photophysical properties show that the nanocrystals exhibit an excitonic interaction of the H-aggregate type.

Observation of light propagation across a 90 degrees corner in chains of microspheres on a patterned substrate.

To demonstrate light-path manipulation in arbitrary shapes we fabricated coupled-resonator optical waveguides (CROWs) having a 90 degrees-corner structure on a lithographically patterned substrate. The spectra of propagation light within the CROWs were directly measured by guide-collection-mode near-field scanning optical microscopy. The spectra revealed that the propagation light through the CROWs has a larger transverse-magnetic polarization mode than a transverse-electric (TE) one. The most plausible cause of the lower intensity in the TE mode is that light leaks out to the Si substrate.