Reaction of Aln clusters with oxygen and ammonia

Aluminum clusters were generated by a laser vaporization method. Ionization potential of Al₂ was found to be lower than that of Al. In the reaction with oxygen at high concentration, the mixed cluster Al₉O₇ survives predominantly as a stable cluster. Ammonia was found to be adsorbed weakly on the Al_n surface.     

Aggregation-driven growth of size-tunable organic nanoparticles using electronically altered conjugated polymers

A novel class of monodisperse conjugated polymer nanoparticles have been readily prepared by the facile reprecipitation of poly{1,3-bis[2-(3-alkylthienyl)]azulene} or poly{1,3-bis[2-(3-alkoxythienyl)]azulene}. The multicomponent poly(bithiophene-alt-azulene) macromolecules were efficiently self-assembled into a wide range of size-tunable nanoparticles from a few tens to five hundred nanometers via the hydrophobic and pi-stacking effects in the mixed chloroform/methanol solutions. Electronically altered polymer structures with different alkyl or alkoxy substitutes exhibited variable self-assembling behaviors to precisely tune the size and the optical/electronic properties of nanoparticles. A strong size dependence of continuous bathochromic absorption and significant enhanced emission were observed with the increase of particle size. A linear relationship between the absorption or fluorescence intensities and the particle size was demonstrated as well, and this is very useful to probe the intermolecular interactions and the size evolutions of conjugated polymer nanoparticles. After the size-dependent optical and electronic properties are created, they can be further optimized to improve the performance of materials prior to the use in novel organic nanodevices in a cost-effective way.     

The polarized reflection and absorption spectra of perylene crystals in monomeric and dimeric forms

The electronic absorption spectra of perylene crystals in the α- and β-forms were measured by the normal incidence reflection method in the spectral region from 20 000 to 60 000 cm^?1. From the absorption spectrum polarized perpendicular to [1$\text{1}$0] axis of the α-form crystal, the bands around 24 000 cm^?1 were determined to be polarized along the long molecular axis. Two strong bands with different polarizations were observed around 50 000 cm^?1 for each of the α- and β-perylene crystals and were assigned to the transitions to the ¹B_2u and ¹B_3u states. The observed polarized absorption spectra as a whole were consistent with the theoretical results by Hummel and Ruedenberg and the reflection method was found to be suitable to the polarized absorption measurement of strong bands of crystals. The observed factor-group splittings were compared with the theoretical values, the oriented gas model being found to be applicable to the β-form crystal.     

The first fully characterized 1,3-polyazulene: high electrical conductivity resulting from cation radicals and polycations generated upon protonation

[reaction: see text] 1,3-Polyazulene prepared by the chemical polymerization of 1,3-dibromoazulene with Ni(COD)(2) was aptly characterized by spectroscopic analysis. The azulene units remain intact in the isolated polymer. Protonation of 1,3-polyazulene by trifluoroacetic acid was found to exhibit high conductivity and paramagnetic properties via the formation of cation radicals and di- and polycations.     

Enhanced ordering in gold nanoparticles self-assembly through excess free ligands

Self-assembly of nanometer-sized particles is an elegant and economical approach to achieve dense patterns over large areas beyond the resolution and throughput capabilities of electron-beam lithography. In this paper, we present results of self-assembly of oleylamine-capped gold nanoparticles with 8.0 ± 0.3 nm diameter into densely packed and well-ordered monolayers with center-to-center distance of ～11 nm. Self-assembly was done in a Langmuir-Blodgett trough and picked up onto Si substrates. The nanoparticles undesirably assembled within micrometer-sized "droplets" that were organic in nature. However, within these droplets, we observed that the addition of the excess ligand, oleylamine, drastically enhanced the self-assembly of the nanoparticles into monolayers with near-perfect ordering. This approach has the potential use in templated self-assembly of nanoparticles for rearranging poorly ordered assembly into a commensurate prepatterned substrate.     

Surface-functionalized silica-coated gold nanoparticles and their bioapplications

Monodisperse Au at SiO₂ nanoparticles has been functionalized with carboxylic groups for further bioconjugation with amino-terminated oligonucleotides. The oligonucleotide-modified Au at SiO₂ nanoprobes have been applied in the fast colorimetric DNA based on the sequence-specific hybridization properties of DNA. Self-assembling behavior of Au at SiO₂ nanoparticles was also investigated.     

Fabrication and hard X-ray photoemission analysis of photocathodes with sharp solar-blind sensitivity using AlGaN films grown on Si substrates

Photocathode devices operating in reflection-mode, where the photoemission is detected on the same side as the light irradiation, were developed for the detection of deep ultraviolet light by using p-Al_xGa_1−xN films grown on Si(1 1 1) substrates. The external quantum efficiencies were as high as 20-15% at 200 nm and 280 nm, while the value was as low as 10⁻²% at 310 nm. The on-off ratio was more than four orders of magnitude, which represents high solar-blind sensitivity. The escape probability of Al_xGa_1−xN photocathode was decreased with increase of AlN mole fraction. The effective barrier potential against the photoelectron emission near the surface was reduced due to the upward shift of conduction band of Al_xGa_1−xN. The photoemission from the Al_xGa_1−xN films terminated with Cs-O adatoms will be discussed in terms of band diagrams that were evaluated by hard X-ray photoelectron spectroscopy.     

AGGREGATION OF COLLAGEN EXPOSED TO UVA IN THE PRESENCE OF RIBOFLAVIN: A PLAUSIBLE ROLE OF TYROSINE MODIFICATION

Riboflavin-sensitized photodynamic modification of collagen led to significant formation of cross-linked molecules. Sodium azide or l,4-diazabicyclo(2,2,2)octane, which are known to be singlet oxygen quenchers, and catalase could not inhibit the modification. Surprisingly, the collagen modification was accelerated in the presence of superoxide dismutase. The aggregation was accompanied by the loss of tyrosine and histidine residues in the collagen. An inhibitory effect of dissolved oxygen on the modification of collagen was observed. Similarly, the loss of tyrosine residues in the irradiated collagen was inhibited in the presence of dissolved oxygen. Dityrosine formation was also observed with the loss of tyrosine. These results indicate that photodynamic modification of tyrosine probably contributes to the riboflavin-sensitized cross-linking of collagen through the formation of dityrosine.     

Photoionization of small silicon clusters: ionization potentials for Si2 to Si40

Photoionization thresholds of Si _n (n=2–40) were examined by vacuum UV radiation (5.7–8.5 eV) generated by stimulated Raman scattering of narrow-bandwidth 193-nm radiation in high pressure hydrogen and deuterium gases. A strong threshold energy dependence on cluster size is observed, featuring major maxima at 10 and 20. The magic behavior atn=10 is consistent with the results of the photofragmentation and CID experiments reported previously.