Association behavior of a nitrilotriacetic-acid-modified dye in a poly(vinyl alcohol) film containing Ni(II)-adsorbed gold nanoparticles.

The association behavior of the dyes 5(6)-carboxyfluorescein and nitrilotriacetic acid (NTA)-modified 5(6)-carboxyfluorescein (F-NTA) in a poly(vinyl alcohol) (PVA) film and in a PVA film containing metal nanoparticles is investigated. Well-dispersed gold nanoparticles (AuNps) and Ni(II)-adsorbed AuNps are formed in the PVA film using in situ photochemical fabrication method. 5(6)-carboxyfluorescein and F-NTA are doped into the films. The F-NTA forms an H-aggregate in the PVA film containing Ni(II)-adsorbed AuNps. It is suggested that the interaction between NTA and Ni(II) adsorbed on the AuNps promotes the formation of the H-aggregate.     

Identification of a new excited state responsible for the in vivo unique absorption band of siphonaxanthin in the green alga Codium fragile

A marine green alga, Codium fragile, exhibits a characteristic in vivo absorption band of a specific keto-carotenoid, siphonaxanthin, at 535 nm. We examined the ultrafast fluorescence kinetics by direct excitation of this band after purification of light-harvesting complex II. On the basis of a high fluorescence anisotropy (0.39) up to 1 ps and a very short lifetime (60 fs), we identified the 535 nm band as a new electronically excited state (Sx) located between the S1 and S2 states. Excited-state dynamics of the Sx state were further discussed in relation to the energy transfer processes in the complexes.     

Porphyrin light-harvesting arrays constructed in the recombinant tobacco mosaic virus scaffold

We have demonstrated the construction of multiple porphyrin arrays in the tobacco mosaic virus (TMV) supramolecular structures by self-assembly of recombinant TMV coat protein (TMVCP) monomers, in which Zn-coordinated porphyrin (ZnP) and free-base porphyrin (FbP) were site-selectively incorporated. The photophysical properties of porphyrin moieties incorporated in the TMV assemblies were also characterized. TMV-porphyrin conjugates employed as building blocks self-assembled into unique disk and rod structures under the proper conditions as similar to native TMV assemblies. The mixture of a ZnP donor and an FbP acceptor was packed in the TMV assembly and showed energy transfer and light-harvesting activity. The detailed photophysical properties of the arrayed porphyrins in the TMV assemblies were examined by time-resolved fluorescence spectroscopy, and the energy transfer rates were determined to be 3.1-6.4x10(9) s(-1). The results indicate that the porphyrins are placed at the expected positions in the TMV assemblies.     

Intramolecular triplet energy transfer via higher triplet excited state during stepwise two-color two-laser irradiation

We studied the energy transfer processes in the molecular array consisting of pyrene (Py), biphenyl (Ph2), and bisphthalimidethiophene (ImT), (Py-Ph2)2-ImT, during two-color two-laser flash photolysis (2-LFP). The first laser irradiation predominantly generates ImT in the lowest triplet excited state (ImT(T1)) because of the efficient singlet energy transfer from Py in the lowest singlet excited state to ImT and, then, intersystem crossing of ImT. ImT(T1) was excited to the higher triplet excited state (Tn) with the second laser irradiation. Then, the triplet energy was rapidly transferred to Py via a two-step triplet energy transfer (TET) process through Ph2. The efficient generation of Py(T1) was suggested from the nanosecond-picosecond 2-LFP. The back-TET from Py(T1) to ImT was observed for several tens of microseconds after the second laser irradiation. The estimated intramolecular TET rate from Py(T1) to ImT was as slow as 3.1 x 104 s-1. Hence, long-lived Py(T1) was selectively and efficiently produced during the 2-LFP.     

Brønsted acid catalyzed formal insertion of isocyanides into a C-O bond of acetals

The Br?nsted acid catalyzed formal insertion of an isocyanide into a C-O bond of an acetal is described. A diverse array of acyclic and cyclic acetals can be applied to the catalytic insertion to form alpha-alkoxy imidates. Functional groups, such as nitro, cyano, halogen, ester, and alkoxy groups, are tolerant to the reaction conditions employed. The course of the reaction is highly dependent on the structure of the isocyanide. The use of an electron-deficient aryl isocyanide, such as 2c and 2d, is required to selectively obtain the monoinsertion product. When aryl isocyanides containing alkyl substituents, such as 2a and 2b, are employed, two molecules of the isocyanide are incorporated, and the double-insertion product is obtained. The reaction of tert-octyl isocyanide also induces a double incorporation, but the subsequent acid-mediated fragmentation leads to the 2-alkoxy imidoyl cyanide. The monoinsertion products, alpha-alkoxy imidates, can readily be hydrolyzed to alpha-alkoxy esters, realizing the formal carbonylation of an acetal.     

Mass spectrometric investigation of the aggregation and coalescence of fullerenes in C60-modified poly(N-vinylcarbazole) by UV-laser ablation

The phenomena of aggregation and coalescence of fullerenes in the UV-laser ablation time-of-flight mass spectrometric investigation of C₆₀-modified poly(N-vinylcarbazole) both in the positive and in the negative ion channels have been observed. The results indicate that in C₆₀ chemically modified PVK (C₆₀–PVK) copolymer the nascent fullerene fragments ruptured from main chain can easily coalesce into large fullerenes through collisions, whereas in the C₆₀-doped PVK the aggregation and coalescence of C₆₀ were relative weak due to nonbounding action and incomplete charge transfer behavior between C₆₀ and PVK. Furthermore, the photoinduced electron transfer behavior between C₆₀ and carbazole units in the C₆₀ chemically modified poly(N-vinylcarbazole) in benzonitrile by laser flash photolysis at 355 nm has also been investigated. Efficiency of the anion radical of C₆₀ in copolymer at 1080 nm is higher than that of the C₆₀-doped poly(N-vinylcarbazole) polymers. The formation of a C₆₀ radical anion may be ascribed to photoinduced electron transfer between C₆₀ pendanted on the main chain backbone and the inter-, and intrachain carbazole units in the copolymer. © 1997 John Wiley & Sons, Inc. 35 : 1185–1190, 1997     

FTIR spectroscopic study on crystallization process of poly(ethylene-2,6-naphthalate)

In situ Fourier transform infrared (FTIR) measurements were carried out to elucidate conformation changes occurring during the isothermal melt crystallization of poly(ethylene-2,6-naphthalate) (PEN). Based on the band assignments for the components of the amorphous, α-crystal form, and β-crystal form of PEN in film samples, the in situ data was analyzed in terms of the amorphous- and crystal-trans conformations. It was observed at a higher isothermal crystallization temperature that the formation of amorphous-trans conformations precedes the growth of crystals. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2741–2747, 1997     

Analysis of visual perception of light emitting diode brightness in dense fog with various droplet sizes

Road signs must provide a conspicuous signal to a wide variety of drivers over a broad range of environmental and geometric conditions. Recently, there are an increasing number of applications in which light emitting diodes (LEDs) are used as the light source, including critical transportation signaling. In the presence of fog, the resulting visual signal is disturbed due to light scattering by airborne water droplets. By measuring LED brightness with human spectral sensitivity in various densities and various droplet sizes (10, 30, 50, and 100 μm), it is understood that the particle size distribution (fog droplet size) and density of fog does affect visibility in fog. The colored LEDs that contain a yellow component had high brightness evaluation, blue component had low brightness evaluation in all densities and different droplet sizes. The result in this paper can contribute to air and land traffic safety and the prevention of accidents.     

Information patterns and Nash equilibria in extensive games: 1

In this paper we explore the relation between information patterns and Nash Equilibria in extensive games. By information we mean what players know about moves made by others, as well as by chance. For the most part we confine ourselves to pure strategies. But in Section 2 behavioral strategies are also examined. It turns out that they can be modeled as pure strategies of an appropriately enlarged game. Our results, applied to the enlarged game, can then be reinterpreted in terms of the behavioral strategies of the original game.