Emission from charge recombination during the pulse radiolysis of arylethynylpyrenes

Emission from several 1-(arylethynyl)pyrenes with a substituent on the aryl group (REPy, R = phenyl (PEPy), 4-dimethylaminophenyl (NPEPy), 4-isopropoxyphenyl (OPEPy), 2-quinonyl (QEPy), and 9-(10-cyanoanthracenyl) (AEPy)) was studied with time-resolved fluorescence measurements during pulse radiolysis in benzene. NPEPy and AEPy showed only monomer emission, while PEPy, OPEPy, and QEPy showed both monomer and excimer emissions during pulse radiolysis. In addition, REPy's also showed long-lived emissions with very weak intensities in the absence of oxygen, which were assigned to the "P-type" delayed fluorescence derived from the triplet-triplet annihilation. The formation of REPy's in the singlet excited state (1REPy*) can be interpreted as the charge recombination between the REPy radical cation and anion (REPy*+ and REPy*-, respectively), which are initially generated from the radiolytic reaction in benzene. Both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of PEPy are localized on the 1-pyrenyl (Py) moiety, while the HOMO of REPy's with an electron donating or withdrawing substituent on the benzene ring (R(D)EPy such as NPEPy and OPEPy or R(A)EPy such as QEPy and AEPy) is mainly localized on the donor moieties (R(D) or Py) and the LUMO on the acceptor ones (Py or R(A), respectively). Therefore, it is suggested that the one-electron oxidation and reduction of REPy's can occur from the donor and acceptor moieties, respectively. This scheme reasonably explains the relationship between the annihilation enthalpy changes (-Delta H' degrees) for the charge recombination of REPy*+ and REPy*- and the singlet excitation energies (E'(S1) of the REPy's. The results are compared with those in electrogenerated chemiluminescence.     

Adsorption and micellization behavior of novel gluconamide-type gemini surfactants

The adsorption and micellization behavior of novel sugar-based gemini surfactants (N,N(')-dialkyl-N,N(')-digluconamide ethylenediamine, Glu(n)-2-Glu(n), where n is the hydrocarbon chain length of 8, 10 and 12) has been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The static surface tension of the aqueous Glu(n)-2-Glu(n) solutions measured at the critical micelle concentration (cmc) is observed to be significantly lower than that of the corresponding monomeric surfactants. This suggests that the gemini surfactants, newly synthesized in the current study, are able to form a closely packed monolayer film at the air/aqueous solution interface. The greater ability in the molecular association is supported by the remarkably (approximately 100-200 times) lower cmc of the gemini surfactants compared with the corresponding monomeric ones. With a combination of the fluorescence and DLS data, a structural transformation of the Glu(n)-2-Glu(n) micelles is suggested to occur with an increase in the concentration. The cryo-TEM measurements clearly confirm the formation of worm-like micelles of Glu(12)-2-Glu(12) at the concentration well above the cmc.     

POLARIZED TIME-RESOLVED FLUORESCENCE SPECTRA OF PHYCOBILISOMES ISOLATED FROM Tolypothrix tenuis EMBEDDED IN POLY(VINYL ALCOHOL) FILM

–Time-resolved fluorescence spectra in the ps time range were measured on phycobilisome (PBS) embedded in poly(vinyl alcohol) films. The cyanobacterium Tolypothrix tenuis was used as a source of PBS because the pigment composition and the structure of the PBS are well defined. Isotropic PBS in the unstretched film and PBS uniaxially oriented in the stretched film were investigated. Diameters of PBS hemidiscs were oriented parallel to the film-stretching direction. The time-resolved fluorescence spectra of the unstretched sample and of the two polarized components in the stretched samples showed several differences in the rise and decay. The delay time, estimated from the time span between the maximum laser pulse and maximal intensity of the phycocyanin and allophycocyanin fluorescence, was much longer than that reported in the aqueous media. This suggests occurrence of a higher thermal deactivation of PBS in polymer film than in aqueous media. The excitation energy transfer from excited phycocrythrin to allophycocyanin was more efficient in the unstretched than in the stretched samples, and it was greater in the parallel polarized component of the stretched sample than in the perpendicular component. The present results are in agreement with a previous suggestion which states that there are two independent pathways of excitation energy transfer in PBS and that there is more than one final emitter of fluorescence. The molecules taking part in various pathways of energy transfer differ in their orientation within PBS.     

Infrared photodissociation spectroscopy of Al(+)(CH(3)OH)(n) (n = 1-4)

Infrared photodissociation spectra of Al(+)(CH(3)OH)(n) (n = 1-4) and Al(+)(CH(3)OH)(n)-Ar (n = 1-3) were measured in the OH stretching region, 3000-3800 cm(-1). For n = 1 and 2, sharp absorption bands were observed in the free OH stretching region, all of which were well reproduced by the spectra calculated for the solvated-type geometry with no hydrogen bond. For n = 3 and 4, there were broad vibrational bands in the energy region of hydrogen-bonded OH stretching vibrations, 3000-3500 cm(-1). Energies of possible isomers for the Al(+)(CH(3)OH)(3),4 ions with hydrogen bonds were calculated in order to assign these bands. It was found that the third and fourth methanol molecules form hydrogen bonds with methanol molecules in the first solvation shell, rather than a direct bonding with the Al(+) ion. For the Al(+)(CH(3)OH)(n) clusters with n = 1-4, we obtained no evidence of the insertion reaction, which occurs in Al(+)(H(2)O)(n). One possible explanation of the difference between these two systems is that the potential energy barriers between the solvated and inserted isomers in the Al(+)(CH(3)OH)(n) system is too high to form the inserted-type isomers.     

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.     

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.     

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.     

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.