Photoinduced electron transfer between fullerenes (C60 and C70) and phthalocyanines such as tetra-tert-butylphthalocyanine (H2TBPc) and its zinc derivative (ZnTBPc) in solution has been investigated with nanosecond laser photolysis method by observing the transient absorption bands in the visible/near-IR regions. By the predominant excitation of fullerenes with 532 nm laser light, slow rises of the transient absorption bands of phthalocyanine cation radicals and fullerene anion radicals were observed instead of the decays of the excited triplet states of fullerenes (TC60* and TC70*) in polar solvents. Electron-transfer from the phthalocyanines to TC60* or TC70* was confirmed. The quantum yield of the electron transfer via TC70* is higher than that via TC60*; ZnTBPc acts as stronger electron donor than H2TBPc. In nonpolar solvent, energy transfer from TC60* (and TC70*) to the phthalocyanines occurs predominantly as confirmed by the consecutive appearance of the triplet states of the phthalocyanines.

The basal plane of graphene has been known to be less reactive than the edges, but some studies observed vacancies in the basal plane after reaction with oxygen gas. Observation of these vacancies has typically been limited to nanometer-scale resolution using microscopic techniques. This work demonstrates the introduction and observation of subnanometer vacancies in the basal plane of graphene by heat treatment in a flow of oxygen gas at low temperature such as 533 K or lower. High-resolution transmission electron microscopy was used to directly observe vacancy structures, which were compared with image simulations. These proposed structures contain C═O, pyran-like ether, and lactone-like groups.

BackgroundHuman T-cell leukemia virus type 1 (HTLV-1) causes chronic infection leading to development of adult T-cell leukemia (ATL) and inflammatory diseases. Non-human primates infected with simian T-cell leukemia virus type 1 (STLV-1) are considered to constitute a suitable animal model for HTLV-1 research. However, the function of the regulatory and accessory genes of STLV-1 has not been analyzed in detail. In this study, STLV-1 in naturally infected Japanese macaques was analyzed.ResultsWe identified spliced transcripts of STLV-1 corresponding to HTLV-1 tax and HTLV-1 bZIP factor (HBZ). STLV-1 Tax activated the NFAT, AP-1 and NF-κB signaling pathways, whereas STLV-1 bZIP factor (SBZ) suppressed them. Conversely, SBZ enhanced TGF-β signaling and induced Foxp3 expression. Furthermore, STLV-1 Tax activated the canonical Wnt pathway while SBZ suppressed it. STLV-1 Tax enhanced the viral promoter activity while SBZ suppressed its activation. Then we addressed the clonal proliferation of STLV-1+ cells by massively sequencing the provirus integration sites. Some clones proliferated distinctively in monkeys with higher STLV-1 proviral loads. Notably, one of the monkeys surveyed in this study developed T-cell lymphoma in the brain; STLV-1 provirus was integrated in the lymphoma cell genome. When anti-CCR4 antibody, mogamulizumab, was administered into STLV-1-infected monkeys, the proviral load decreased dramatically within 2 weeks. We observed that some abundant clones recovered after discontinuation of mogamulizumab administration.ConclusionsSTLV-1 Tax and SBZ have functions similar to those of their counterparts in HTLV-1. This study demonstrates that Japanese macaques naturally infected with STLV-1 resemble HTLV-1 carriers and are a suitable model for the investigation of persistent HTLV-1 infection and asymptomatic HTLV-1 carrier state. Using these animals, we verified that mogamulizumab, which is currently used as a drug for relapsed ATL, is also effective in reducing the proviral load in asymptomatic individuals.

Photoinduced electron transfer between C60/C70 and zinc tetraphenylporphyrin (ZnTPP) in a polar solvent has been investigated with a nanosecond laser photolysis method by observing the transient absorption bands in the near-IR region. The transient absorption bands of the C60/C70 radical anion (C60 •-/C70 •-) in the near-IR region gave evidence of electron transfer for the system ZnTPP and C60/C70. In ZnTPP solution where C60 and C70 were photoexcited predominantly, electron transfer takes place from the ground state of ZnTPP to the triplet states of C60/C70 (3C60*/3C70*). In the concentrated ZnTPP solution where ZnTPP was predominantly photoexcited, the triplet state of ZnTPP donates the electron to the ground state of C60/C70, producing C60 •-/C70 •-. The efficiency of electron transfer via the 3C60*/3C70* route is higher than that via 3ZnTPP*.

Emission measurements were performed on a series of σ-π conjugated organosilicon copolymers, -[(SiMe2)mA]n-(m ) 1, 2, 3, 4, and 6), with alternating dimethylsilylene and π-conjugated units (A ) phenylene, diphenylene, and anthranylene) in various solvents. The copolymers with m g 2 exhibit a broad emission ascribable to an intramolecular charge transfer (CT) excited state resulting from the charge transfer between the dimethylsilylene and aromatic units. The solvatochromism of the emission spectra was observed for the organosilicon copolymers, where the emission maximum shifted to longer wavelength in polar solvents. The influence of the dimethylsilylene chain-length and the π-conjugated unit on the CT emission was investigated. The molecular orbital calculations on a model compound suggest that the vibronically structured emission is attributed to the π-character of the aromatic unit, and the structureless broad emission is ascribed to the σ-character of the Si-Si bond in the excited states. The emission lifetime and the quantum yield also show the dimethylsilylene chain-length dependence.

Photochemical reactions of 6H-purine-6-thione (PuT) via the excited triplet state [ 3 (PuT)*] have been studied by means of laser flash photolysis in organic solvents. Transient absorption bands at 475 and 690 nm were assigned to 3 (PuT)*. Intersystem quantum yield and the lowest triplet energy of 3 (PuT)* were evaluated to be 0.99 and 63 kcal/mol, respectively. The self-quenching rate constant is quite large (2.3 × 10 9 M -1 s -1 in THF). In photoinduced electron transfer, 3 (PuT)* acts as electron acceptor for tetramethylbenzidine, while 3 (PuT)* acts as electron donor for p-dinitrobenzene. Rate constants for H-atom abstraction (k hT ) of 3 (PuT)* from benzenethiols, tocopherol, and 1,4-cyclohexadiene are on the order of 10 8 M -1 s -1 . From the Hammett plots of k hT for substituted benzenethiols, a negative F value indicates that 3 (PuT)* has electrophilic character. In the addition reaction of 3 (PuT)* toward various alkenes, the electrophilic character of 3 (PuT)* was also confirmed. By steady-light photolysis of PuT, purine was produced via 3 (PuT)* after H-atom abstraction. On combination of these results, the character of the lowest 3 (PuT)* was presumed.

Photoinduced electron-transfer reactions between dithienothiophene (DTT) and the electron acceptors, p-dinitrobenzene (DNB) and CCl4, have been investigated using nanosecond laser flash photolysis and time-resolved fluoresence spectroscopy. Generation of the radical cations of DTTs and radical anion of DNB in acetonitrile solution was confirmed by transient absorption spectra in the visible and near-IR regions. Observed transient absorption bands corresponded to those of radical ions generated by γ irradiation in a frozen matrix. Electron transfer occurred both from the singlet and triplet excited states of DTT to DNB at the diffusion-controlled rate, ∼1010 M-1 s-1. When CCl4 was used as an acceptor, electron transfer from the singlet excited state occurred at the diffusion-controlled rate, while the reaction from the triplet excited state occurred at <109 M-1 s-1 due to small ΔG 0 for this reaction. For both acceptors, the singlet route tended to dominate the triplet route when concentration of the acceptor was increased. The radical ions decayed with second-order kinetics by back-electron transfer at a rate closed to the diffusion-controlled limit. In cyclohexane, generation of radical ions was completely suppressed and the triplet excited state of DTT was deactivated by energy transfer to DNB.

We have studied the magnetic field effects (MFEs) on the charge-transfer fluorescence and transient photocurrent of a 1,2,4,5-tetracyanobenzene-doped poly(N-vinylcarbazole) film, which reflect the recombination and escape yields of the carriers, respectively. The recombination yield dependence of the external magnetic field (B) clearly shows two types of the MFEs, growth with increasing B due to the hyperfine mechanism (HFM) and a negative dip due to the level-crossing mechanism (LCM). On the other hand, the escape yield indicates complementary MFEs with a sharp decrease in yield with increasing B and then a positive dip. Simultaneous observation of the HFM- and LCM-MFEs proves the stepwise hole-hopping mechanism rather the long-range hole-jumping one. The quantitative analysis of the recombination and escape MFEs is performed using the stochastic Liouville equations (SLE) for a one-dimensional lattice model in which the stepwise hole hops take place between the nearest neighbor carbazole units with spin conservation. The SLE analysis provides the recombination and hole transfer rate constants of 7.0 x 10(7) and 4.5 x 10(8) s(-1), respectively. The boundary site number for the ion pairs in the one-dimensional model is estimated by the best fit to the experimental results. The interionic distance of the boundary ion pair in the one-dimensional model including eight sites agrees with the thermalization distance in the Onsager model. Hence, it is concluded that the elementary processes in the Onsager model applied to molecular amorphous solids are the stepwise hole hops rather than a long-range hole jump.