Mamoru Fujitsuka

Au/TiO2 superstructure-based plasmonic photocatalysts exhibiting efficient charge separation and unprecedented activity.

Plasmonic photocatalysts were successfully synthesized by the modification of TiO2 mesocrystals with Au nanoparticles (NPs) by a simple impregnation method. The Au NP sensitizers show a strong photoelectrochemical response in the visible-light region (400-800 nm) due to their surface plasmon resonance (SPR). The diffuse reflectance spectroscopy measurements on a wide range of time scales (from picoseconds to minutes) demonstrate that a substantial part of electrons, injected from the Au NPs to the TiO2 mesocrystals through the SPR excitation, directionally migrate from the basal surfaces to the edges of the plate-like mesocrystals through the TiO2 nanocrystal networks and are temporally stored there for further reactions. This anisotropic electron flow significantly retarded the charge recombination of these electrons with the holes in the Au NPs, thereby improving the visible-light-photocatalytic activity (for organic-pollutant degradation) by more than an order of magnitude, as compared to that of conventional Au/TiO2 NP systems.

Metal-Free Photocatalyst for H2 Evolution in Visible to Near-Infrared Region: Black Phosphorus/Graphitic Carbon Nitride

In the drive toward green and sustainable chemistry, exploring efficient and stable metal-free photocatalysts with broadband solar absorption from the UV to near-infrared region for the photoreduction of water to H2 remains a big challenge. To this end, a binary nanohybrid (BP/CN) of two-dimensional (2D) black phosphorus (BP) and graphitic carbon nitride (CN) was designed and used as a metal-free photocatalyst for the first time. During irradiation of BP/CN in water with >420 and >780 nm light, solid H2 gas was generated, respectively. Owing to the interfacial interaction between BP and CN, efficient charge transfer occurred, thereby enhancing the photocatalytic performance. The efficient charge-trapping and transfer processes were thoroughly investigated with time-resolved diffuse reflectance spectroscopic measurement. The present results show that BP/CN is a metal-free photocatalyst for artificial photosynthesis and renewable energy conversion.

Far-red fluorescence probe for monitoring singlet oxygen during photodynamic therapy.

Singlet oxygen ((1)O2), molecular oxygen in the lowest excited state, has a critical role in the cell-killing mechanism of photodynamic therapy (PDT). Although (1)O2 phosphorescence measurement has been mainly used to monitor (1)O2 formation during PDT, its intensity is far insufficient to obtain two-dimensional images of intracellular (1)O2 with the subcellular spatial resolution using the currently available near-IR detector. Here, we propose a new far-red fluorescence probe of (1)O2, namely, Si-DMA, composed of silicon-containing rhodamine and anthracene moieties as a chromophore and a (1)O2 reactive site, respectively. In the presence of (1)O2, fluorescence of Si-DMA increases 17 times due to endoperoxide formation at the anthracene moiety. With the advantage of negligible self-oxidation by photoirradiation (ΦΔ < 0.02) and selective mitochondrial localization, Si-DMA is particularly suitable for imaging (1)O2 during PDT. Among three different intracellular photosensitizers (Sens), Si-DMA could selectively detect the (1)O2 that is generated by 5-aminolevulinic acid-derived protoporphyrin IX, colocalized with Si-DMA in mitochondria. On the other hand, mitochondria-targeted KillerRed and lysosomal porphyrins could not induce fluorescence change of Si-DMA. This surprising selectivity of Si-DMA response depending on the Sens localization and photosensitization mechanism is caused by a limited intracellular (1)O2 diffusion distance (∼300 nm) and negligible generation of (1)O2 by type-I Sens, respectively. For the first time, we successfully visualized (1)O2 generated during PDT with a spatial resolution of a single mitochondrial tubule.

pH-Induced Intramolecular Folding Dynamics of i-Motif DNA

Using the combination of fluorescence resonance energy transfer (FRET) and fluorescence correlation spectroscopy (FCS) technique, we investigate the mechanism and dynamics of the pH-induced conformational change of i-motif DNA in the bulk phases and at the single-molecule level. Despite numerous studies on i-motif that is formed from cytosine (C)-rich strand at slightly acidic pH, its detailed conformational dynamics have been rarely reported. Using the FRET technique to provide valuable information on the structure of biomolecules such as a protein and DNA, we clearly show that the partially folded species as well as the single-stranded structure coexist at neutral pH, supporting that the partially folded species may exist substantially in vivo and play an important role in a process of gene expression. By measuring the FCS curves of i-motif, we observed the gradual decrease of the diffusion coefficient of i-motif with increasing pH. The quantitative analysis of FCS curves supports that the gradual decrease of diffusion coefficient (D) associated with the conformational change of i-motif is not only due to the change in the intermolecular interaction between i-motif and solvent accompanied by the increase of pH but also due to the change of the shape of DNA. Furthermore, FCS analysis showed that the intrachain contact formation and dissociation for i-motif are 5-10 times faster than that for the open form. The fast dynamics of i-motif with a compact tetraplex is due to the intrinsic conformational changes at the fluorescent site including the motion of alkyl chain connecting the dye to DNA, whereas the slow intrachain contact formation observed from the open form is due to the DNA motion corresponding to an early stage interaction in the folding process of the unstructured open form.

Au/La2Ti2O7 Nanostructures Sensitized with Black Phosphorus for Plasmon-Enhanced Photocatalytic Hydrogen Production in Visible and Near-Infrared Light

Efficient utilization of solar energy is a high-priority target and the search for suitable materials as photocatalysts that not only can harvest the broad wavelength of solar light, from UV to near-infrared (NIR) region, but also can achieve high and efficient solar-to-hydrogen conversion is one of the most challenging missions. Herein, using Au/La2 Ti2 O7 (BP-Au/LTO) sensitized with black phosphorus (BP), a broadband solar response photocatalyst was designed and used as efficient photocatalyst for H2 production. The optimum H2 production rates of BP-Au/LTO were about 0.74 and 0.30 mmol g-1  h-1 at wavelengths longer than 420 nm and 780 nm, respectively. The broad absorption of BP and plasmonic Au contribute to the enhanced photocatalytic activity in the visible and NIR light regions. Time-resolved diffuse reflectance spectroscopy revealed efficient interfacial electron transfer from excited BP and Au to LTO which is in accordance with the observed high photoactivities.

Europium-Based Metal−Organic Framework as a Photocatalyst for the One-Electron Oxidation of Organic Compounds

Lanthanide-based metal-organic frameworks (Ln-MOFs) are fascinating because of their versatile coordination geometry, unique luminescent and magnetic properties, and possible high framework stability to water. We synthesized nanosized europium-based MOF (Eu-MOF) particles and investigated the photoinduced electron transfer between the excited Eu-MOF nanoparticles and various organic compounds, such as aromatic sulfides and amines. From the time-resolved emission measurements, the bimolecular quenching rate constants of luminescence from the Eu(3+) ions in the MOF framework by electron donors were determined and explained in terms of the Marcus theory of electron-transfer reactions. Furthermore, spatially resolved emission quenching images obtained by confocal fluorescence microscopy revealed that small (large) quencher molecules quickly (slowly) and homogeneously (inhomogeneously) penetrate microsized Eu-MOF crystals. These observations led us confidently to assume the possibility that Eu-MOFs work as a size-selective photocatalyst for the one-electron oxidation of organic compounds.

Photochemistry of singlet oxygen sensor green.

To detect singlet oxygen ((1)O2), the commercially available fluorescent sensor named Singlet Oxygen Sensor Green (SOSG) has been the most widely used from material studies to medical applications, for example, photodynamic therapy. In light of the previous studies, SOSG is a dyad composed of fluorescein and anthracene moieties. In the present study, we carried out quantitative studies on photochemical dynamics of SOSG for the first time, such as the occurrence of intramolecular photoinduced electron transfer (PET), (1)O2 generation, and two-photon ionization. It was revealed that these relaxation pathways strongly depend on the irradiation conditions. The visible-light excitation (ex. 532 nm) of SOSG induced intramolecular PET as a major deactivation process (kPET = 9.7 × 10(11) s(-1)), resulting in fluorescence quenching. In addition, intersystem crossing occurred as a minor deactivation process that gave rise to (1)O2 generation via the bimolecular triplet-triplet energy transfer (kq = 1.2 × 10(9) M(-1) s(-1)). Meanwhile, ultraviolet-light excitation (355 nm) of SOSG caused the two-photon ionization to give a SOSG cation (Φion = 0.003 at 24 mJ cm(-2)), leading to SOSG decomposition to the final products. Our results clearly demonstrate the problems of SOSG, such as photodecomposition and (1)O2 generation. In fact, these are not special for SOSG but common drawbacks for most of the fluorescein-based sensors.

Defect-Mediated Photoluminescence Dynamics of Eu3+-Doped TiO2 Nanocrystals Revealed at the Single-Particle or Single-Aggregate Level†

Lanthanide-doped materials are finding use in a wide variety of applications in optics as gain media for amplifiers and lasers and as biolabels, white-light emitters, and full-color phosphors for displays. Since direct excitation of the parity-forbidden intra-f-shell lanthanide ion crystal-field transitions is inefficient, it is anticipated that the luminescence of lanthanide ions incorporated in a wide-band-gap semiconductor lattice (e.g., ZnO and TiO2) could be sensitized efficiently by exciton recombination in the host (Figure 1). Recently, we synthesized Eu-doped TiO2 (TiO2:Eu ) nanocrystals by Ar/O2 radio-frequency thermal plasma oxidation and observed bright red emission either by exciting the TiO2 host with UV light of shorter wavelength than 405 nm or by directly exciting Eu at a wavelength beyond the absorption edge (405 nm, 3.06 eV) of TiO2. Various types of defect states have been considered to play an important role in energy transfer between TiO2 and the activating Eu ions. For example, with increasing annealing temperature, the photoluminescence (PL) intensity of visible emissions due to Eu ions increases at first but then decreases and reaches a maximum at an annealing temperature of 700 8C. In this respect, the luminescence of Eu depends critically on the locations of dopants in the host. However, the mechanism of the energy-transfer process from the defect energy levels of the host to dopants has not yet been clarified owing to several difficulties, such as the inhomogeneous distribution of ions in the material. Single-molecule (single-particle) fluorescence spectroscopy has already yielded new insight into the photophysics and photochemistry of inorganic and organic nanocrystals. There are, however, only a few reports on the PL behavior of lanthanide-doped materials. We have now investigated the PL dynamics of undoped TiO2 and TiO2:Eu 3+

A nanocomposite superstructure of metal oxides with effective charge transfer interfaces

The alignment of nanoparticle building blocks into ordered superstructures is one of the key topics in modern colloid and material chemistry. Metal oxide mesocrystals are superstructures of assembled nanoparticles of metal oxides and have potentially tunable electronic, optical and magnetic properties, which would be useful for applications ranging from catalysis to optoelectronics. Here we report a facile and general approach for synthesizing metal oxide mesocrystals and developing them into new nanocomposite materials containing two different metals. The surface and internal structures of the mesocrystals were fully characterized by electron microscopy techniques. Single-particle confocal fluorescence spectroscopy, electron paramagnetic resonance spectroscopy and time-resolved diffuse reflectance spectroscopy measurements revealed that efficient charge transfer occurred between n-type and p-type semiconductor nanoparticles in the composite mesocrystals. This behaviour is desirable for their applications ranging from catalysis, optoelectronics and sensing, to energy storage and conversion.

Single-molecule observation of photocatalytic reaction in TiO2 nanotube: importance of molecular transport through porous structures.

We have investigated the photocatalytic activity of individual porous TiO(2) nanotubes by the single-molecule counting of (*)OH using a specific fluorescent probe. The time- and space-resolved observation of emissive fluorescein generated by the photocatalytic reaction clearly reveals the importance of the transport behavior of reagents through the porous structures on the photocatalytic activity and the existence of the spatial heterogeneity of reactive sites even in an isolated TiO(2) nanotube. An experiment on a single nanotube provided information that was useful for elucidating the reaction mechanism of the heterogeneous (photo)catalyst and for designing advanced porous materials.