Molecular Characteristics of Water-Insoluble Tin-Porphyrins for Designing the One-Photon-Induced Two-Electron Oxidation of Water in Artificial Photosynthesis.

Faced with the new stage of water oxidation by molecular catalysts (MCs) in artificial photosynthesis to overcome the bottle neck issue, the "Photon-flux density problem of sunlight," a two-electron oxidation process forming H2O2 in place of the conventional four-electron oxidation evolving O2 has attracted much attention. The molecular characteristics of tin(IV)-tetrapyridylporphyrin (SnTPyP), as one of the most promising MCs for the two-electron water oxidation, has been studied in detail. The protolytic equilibria among nine species of SnTPyP, with eight pKa values on the axial ligands' water molecules and peripheral pyridyl nitrogen atoms in both the ground and excited states, have been clarified through the measurements of UV-vis, fluorescence, 1H NMR, and dynamic fluorescence decay behaviour. The oxidation potentials in the Pourbaix diagram and spin densities by DFT calculation of the one-electron oxidized form of each nine species have predicted that the fully deprotonated species ([SnTPyP(O-)2]2-) and the singly deprotonated one ([SnTPyP(OH)(O-)]-) serve as the most favourable MCs for visible light-induced two-electron water oxidation when they are adsorbed on TiO2 for H2 formation or SnO2 for Z-scheme CO2 reduction in the molecular catalyst sensitized system of artificial photosynthesis.

A Molecular Z-Scheme Artificial Photosynthetic System Under the Bias-Free Condition for CO2 Reduction Coupled with Two-electron Water Oxidation: Photocatalytic Production of CO/HCOOH and H2 O2.

Bio-inspired molecular-engineered systems have been extensively investigated for the half-reactions of H2 O oxidation or CO2 reduction with sacrificial electron donors/acceptors. However, there has yet to be reported a device for dye-sensitized molecular photoanodes coupled with molecular photocathodes in an aqueous solution without the use of sacrificial reagents. Herein, we will report the integration of SnIV - or AlIII -tetrapyridylporphyrin (SnTPyP or AlTPyP) decorated tin oxide particles (SnTPyP/SnO2 or AlTPyP/SnO2 ) photoanode with the dye-sensitized molecular photocathode on nickel oxide particles containing [Ru(diimine)3 ]2+ as the light-harvesting unit and [Ru(diimine)(CO)2 Cl2 ] as the catalyst unit covalently connected and fixed within poly-pyrrole layer (RuCAT-RuC2 -PolyPyr-PRu/NiO). The simultaneous irradiation of the two photoelectrodes with visible light resulted in H2 O2 on the anode and CO, HCOOH, and H2 on the cathode with high Faradaic efficiencies in purely aqueous conditions without any applied bias is the first example of artificial photosynthesis with only two-electron redox reactions.

Heat trapping in a nano-layered microenvironment: estimation of temperature by thermal sensing molecules.

We have previously found reversible photo-induced expansion and contraction of organic/inorganic clay hybrids, and even sliding of niobate nano-sheets at the macroscopic level of organic/inorganic niobate hybrids, induced by the molecular photo-isomerization of the polyfluoroalkylated azobenzene derivative (C3F-Azo-C6H) intercalated within the interlayer, which is viewed as an artificial muscle model unit. Based on systematic investigations of the steady state photo-isomerization and transient behavior of the reaction, we comprehended that the phenomena is caused by trapping of excess energy liberated during the isomerization, as well as the relaxation processes upon excitation of azobenzene chromophores in the interlayers of the hybrid. In this paper, quantitative estimation of transient 'heat' trapped in various microenvironments has been studied by each co-intercalation of temperature sensing dye molecules - rhodamine B (RhB) or tris(bipyridine)ruthenium(ii) chloride (Rubpy) with C3F-Azo-C6H within clay (SSA) nano-layers. The amount of dye molecules co-intercalated was kept to trace amounts that did not alter the bi-layered structure of the hybrid. The temperature of the microenvironment surrounding the probe molecules was estimated from the emission lifetime analysis. The evidently reduced emission lifetimes in C3F-Azo-C6H/SSA and C3H-Azo-C6H/SSA hybrids in the film state, indicated the elevation of temperature of the microenvironment upon excitation of the chromophores, which demonstrated our previous hypothesis rationalizing that the high reactivity of isomerization in the hybrid film state is caused by heat trapping via multi-step dissipation of the excess energy. With the hybrid of a hydrocarbon analogue (C3H-Azo-C6H), a distinct difference in temperature gradient was found to show the crucial role of the perfluoroalkyl chain of the surfactant that traps the excess energy to retard its dissipation leading to three-dimensional morphological motion.

Synthesis of a photo-responsive single-walled nanoscroll and its photo-reactivity in a nano-layered microenvironment.

A photo-responsive nanoscroll composed of niobate nanosheets and a polyfluoroalkyl azobenzene derivative (C3F-Azo-C6H) is one of the most interesting layered materials because the reversible winding and unwinding motion could be efficiently induced by photo-irradiations. Previously, we have studied a double-walled nanoscroll (DWNS) of niobate that could be synthesized by the intercalation of a cationic polyfluorinated surfactant only into the interlayer I of the layered niobate among the two interlayers, I and II. In this study, we have successfully synthesized another novel photo-responsive single-walled nanoscroll (SWNS) of niobate by a stepwise guest-guest ion-exchange method. All niobate nanosheets that were exfoliated at both interlayers I and II were efficiently converted to nanoscrolls by the intercalation of C3F-Azo-C6H. The synthetic yield has been quantitatively estimated. Though the photo-isomerization reaction of C3F-Azo-C6H was induced in the SWNS, its photo-reactivity was the lowest when compared with those of the nanosheet-stacked film and the DWNS. The photo-reactivity of C3F-Azo-C6H decreased in the order of DWNS > nanosheet-stacked film > SWNS. The different flexibility of the layered miroenvironment might influence the photo-reactivity of C3F-Azo-C6H in the niobate hybrid. The SWNS exhibited a reversible expansion and shrinkage of its interlayer spaces upon photo-irradiation, while the winding and unwinding motion was not observed, contrary to the DWNS. The direction of the expansion and shrinkage of the interlayer of the SWNS was opposite to those of the nanosheet-stacked film and the DWNS. Based on the experimental results, the tilt angle of C3F-Azo-C6H against the nanosheet surface and the matching structures of the top and bottom surfaces of the nanosheet could be the probable key factors that control the photo-reactivity of C3F-Azo-C6H in the layered microenvironment; the morphological changes of the nano hybrids was also discussed.

Which types of clay minerals fix cesium ions effectively? the "cavity-charge matching effect".

How can radioactive Cs+ ions be removed from aqueous solution? From this perspective, the adsorption of Cs+ was investigated by using five types of clay minerals possessing different charge exchange capacities. The fixation ability for Cs+ depended on the charge exchange capacity of the clay minerals. Phlogopite and vermiculite, where the number of charges is almost equal to half the number of siloxane ditrigonal cavities in the structure, exhibited a strong Cs+ fixation ability among these clay minerals. In these clay minerals, effective interlayer collapse, which leads to quasi-irreversible adsorption of Cs+, is expected from the introduction of Cs+ into the layer space. This is named the "cavity-charge matching effect". This study clarifies why only phlogopite and vermiculite can fix Cs+ quite strongly among various types of clay minerals. These findings are beneficial for removing radioactive Cs+ ions from the environment using clay minerals through the cavity-charge matching effect.

Synthesis of double-wall nanoscrolls intercalated with polyfluorinated cationic surfactant into layered niobate and their magnetic alignment.

The orientation of nanomaterials with an anisotropic nature such as nanoscrolls is very important for realizing their efficient and sophisticated functions in devices, including nanostructured electrodes in artificial photosynthetic cells. In this study, we successfully synthesized a nanoscroll by intercalation of a cationic polyfluorinated surfactant into the interlayer spaces of layered niobate and successfully controlled its orientation by applying an external magnetic field in water. The exfoliated niobate nanosheets were efficiently rolled-up to form nanoscrolls, which have a fine layered structure (d020 = 3.64 nm), by mixing with heptafluorobutanoylaminoethylhexadecyldimethylammonium bromide (C3F-S) in water, whereas the corresponding hydrocarbon analogue (C3H-S) did not form nanoscrolls. The synthetic yield for the purified and isolated nanoscrolls from the nanosheets was estimated to be 62% by weight. It was confirmed by atomic force microscopy (AFM) that most of the niobate nanosheets (98%) were converted to nanoscrolls. An external magnetic field was applied to the nanoscrolls to force them to align. After the magnetic treatment, the orientation of the nanoscrolls was investigated by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The non-uniform ring distribution of the SAXS patterns indicates that the nanoscrolls dispersed in water were aligned well on applying the magnetic field. The long axis of the nanoscroll was oriented in the direction of the applied field and long nanoscrolls were aligned more efficiently. When the intercalated C3F-S molecules were removed from the nanoscrolls by treating with an acid, the resultant nanoscrolls did not exhibit magnetic alignment, strongly suggesting that C3F-S plays an important role in the orientation control of the nanoscrolls by the magnetic field.

Dense Deposition of Gold Nanoclusters Utilizing a Porphyrin/Inorganic Layered Material Complex as the Template.

We examined the deposition of gold clusters through the reduction of a gold precursor sensitized by nonaggregated, assembled porphyrin molecules on an inorganic layered material surface in order to develop a novel strategy for constructing assemblies of gold clusters. Visible light irradiation on nonaggregated, assembled porphyrin on the inorganic surface in the presence of the gold precursor and an electron donor induced the deposition of gold NPs on the surface of the inorganic layered material. Uniform gold clusters, with an average diameter of 1.5 nm, were deposited on the surface without aggregation. The average interparticle distance between adjacent gold clusters (center to center) was 2.3 nm, which agrees well with the average intermolecular distance of the nonaggregated, assembled porphyrin molecules on the inorganic surface. Thus, the generated gold clusters appear to reflect the nonaggregated, assembled structure of the porphyrin molecules on the inorganic surface. This method, termed the photosensitized template reduction (PTR) method, is a useful and novel technique for the deposition of metal nanoparticles on the surfaces of supporting materials.

Direct detection of key reaction intermediates in photochemical CO2 reduction sensitized by a rhenium bipyridine complex.

Photochemical CO2 reduction sensitized by rhenium-bipyridyl complexes has been studied through multiple approaches during the past several decades. However, a key reaction intermediate, the CO2-coordinated Re-bipyridyl complex, which should govern the activity of CO2 reduction in the photocatalytic cycle, has never been detected in a direct way. In this study on photoreduction of CO2 catalyzed by the 4,4'-dimethyl-2,2'-bipyridine (dmbpy) complex, [Re(dmbpy)(CO)3Cl] (1), we successfully detect the solvent-coordinated Re complex [Re(dmbpy)(CO)3DMF] (2) as the light-absorbing species to drive photoreduction of CO2. The key intermediate, the CO2-coordinated Re-bipyridyl complex, [Re(dmbpy)(CO)3(COOH)], is also successfully detected for the first time by means of cold-spray ionization spectrometry (CSI-MS). Mass spectra for a reaction mixture with isotopically labeled (13)CO2 provide clear evidence for the incorporation of CO2 into the Re-bipyridyl complex. It is revealed that the starting chloride complex 1 was rapidly transformed into the DMF-coordinated Re complex 2 through the initial cycle of photoreduction of CO2. The observed induction period in the time profile of the CSI-MS signals can well explain the subsequent formation of the CO2-coordinated intermediate from the solvent-coordinated Re-bipyridyl complex. An FTIR study of the reaction mixture in dimethyl sulfoxide clearly shows the appearance of a signal at 1682 cm(-1), which shifts to 1647 cm(-1) for the (13)CO2-labeled counterpart; this is assigned as the CO2-coordinated intermediate, Re(II)-COOH. Thus, a detailed understanding has now been obtained for the mechanism of the archetypical photochemical CO2 reduction sensitized by a Re-bipyridyl complex.

Hydrogen evolution coupled with the photochemical oxygenation of cyclohexene with water sensitized by tin(IV) porphyrins by visible light.

Hydrogen evolution coupled with the photochemical oxygenation of cyclohexene with water was observed in the system sensitized by Sn(IV)-porphyrin adsorbed on Pt loaded TiO2 nano-particles in aqueous acetonitrile solution upon visible light irradiation.

Remarkable enhancement of the photoreactivity of a polyfluoroalkyl azobenzene derivative in an organic-inorganic nano-layered microenvironment.

Organic-inorganic hybrids composed of polyfluoroalkyl azobenzene surfactant (abbreviated as C3F-Azo-C6H) and inorganic layered compounds are able to undergo reversible three-dimensional morphology changes such as interlayer space changes and nanosheet sliding in a giant scale due to reversible trans-cis isomerization of the azobenzene moiety upon photo-irradiation. In this paper, we have systematically studied the relationship between the layered hybrid microstructures of C3F-Azo-C6H-clay and their photoreactivity for understanding the mechanism of the photo-induced morphology change. The photoreactivity was found to be very much affected by the surrounding microenvironments. As compared with it in solution, the cis-trans photo-isomerization in C3F-Azo-C6H-clay nano-layered film was substantially enhanced with the quantum yield exceeding unity (Φ = 1.9), while the trans-cis isomerization was rather retarded. The corresponding hydrocarbon analogue of the azobenzene surfactant (C3H-Azo-C6H) did not show such an enhancement. The enhancement was discussed in terms of a cooperative effect among adjacent azobenzene moieties along with polyfluoroalkyl chains and the inorganic clay nanosheet to prevent a dissipation of the excess energy being liberated during the photo-isomerization within the nano-layered microenvironment.

Plasmon-assisted water splitting using two sides of the same SrTiO3 single-crystal substrate: conversion of visible light to chemical energy.

A plasmon-induced water splitting system that operates under irradiation by visible light was successfully developed; the system is based on the use of both sides of the same strontium titanate (SrTiO3) single-crystal substrate. The water splitting system contains two solution chambers to separate hydrogen (H2) and oxygen (O2). To promote water splitting, a chemical bias was applied by regulating the pH values of the chambers. The quantity of H2 evolved from the surface of platinum, which was used as a reduction co-catalyst, was twice the quantity of O2 evolved from an Au-nanostructured surface. Thus, the stoichiometric evolution of H2 and O2 was clearly demonstrated. The hydrogen-evolution action spectrum closely corresponds to the plasmon resonance spectrum, indicating that the plasmon-induced charge separation at the Au/SrTiO3 interface promotes water oxidation and the subsequent reduction of a proton on the backside of the SrTiO3 substrate. The chemical bias is significantly reduced by plasmonic effects, which indicates the possibility of constructing an artificial photosynthesis system with low energy consumption.

Size-matching effect on inorganic nanosheets: control of distance, alignment, and orientation of molecular adsorption as a bottom-up methodology for nanomaterials.

We have been investigating complexes composed of nanolayered materials with anionic charges such as clay nanosheets and dye molecules such as cationic porphyrins. It was found that the structure of dye assembly on the layered materials can be effectively controlled by the use of electrostatic host-guest interaction. The intermolecular distance, the molecular orientation angle, the segregation/integration behavior, and the immobilization strength of the dyes can be controlled in the clay-dye complexes. The mechanism to control these structural factors has been discussed and was established as a size-matching effect. Unique photochemical reactions such as energy transfer through the use of this methodology have been examined. Almost 100% efficiency of the energy-transfer reaction was achieved in the clay-porphyrin complexes as a typical example for an artificial light-harvesting system. Control of the molecular orientation angle is found to be useful in regulating the energy-transfer efficiency and in preparing photofunctional materials exhibiting solvatochromic behavior. Through our study, clay minerals turned out to serve as protein-like media to control the molecular position, modify the properties of the molecule, and provide a unique environment for chemical reactions.

High density intercalation of porphyrin into transparent clay membrane without aggregation.

Cationic porphyrin was successfully intercalated into transparent clay membrane by developing the new strategy for the sample preparation conditions. When water:ethanol = 1:2 (v:v) was used as solvent for porphyrin penetration process, high density intercalation of porphyrin into the clay membrane was achieved. In the interlayer space, porphyrin molecules do not aggregate owing to intercharge distance matching effect (size-matching effect), even at high density condition. Judging from XRD and absorption measurements, the orientations of the porphyrins in the clay layers should be almost parallel to the clay nanosheet as monolayer. Because the fluorescence quantum yield did not depend on its loading level, it is turned out that intercalated TMPyP in the clay film keeps the photoactivity even under the high density conditions.

Intercalation of a surfactant with a long polyfluoroalkyl chain into a clay mineral: unique orientation of polyfluoroalkyl groups in clay layers.

Eight novel polyfluorinated surfactants (C(n)F(2n+1)CONH(CH2)2 N(+)(CH3)2C16H33 Br(-); abbreviated as CnF-S, where n = 1, 2, 3, 4, 5, 6, 8, 10) were synthesized and their intercalation into cation-exchangeable clay was investigated. All of the polyfluorinated surfactants intercalated in amounts exceeding the cation exchange capacity (CEC) of the clay. The C4F-S and C5F-S surfactants exhibited intercalation up to 480% of the CEC as a saturated adsorption limit. On the basis of X-ray analysis, CnF-S surfactants intercalated between clay nanosheets to form a bilayer structure in which the surfactant molecules tilt at an angle of ∼60° with respect to the clay surface. The saturated adsorption limits and layer distances differed between surfactants with short (n = 1, 2) and long (n = 3-10) perfluoroalkyl chains. For long-chain surfactants, their saturated adsorption limits were independent of the perfluoroalkyl chain length and the layer distances systematically increased with increasing perfluoroalkyl chain length. These results suggest that the microscopic orientation differed between the short and long chains. X-ray analysis showed that the long-chain surfactants orient the perfluoroalkyl chains at a tilt of 41 ± 5° with respect to the clay layer. This value was in good agreement with polarized IR measurements of 42 ± 2° for this angle.

Two distinct amyloid beta-protein (Abeta) assembly pathways leading to oligomers and fibrils identified by combined fluorescence correlation spectroscopy, morphology, and toxicity analyses.

Nonfibrillar assemblies of amyloid ß-protein (Aß) are considered to play primary roles in Alzheimer disease (AD). Elucidating the assembly pathways of these specific aggregates is essential for understanding disease pathogenesis and developing knowledge-based therapies. However, these assemblies cannot be monitored in vivo, and there has been no reliable in vitro monitoring method at low protein concentration. We have developed a highly sensitive in vitro monitoring method using fluorescence correlation spectroscopy (FCS) combined with transmission electron microscopy (TEM) and toxicity assays. Using Aß labeled at the N terminus or Lys(16), we uncovered two distinct assembly pathways. One leads to highly toxic 10-15-nm spherical Aß assemblies, termed amylospheroids (ASPDs). The other leads to fibrils. The first step in ASPD formation is trimerization. ASPDs of ∼330 kDa in mass form from these trimers after 5 h of slow rotation. Up to at least 24 h, ASPDs remain the dominant structures in assembly reactions. Neurotoxicity studies reveal that the most toxic ASPDs are ∼128 kDa (∼32-mers). In contrast, fibrillogenesis begins with dimer formation and then proceeds to formation of 15-40-nm spherical intermediates, from which fibrils originate after 15 h. Unlike ASPD formation, the Lys(16)-labeled peptide disturbed fibril formation because the Aß(16-20) region is critical for this final step. These differences in the assembly pathways clearly indicated that ASPDs are not fibril precursors. The method we have developed should facilitate identifying Aß assembly steps at which inhibition may be beneficial.

Hydrophilicity control of visible-light hydrogen evolution and dynamics of the charge-separated state in dye/TiO2/Pt hybrid systems.

Visible-light-driven H(2) evolution based on Dye/TiO(2)/Pt hybrid photocatalysts was investigated for a series of (E)-3-(5'-{4-[bis(4-R(1)-phenyl)amino]phenyl}-4,4'-(R(2))(2)-2,2'-bithiophen-5-yl)-2-cyanoacrylic acid dyes. Efficiencies of hydrogen evolution from aqueous suspensions in the presence of ethylenediaminetetraacetic acid as electron donor under illumination at λ>420 nm were found to considerably depend on the hydrophilic character of R(1), varying in the order MOD (R(1)=CH(3)OCH(2), R(2)=H)≈MO4D (R(1)=R(2)=CH(3)OCH(2))>HD (R(1)=R(2)=H)>PD (R(1)=C(3)H(7), R(2)=H). In the case of MOD/TiO(2)/Pt, the apparent quantum yield for photocatalyzed H(2) generation at 436 nm was 0.27±0.03. Transient absorption measurements for MOD- or PD-grafted transparent films of TiO(2) nanoparticles dipped into water at pH 3 commonly revealed ultrafast formation (<100 fs) of the dye radical cation (Dye(·+) ) followed by multicomponent decays, which involve minor fast decays (<5 ps) almost independent of R(1) and major slower decays with significant differences between the two samples: 1) the early decay of the major components for MOD is about 2.5 times slower than that for PD and 2) a redshift of the spectrum occurred for MOD with a time constant of 17 ps, but not for PD. The substituent effects on H(2) generation as well as on transient behavior have been discussed in terms substituent-dependent charge recombination (CR) of Dye(·+) with electrons in bulk, inner-trap, and/or interstitial-trap states, arising from different solvent reorganization.