Control of photobleaching in photodynamic therapy using the photodecarbonylation reaction of ruthenium phthalocyanine complexes via stepwise two-photon excitation

In this study, we have investigated the photochemical properties and photodynamic effects of ruthenium phthalocyanine (RuPc(CO)(Py)) and naphthalocyanine (RuNc(CO)(Py)) complexes. When a nanosecond-pulsed laser is used, the photodecarbonylation of our Ru complexes efficiently proceeds via stepwise two-photon excitation, while the reaction yields are negligibly small when a continuous-wave (CW) laser is employed. The pulsed laser selective photodecarbonylation decreases the Q-band absorbance, which satisfies what the photodynamic therapy (PDT) requires of the photobleaching. For RuPc(CO)(Py), the photochemical reactions including both the photodecarbonylation and just photobleaching occur in HeLa cells in vitro. Toxicity and phototoxicity tests indicate that our RuPc(CO)(Py) and RuNc(CO)(Py) complexes in concentrations of 0.3-1 microM and 1-2 microM, respectively, are applicable as PDT agents. The phototoxicity is consistent with the photochemical properties of these complexes, namely, excited triplet lifetimes (10 and 4.8 micros for the Pc and Nc complexes, respectively) and singlet oxygen yields (0.48 and 0.35 for the Pc and Nc complexes, respectively). On the basis of these results, we propose a novel concept for achieving a greater depth of necrosis in PDT as follows: (1) PDT of upper cellular layers using CW-laser irradiation; (2) efficient photobleaching in upper cellular layers using pulsed dye-laser irradiation, which results in an increase in the therapeutic depth of red light; (3) PDT directed toward deeper tumor tissues using CW laser irradiation. In addition, these Ru complexes are promising as CO release agents for investigative biochemistry.     

Two- and three-dimensional smectic ordering of single-handed helical polymers

Rodlike polymers with precisely defined architectures are ideal building blocks for self-assembled structures leading to novel nanometer-scale devices. We found that the living polymerization of a single isocyanide enantiomer bearing an l-alanine pendant with a long n-decyl chain simultaneously produced diastereomeric right- and left-handed helices with different molecular weights and narrow molecular weight distributions. Each single-handed, rodlike helical polymer with a controlled length and handedness isolated by a facile solvent fractionation method with acetone self-assembled to form well-defined two- and three-dimensional smectic ordering on the nanometer scale on a substrate and in a liquid crystalline state as evidenced by direct atomic force microscopic observations and X-ray diffraction measurements, respectively.     

Macrocyclic Dinuclear Palladium Complex as a Novel Doubly Threaded [3]Rotaxane Scaffold and Its Application as a Rotaxane Cross‐Linker

A dinuclear Pd^II complex possessing a cyclic ligand was developed as a novel doubly threaded [3]rotaxane scaffold and applied as a rotaxane cross‐linker reagent. The dinuclear complex (PdMC)₂ was prepared by one‐step macrocyclization followed by the double palladation reaction. ¹H NMR analysis and UV/Vis measurements revealed the formation of a doubly threaded pseudo[3]rotaxane by the complexation of (PdMC)₂ with 2 equivalents of 2,6‐disubstituted pyridine 3 through double metal coordination. The treatment of (PdMC)₂ with 2 equivalents of 4‐vinylpyridine (VP) afforded a doubly threaded [3]rotaxane cross‐linker (PdMC‐VP)₂ . Radical co‐polymerization of VP and t‐butylstyrene in the presence of (PdMC‐VP)₂ afforded a stable rotaxane cross‐linked polymer (RCP). An elastic RCP was also prepared by using n‐butyl acrylate as a monomer. The obtained RCPs exhibited higher swelling ability and higher mechanical toughness compared with the corresponding covalent cross‐linked polymers.     

Environmentally benign deprotection of dithioacetals using 30% hydrogen peroxide catalyzed by Fe(acac)3 and sodium iodide

The reaction of dithioacetals with 30% hydrogen peroxide in the presence of catalytic amounts of iron(III) acetylacetonate and sodium iodide efficiently produced the corresponding carbonyl compounds in high yields.     

Improvement of focusing characteristics of a spiral plasmonic lens

We designed and fabricated a spiral plasmonic lens (PL) with multi-circular grooves to increase light intensity in a farfield region via the constructive interference of the light scattered by the multi-circular grooves. To compare the beam focusing characteristics of a spiral PL with multi-circular grooves with those of a conventional spiral PL, we simulated the electric field distribution of the PLs operating at a 405 nm wavelength. We confirmed that the light intensity increased about twofold at 0.75 μm above the PL surface owing to the effect of the multi-circular grooves. Furthermore, the circular grooves negligibly affect the full width at half-maximum of the focal spot, keeping the subwavelength size (～200 nm) of incident light.     

Core Assembly Mechanism of Quinocarcin/SF-1739: Bimodular Complex Nonribosomal Peptide Synthetases for Sequential Mannich-type Reactions

1. Download : Download high-res image (166KB)
2. Download : Download full-size image

     

Acoustically induced spin-orbit interactions revealed by two-dimensional imaging of spin transport in GaAs

Magneto-optic Kerr microscopy was employed to investigate the spin-orbit interactions of electrons traveling in semiconductor quantum wells using surface acoustic waves (SAWs). Two-dimensional images of the spin flow induced by SAWs exhibit anisotropic spin precession behaviors caused by the coexistence of different types of spin-orbit interactions. The dependence of spin-orbit effective magnetic fields on SAW intensity indicates the existence of acoustically controllable spin-orbit interactions resulting from the strain and Rashba contributions induced by the SAWs.