Unexpected formation of benziphthalocyanine dimer: An easily synthesizable dimer of phthalocyanine analogue

Methylene-bridged benziphthalocyanine dimer 2 was unexpectedly generated by the reaction of dihydroxybenziphthalocyanine 1 and formaldehyde in the presence of a catalytic amount of a base at room temperature. Single-crystal X-ray diffraction analysis of 2 revealed a V-shaped structure. Dimer 2 exhibited longer-wavelength absorption and fluorescence bands than monomer 1 in the near-IR region.     

Synthesis of All Stereoisomers of Monomeric Spectomycin A1/A2 and Evaluation of Their Protein SUMOylation-Inhibitory Activity

A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B₂(pin)₂). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity.     

CHOICE OF COATINGS FOR THE OPTICAL ELEMENTS IN THE IRRADIATION SYSTEM OF VACUUM-ULTRAVIOLET RADIATION ABOVE 50 nm

The spectral throughput of a vacuum-ultraviolet irradiation system at the SOR-RING facility was examined with various combinations of aluminum-and gold-coated optical elements in a 2.2-m modified Wadsworth monochromator. We found that the optimum was a combination of an aluminum-coated collimating mirror, concave grating, and plane deflecting mirror, and a combination of a gold-coated collimating mirror, concave grating and an aluminum-coated plane deflecting mirror in the wavelength regions 190-110 nm and 110-50 nm, respectively.     

Formation of fractal porous silica by hydrolysis of TEOS in a bicontinuous microemulsion

Mesoporous silica particles have been prepared by hydrolysis of TEOS (Si(OC₂H₅)₄) in bicontinuous microemulsions containing polyoxyethylene (POE) dodecylether, isooctane and water. TEOS was dissolved in a continuous water phase and hydrolyzed by the dispersed water at around the phase inversion temperature (60°C). Undulating solid materials with layered mesostructures were produced from middle-phase microemulsions in the three phase region (o/w=0.2–0.7). On the other hand, the solids obtained from the lower aqueous phase in the three phase region were found to have a heterogeneous disordered structure. Measurements of the fractal dimensions were performed in the macropore region using a box-counting method for the outline of the SEM texture. We found that the macropore size distribution in the particles prepared from the middle-phase microemulsion follows the fractal rule with a dimension of 1.7. From the results of nitrogen adsorption/desorption curves on the silica, a steep increase in the adsorption amounts was observed at a relative pressure below 0.2, and adsorption/desorption hysteresis was also observed at a relative pressure between 0.3 and 0.5. These studies suggest that the silica synthesized in the bicontinuous microemulsion mesostructure has a very broad size range from micro to macropores with a fractal distribution.     

Fluorogenic and fluorescent labeling reagents with a benzofurazan skeleton

Fluorogenic and fluorescent labeling reagents having a benzofurazan (2,1,3-benzoxadiazole) skeleton such as 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), 4-N,N-dimethylaminosulfonyl-7-fluoro-2,1,3-benzoxadiazole (DBD-F), 4-aminosulfonyl-7-fluoro-2,1,3-benzoxadiazole (ABD-F), ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), 4-hydrazino-7-nitro-2,1,3-benzoxadiazole (NBD-H), 4-N,N-dimethylaminosulfonyl-7-hydrazino-2,1,3-benzoxadiazole (DBD-H), 4-nitro-7-N-piperazino-2,1,3-benzoxadiazole (NBD-PZ), 4-N,N-dimethylaminosulfonyl-7-N-piperazino-2,1,3-benzoxadiazole (DBD-PZ), 4-(N-chloroformylmethyl-N-methyl)amino-7-N,N-dimethylaminosulfonyl-2,1,3-benzoxadiazole (DBD-COCl) and 7-N,N-dimethylaminosulfonyl-4-(2,1,3-benzoxadiazolyl) isothiocyanate (DBD-NCS) are reviewed in terms of synthetic method, reactivity, fluorescence characteristics, sensitivity and application to analytes.     

Photoelectron spectra and angular distribution in reson three-photon ionization of atomic iron: J dependence

Kenetic energies and angular distributions of photoelectrons emitted by three-photon ionization fo atomic iron through two-photon resonant state e⁷D_J and e⁵ D_J, were measured, by using visible lasers. J-resolved photoelectron bands attributab to the a⁶D_J and a⁴F_j ionic states are reported.     

A converse of Loewner–Heinz inequality and applications to operator means

Let f(t)$f(t)$ be an operator monotone function. Then A?B$A?B$ implies f(A)?f(B)$f(A)?f(B)$, but the converse implication is not true. Let A?B$A?B$ be the geometric mean of A,B?0$A,B?0$. If A?B$A?B$, then B⁻¹?A?I$B^{-1}?A?I$; the converse implication is not true either. We will show that if f(λB+I)⁻¹?f(λA+I)?I$f{(\lambda B+I)}^{-1}?f(\lambda A+I)?I$ for all sufficiently small λ>0$\lambda >0$, then f(λA+I)?f(λB+I)$f(\lambda A+I)?f(\lambda B+I)$ and A?B$A?B$. Moreover, we extend it to multi-variable matrices means.     

Hydrodynamic limit for a spin system on a multidimensional lattice

Summary The hydrodynamic limit for a Markov process of [0, )-valued spin fields on a periodic multidimensional lattice is studied. In the process a positive real number, called energy, is attached to each site of the lattice and each couple of adjacent sites exchange thier energy by random amounts at random times. The law of the exchange is such that the sum of the total energy is conserved, and that the process is reversible and of gradient type for the energy distribution. We show that under diffusion type scaling of space and time, the macroscopic energy distribution converges to a deterministic limit which is characterized by a non-linear diffusion equation /t=2^–1P(), whereP is an increasing function which in a typical case equals const·².