Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

High-Affinity Ratiometric Fluorescence Probe Based on 6-Amino-2,2′-Bipyridine Scaffold for Endogenous Zn2+ and Its Application to Living Cells

Zinc is an essential trace element involved in many biological activities; however, its functions are not fully understood. To elucidate the role of endogenous labile Zn²⁺, we developed a novel ratiometric fluorescence probe, 5-(4-methoxyphenyl)-4-(methylsulfanyl)-[2,2′-bipyridin]-6-amine (6 (rBpyZ)) based on the 6-amino-2,2′-bipyridine scaffold, which acts as both the chelating agent for Zn²⁺ and the fluorescent moiety. The methoxy group acted as an electron donor, enabling the intramolecular charge transfer state of 6 (rBpyZ), and a ratiometric fluorescence response consisting of a decrease at the emission wavelength of 438 nm and a corresponding increase at the emission wavelength of 465 nm was observed. The ratiometric probe 6 (rBpyZ) exhibited a nanomolar-level dissociation constant (K_d = 0.77 nM), a large Stokes shift (139 nm), and an excellent detection limit (0.10 nM) under physiological conditions. Moreover, fluorescence imaging using A549 human lung adenocarcinoma cells revealed that 6 (rBpyZ) had good cell membrane permeability and could clearly visualize endogenous labile Zn²⁺. These results suggest that the ratiometric fluorescence probe 6 (rBpyZ) has considerable potential as a valuable tool for understanding the role of Zn²⁺ in living systems.     

A New Imaging Method with a Spatial Filter for Incoherent Stream

A new imaging method using an incoherent-type pupil filter: SFINCS (Spatial Filter for INCoherent Stream) is presented. The new filter divides the imaging beam into several incoherent beams at the pupil plane thereby enlarging the depth-of-focus (DOF). The capabilities of SFINCS are studied by simulations and several ways to realize the method are also discussed. The experimental results show that SFINCS has excellent DOF expanding capabilities for a point-image such as a hole pattern in VLSI lithography, and that 1.7 μm DOF is obtained with a 0.30 μm hole pattern by an i-line projection lens with 0.57 NA (numerical aperture).Presented at the International Commission for Optics Topical Meeting, Kyoto, 1994.     

M1 gamma strength for zirconium nuclei in the photoneutron channel

Photoneutron cross sections were measured for 91Zr, 92Zr, and 94Zr near the neutron separation energy with quasimonochromatic gamma rays. The data exhibit some extra components around the neutron threshold. A coherent analysis of the photoneutron data for 92Zr together with the neutron capture on 91Zr based on the microscopic Hartree-Fock-Bogoliubov plus quasiparticle random-phase approximation model for the E1 strength has revealed the presence of an M1 resonance at 9 MeV. The microscopic approach systematically shows the same M1 strength in the photoneutron cross section for 91Zr and 94Zr. The total M1 strength is about 75% larger than the strength predicted by the systematics, being qualitatively consistent with the giant M1 resonance observed in the inelastic proton scattering.     

Asymptotic solutions of the elastic wave equation and reflected waves near boundaries

In the first half of this paper, we construct asymptotic solutions of linear anisotropic elastic equations. In the latter half, we investigate waves reflected by boundaries for plane incident waves in terms of these solutions. Especially, it is examined whether or not the mode-conversion occurs near points where the incident waves hit the boundaries perpendicularly.     

Singularities of Euler Flow? Not Out of the Blue!

Does three-dimensional incompressible Euler flow with smooth initial conditions develop a singularity with infinite vorticity after a finite time? This blowup problem is still open. After briefly reviewing what is known and pointing out some of the difficulties, we propose to tackle this issue for the class of flows having analytic initial data for which hypothetical real singularities are preceded by singularities at complex locations. We present some results concerning the nature of complex space singularities in two dimensions and propose a new strategy for the numerical investigation of blowup.     

A removable isolated singularity theorem for the stationary Navier-Stokes equations

We show that an isolated singularity at the origin 0 of a smooth solution (u,p) of the stationary Navier-Stokes equations is removable if the velocity u satisfies u∈Lⁿ or |u(x)|=o(|x|^-1) as x→0. Here n?3 denotes the dimension. As a byproduct of the proof, we also obtain a new interior regularity theorem.     

Reporting of quantitative oxygen mapping in EPR imaging

Oxygen maps derived from electron paramagnetic resonance spectral-spatial imaging (EPRI) are based upon the relaxivity of molecular oxygen with paramagnetic spin probes. This technique can be combined with MRI to facilitate mapping of pO(2) values in specific anatomic locations with high precision. The co-registration procedure, which matches the physical and digital dimensions of EPR and MR images, may present the pO(2) map at the higher MRI resolution, exaggerating the spatial resolution of oxygen, making it difficult to precisely distinguish hypoxic regions from normoxic regions. The latter distinction is critical in monitoring the treatment of cancer by radiation and chemotherapy, since it is well-established that hypoxic regions are three or four times more resistant to treatment compared to normoxic regions. The aim of this article is to describe pO(2) maps based on the intrinsic resolution of EPRI. A spectral parameter that affects the intrinsic spatial resolution of EPRI is the full width at half maximum (FWHM) height of the gradient-free EPR absorption line in frequency-encoded imaging. In single point imaging too, the transverse relaxation times (T(2)(?)) limit the resolution since the signal decays by exp(-t(p)/T(2)(?)) where the delay time after excitation pulse, t(p), is related to the resolution. Although the spin densities of two point objects may be resolved at this separation, it is inadequate to evaluate quantitative changes of pO(2) levels since the linewidths are proportionately affected by pO(2). A spatial separation of at least twice this resolution is necessary to correctly identify a change in pO(2) level. In addition, the pO(2) values are blurred by uncertainties arising from spectral dimensions. Blurring due to noise and low resolution modulates the pO(2) levels at the boundaries of hypoxic and normoxic regions resulting in higher apparent pO(2) levels in hypoxic regions. Therefore, specification of intrinsic resolution and pO(2) uncertainties are necessary to interpret digitally processed pO(2) illustrations.