Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

Vacuum‐driven fluid manipulation by a piezoelectric diaphragm micropump for microfluidic droplet generation with a rapid system response time

Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (V_p‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐V_p‐p increments over the range of 200?250 V_p‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications.     

Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

Cusp Cross-Sections of Hyperbolic Orbifolds by Heisenberg Nilmanifolds I

Long and Reid [Algebr. Geom. Topol. 2: 285–296, 2002] have shown that the diffeomorphism class of every Riemannian flat manifold of dimension n≥ 3 arises as a cusp cross-section of a complete finite volume real hyperbolic (n+1)-orbifold. For the complex hyperbolic case, McReynolds [Algebr. Geom. Topol. 4: 721–755, 2004] proved that every 3-dimensional infranilmanifold is diffeomorphic to a cusp cross-section of a complete finite volume complex hyperbolic 2-orbifold. Moreover, he gave a necessary and sufficient condition for a Heisenberg infranilmanifold to be realized as a cusp cross-section of finite volume (arithmetically) complex hyperbolic orbifold. We study these realization problems by using Seifert fibrations.     

Compulsorily Phase Locked Interferometer Using Orthogonally Polarized Light Source of a Modulated LD with High Extinction Ratio

This paper describes a compulsorily phase locked differential interferometer using an orthogonally polarized light source of a modulated LD with high extinction ratio to reduce non-linearity of the interferometer caused by polarization cross-talk. The current modulated LD is used as a light source to make the interferometer compact and for the scanning phase of the interferometer. The interferometer is operated compulsorily at the maximum inclination point of the fringe intensity curve by fringe scanning and an electric system. A Wollaston prism of high extinction ratio (50 dB) is used to combine the polarizing beams and to make the polarization cross-talk very small. In one light source the polarized output beams are on the same propagation axis; in the other they have a small crossing angle (2.5 mrad ∼ 10 mrad) to completely exclude non-linearity of the interferometer causded by polarization cross-talk. Using jets of a gas mixture of nitrogen and ethylene, this interferometer was demonstrated to be useful in detecting the photothermal effect of a photothermal velocimeter under phase fluctuation in a turbulent flow.     

Anisotropic friction model of DNA electrophoresis in polymer solutions: Comparison with direct observations

The electrophoresis of DNA chains in uncrosslinked polymer solutions with a Brownian dynamics simulation with an anisotropic friction tensor was analyzed. According to the degree of anisotropy, three types of migration behavior are obtained: fluctuation without or with periodicity between U‐shaped and compact conformations, or migration with linear conformation. We found good agreement between our simulation results and the direct observations of DNA by fluorescence microscopy. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1316–1322, 2003     

χ polarization induced in molecular glass of conjugated compound by all-optical poling

The paper presents the first report on χ⁽²⁾ polarization induced in molecular glass of conjugated compound by all-optical poling. Transparent thin film of molecular glass of 1,4-bis[2-[4-[N,N-di(p-tolyl)amino]phenyl]vinyl]benzene (BTAPVB) was prepared using a spin-cast technique. Dipolar as well as octupolar components in BTAPVB contributed to the formation of photoinduced χ⁽²⁾ polarization. Growth rate of χ⁽²⁾ polarization has good linear relation with E_ω⁴E_2ω, which suggested that the simultaneous processes of two-photon (ω + 2ω) and three-photon (ω + ω + ω) excitation on the same electronic level contributed to the formation of photoinduced χ⁽²⁾ polarization.     

Total synthesis of tylosin

Tylosin has been synthesized byregio- and stereoselective introduction of the amino disaccharide moiety and D-mycinose onto the previously synthesized 16-membered-ring aglycone.