Mössbauer and ESR study of the formation of phthalocyanineiron(II) pyridine adduct in the supercage of NaY,KY, and RbY zeolite

Phthalocyanineiron(II) (FePc) and phthalocyaninato[(2-)bispyridine]iron(II) (FePc(py)₂) synthesized in supercage of NaY, KY and RbY zeolite have been characterized by Mössbauer and ESR spectroscopy. The yield of formation of the pyridine adduct depends on the ionic radius of the alkali ions introduced into the supercage, but not on the number of iron ions trapped in the cages, suggesting that free space in the supercage was the most important factor for the formation of the FePc-py-adducts.     

Characterization of cationic acid phosphatase isozyme from rat liver mitochondria.

Acid phosphatase isozyme was highly purified from rat liver mitochondrial fraction. The enzyme showed an isoelectric point value of above 9.5 on isoelectric focusing, and the apparent molecular weight was estimated to be 32000 by Sephadex G-100 gel filtration or 16000 by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The enzyme catalyzed the hydrolysis of adenosine 5'-triphosphate, adenosine 5'-diphosphate, thiamine pyrophosphate, inorganic pyrophosphate, and phosphoprotein such as casein and phosvitin, but not of several phosphomonoesters, except for p-nitrophenyl phosphate and o-phosphotyrosine. The enzyme was not inhibited by L-(+)-tartrate, and was significantly activated by Fe2+ and reducing agents such as ascorbic acid, L-cysteine,and dithiothreitol. The enzyme was found to be distributed in various rat tissues including liver, spleen, kidney, small intestine, lung, stomach, brain and heart, but not in skeletal muscle.     

Adsorption of fission products on a metal surface in nitric acid solutions: Radiochemical study using a multitracer

Adsorption behavior of fission products in nitric acid solution on various alloys and metals was studied by using a multitracer produced by neutron irradiation of UO₂. The adsorption behavior of the fission products ⁹⁹Mo, ¹³¹I, ¹³²Te, ¹⁴⁰La, and ¹⁴³Ce, and ²³⁹Np was simultaneously studied. Some chemical decontamination tests were also examined. Clear adsorption of ⁹⁹Mo, ¹³¹I, and ¹³²Te was observed, whereas adsorption of ¹⁴⁰La, ¹⁴³Ce, and ²³⁹Np was not. The adsorption characteristics were discussed by considering anion-exchange reaction and surface complexation.     

Unambiguous Determination of the Absolute Configurations of Acetylene Alcohols by Combination of the Sonogashira Reaction and the CD Exciton Chirality Method – Exciton Coupling between Phenylacetylene and Benzoate Chromophores

The CD exciton chirality method was applied to various phenylacetylene alcohols to determine their absolute configurations; the long axis polarized –^* transition (_max=252nm) of the 4-methoxyphenylacetylene chromophore couples with the transition (_max=257nm) of the 4-methoxybenzoate group to generate intense exciton split CD Cotton effects, from the signs of which the absolute configurations of phenylacetylene alcohols were unambiguously determined. As an extension of the results, a new methodology for determining the absolute configurations of acetylene alcohols having the HCCCH(OH)-moiety by combination of the Sonogashira reaction and the CD exciton chirality method has been developed and applied. Since the –^* transition of acetylene triple bond is located below 180nm, it is difficult to observe ideal bisignate CD Cotton effects due to the exciton coupling between acetylene and benzoate chromophores. To observe the ideal exciton split Cotton effects necessary for the unambiguous determination of absolute configuration, the terminal acetylene group was converted, by the Sonogashira reaction, to the 4-methoxyphenylacetylene moiety, which exhibits an intense –^* absorption band polarized along the long axis of the chromophore at 252nm. As a partner of exciton coupling, 4-methoxybenzoate showing a –^* band at 257nm was introduced into the alcohol moiety, and the benzoates formed showed intense bisignate CD Cotton effects, from the signs of which the absolute configurations of original acetylene alcohols could be determined in an unambiguous manner.     

Synthesis and photoinduced electron transfer processes of rotaxanes bearing [60]fullerene and zinc porphyrin: effects of interlocked structure and length of axle with porphyrins

Three rotaxanes, with axles with two zinc porphyrins (ZnPs) at both ends penetrating into a necklace pending a C60 moiety, were synthesized with varying interlocked structures and axle lengths. The intra-rotaxane photoinduced electron transfer processes between the spatially positioned C60 and ZnP in rotaxanes were investigated. Charge-separated (CS) states (ZnP*+, C60*-)rotaxane are formed via the excited singlet state of ZnP (1ZnP*) to the C60 moiety in solvents such as benzonitrile, THF, and toluene. The rate constants and quantum yields of charge separation via 1ZnP decrease with axle length, but they are insensitive to solvent polarity. When the axle becomes long, charge separation takes place via the excited triplet state of ZnP (3ZnP*). The lifetime of the CS state increases with axle length from 180 to 650 ns at room temperature. The small activation energies of charge recombination were evaluated by temperature dependence of electron-transfer rate constants, probably reflecting through-space electron transfer in the rotaxane structures.     

X-ray absorption spectroscopic study on the electronic structure of Li(1)(-)(x)()CoPO(4) electrodes as 4.8 V positive electrodes for rechargeable lithium ion batteries

Changes in the electronic structure of olivine Li(1-x)CoPO(4), 4.8 V positive electrode material for lithium ion batteries, were investigated using the X-ray absorption spectroscopy (XAS) technique. The threshold energy in the Co K-edge increased with electrochemical Li removal, indicating the oxidation of cobalt ions due to charge compensation. Moreover, P and O K-edge XAS showed a slight shift in threshold energy with Li removal. Although it is generally believed that the electrons of PO(4) polyanion do not contribute to the oxidation process, present experimental results indicate changes in the electronic structure around PO(4) units. Such results would be interpreted by the idea of the hybridization effect between the Co 3d and O 2p orbitals and of the polarization effect introduced by Li ions.     

Selective growth of ag nanowires on Si(111) surfaces by electroless deposition

Electroless deposition of Ag on atomically flat H-terminated Si(111) surfaces in aqueous alkaline solutions containing Ag ions produced two different sizes of Ag nanowires along atomic step edges: (1) a narrow nanowire of 10 nm in width and 0.5 nm in height and (2) a wide nanowire of 35 nm in width and 11 nm in height. The narrow and wide nanowires were formed by immersion in the solutions containing less than 1 ppb and 8 ppm dissolved-oxygen concentrations, respectively. This result indicates that the dissolved oxygen initiates the formation of Ag nucleation sites and that the fabrication method has a possibility of controlling the size of Ag nanowires.     

Catalytic enantioselective Michael addition of 1,3-dicarbonyl compounds to nitroalkenes catalyzed by well-defined chiral ru amido complexes

Well-defined chiral Ru amido complexes promoted asymmetric Michael addition of 1,3-dicarbonyl compounds including malonates, beta-keto esters, and 1,3-diketones to nitroalkenes to give the corresponding adducts with excellent ees and in excellent yields.     

Evaluation of transversal and longitudinal dispersion in a flow injection system by exploiting laser induced fluorescence: influence of flow-cell positioning

A fully mechanized set-up was built for the experimental determination of bi-dimensional dispersion with high spatial resolution (2400 μm²). Gravitational and wall effects in a single stream were evaluated by using time-based sampling and a micro-flow cell. Vertical upward and downward flows as well as horizontal flows were investigated. Ethylene glycol (MEG) and Rhodamine B in MEG were used as carrier and sample solutions, respectively. Longitudinal profiles were obtained by laser induced total fluorescence (LIF) at up to 19 transversal sites and combined to generate high-resolution bi-dimensional profiles. A two frontal maxima pattern was observed for all flows. The volumetric fraction of RB shape was highly stretched for downward flow and there was high asymmetry for horizontal flow. The sensitivity of three dispersion parameters was evaluated: maximum peak value, peak half-width at half-height, and peak area.Data modeling showed that the tanks-in-series was more sensitive to wall effects, had good adjustment with only one tank for upward and horizontal flow and needed two tanks for downward flow which was attributed to the latter having higher dispersion. A black box empirical modeling described better the gravitational effect and allowed to identify a parameter sensitive to upward and downward flow as well as hinting to two inner streams within the horizontal flow. It also pointed to a wall dispersion contribution of twice that of the liquid-liquid dispersion.     

Oxovanadium(V)-catalyzed enantioselective Meerwein-Ponndorf-Verley cyanation of aldehydes using acetone cyanohydrin

Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect.