Water vapor adsorption onto activated carbons prepared from cattle manure compost (CMC)

Activated carbons were prepared from cattle manure compost (CMC) using zinc chloride activation. The structural and surface chemical characteristics of CMC-based activated carbons were determined by N₂ adsorption-desorption and Boehm titration, respectively. The water vapor adsorption properties of the prepared activated carbons with various pore structure and surface nature were examined, and the mechanism of water adsorbed onto activated carbon was also discussed. The results show that the adsorption of water vapor on carbons begins at specific active sites at low relative humidity (RH), followed by micropore filling at medium RH through the formation of pentamer cluster of water molecules in the narrow micropores. The water vapor adsorption capacity of activated carbon is predominantly dependent on its pore volume and surface area. Although capillary condensation is not the mechanism for water adsorption onto activated carbon, water can adsorb on narrow mesopore to some extent.     

Local crystal structure of nano-manganese-oxide gold adsorbent

The local crystal structure of dried and deuterated nano-manganese-oxide powder samples was studied via atomic pair distribution function analysis of X-ray and neutron powder diffraction data. The protonated sample shows ultrahigh efficiency as a gold adsorbent even from ppt-level aqueous solutions such as seawater. We show that the nano-manganese-oxide particles have an R-MnO₂-type local crystal structure. The possible role of the protons on the surface of the nano-particles is discussed.     

Polymer electrolyte membranes based on polystyrenes with phosphonic acid via long alkyl side chains

A series of polystyrenes with phosphonic acid ( 5 ) via long alkyl side chains (4, 6, and 8 methylene units) were prepared by the radical polymerization of the corresponding diethyl ω‐(4‐vinylphenoxy)alkylphosphonates, followed by the hydrolysis with trimethylsilyl bromide. The resulting phosphonated polystyrene membranes had a high oxidative stability against Fenton's reagent at room temperature. The membranes prepared from 5 exhibited a very low water uptake, similar to that of Nafion 117 over the wide range of 30 to 80% relative humidity (RH). The proton conductivities of these membranes are lower than that of Nafion 117 in the range of 30 to 90% RH, but comparable or higher than those of the reported phosphonated polymers with higher IEC values, such as the phosphonated poly(N‐phenylacrylamide) (PDPAA, IEC: 6.72 mequiv/g) and fluorinated polymers with pendant phosphonic acids (M47, IEC: 8.5 mequiv/g), at low RH conditions despite the much lower IEC values (3.0–3.8 mequiv/g) of these membranes. These results suggest that the flexible pendant side chains of 5 would contribute to the formation of hydrogen‐bonding networks by considering the very low water uptake of these polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Quantum Mutual Entropy Defined by Liftings

A lifting is a map from the state of a system to that of a compound system, which was introduced in Accardi and Ohya (Appl. Math. Optim. 39:33–59, 1999). The lifting can be applied to various physical processes.     

Preconcentration of trace silver with yeast for river water analysis

A new preconcentration method with yeast is presented. The method was evaluated for the determination of trace silver in river waters by graphite furnace atomic absorption spectrometry (GFAAS). A suitable cultivation bed for preconcentration of silver was 1.75 mg ml-1 2-ammonium hydrogen phosphate. The optimal cultivation time and temperature were 2 h and 25 degrees C. Under optimal conditions, silver in aqueous sample was concentrated to 6.9-fold by yeast. The detection limit was 4.6 pg ml-1 (3S/N) for silver in river water. The yeast preconcentration method was applied to the determination of silver in river waters. The recovery of spiked silver was in the range of 89 to 110%. By the preconcentration, it was found that ultra trace silver in river waters could be determined without interferences of matrix elements, after only the cultivation and with no chemical treatment.     

Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.     

Pentagon stability: cyclic delocalization of lone pairs through sigma conjugation and design of polycyclophosphanes

The orbital-phase theory was applied to propose pentagon stability in a well-defined manner. Cyclic delocalization of the lone pair electrons on the five-membered ring atoms through the vicinal sigma bonds was shown to be favored by the orbital-phase properties. The pentagon stability was found to be outstanding in saturated phosphorus five-membered rings in the puckered conformation, and was substantiated by the negative strain energy of cyclopentaphosphane, P(5)H(5) (3). The relative increments of the remarkable increase in the strain energies of protonation on the different atoms in the most stable conformers supported the significance of the cyclic delocalization of the lone pairs. Pentagon stability led to the design of three novel polycyclic phosphanes, P(12)H(4) (18), P(13)H(3) (19), and P(14)H(2) (20), with low strain energies due to many puckered pentagon units in them. The low stability of the dodecahedron P(20) (22) was suggested by the high strain energy due to its planar pentagon units. The pentagon stability is less significant in the saturated nitrogen ring molecules due to the greater energy gap between the n and sigma orbitals.     

Asymmetric synthesis of 4'-ethoxy-2',3'-didehydro-2',3'-dideoxynucleosides by palladium-catalyzed kinetic discrimination between the corresponding diastereoisomeric lactol acetates

4'-Substituted nucleoside analogues have been synthesized using palladium-catalyzed asymmetric allylic amination conditions. A kinetic discrimination between the diastereomeric lactol acetates (3) produced the desired aminated products (6a-d) and recovered acetate (alpha-3) in high yields and <97:3 diastereoselectivity. Epimerization of the recovered lactol acetate (alpha-3) produced a 60:40 alpha/beta mixture of (3), which could be resubjected, in principle, to the palladium-catalyzed asymmetric allylic amination conditions.