Phase behavior of binary mixtures composed of ethylene carbonate and various organic solvents

Phase behaviors of the binary mixtures composed of ethylene carbonate (EC) and aliphatic alcohols, ω-phenyl alcohols, and alkylbenzenes were investigated. In addition, heat of solution of EC into these organic solvents was measured. The EC/methanol and EC/ethanol systems gave homogeneous solution at the temperature above their liquidus lines, while the mixtures of EC and alcohols with longer alkyl chain showed a miscibility gap in a liquid phase and provided the monotectic-type phase diagram. The liquid–liquid phase separation region expanded with the increase in the alkyl chain length. A similar phase behavior was also observed for the mixtures of EC and alkylbenzenes. On the other hand, the EC mixtures with ω-phenyl alcohols showed no miscibility gap in a liquid phase at least up to 4-phenylbutan-1-ol which has C4 alkyl chain intervening between phenyl and hydroxyl groups. This result demonstrates that both of the hydroxyl and phenyl groups act to facilitate the mixing of aliphatic compounds with EC. The phase behavior of these EC mixtures was analyzed applying the modified regular solution model in which the pair interaction energy was regarded as free energy. The model calculation with the use of heat of solution of EC at infinite dilution as the pair interaction enthalpy reproduced well both of the experimentally obtained liquidus line and mutual solubility curve as well as monotectic point.     

Pycnalin, a new α-glucosidase inhibitor from Acer pycnanthum

A new compound, pycnalin (1), together with four known compounds, ginnalins A (2), B (3), C (4), and 3,6-di-O-galloyl-1,5-anhydro-D-glucitol (3,6-di-GAG) (5), were isolated from Acer pycnanthum. The structure of 1 was determined on the basis of 2D-NMR spectral data and synthesis of 1. Pycnalin (1) is the first 1,5-anhydro-D-mannitol linked to a gallic acid, while compounds 2-5 were 1,5-anhydro-D-glucitol linked to gallic acids. All compounds were tested in vitro for α-glucosidase inhibitory and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activities. Pycnalin (1) exhibited moderate α-glucosidase inhibitory activity as well as free radical scavenging activity. Ginnalin A (2) and 3,6-di-GAG (5), which have two galloyl groups, exhibited potent α-glucosidase inhibition, compared to those of other compounds 1, 3, and 4 containing a galloyl group. These results suggest that α-glucosidase inhibition is influenced by the number of galloyl groups.     

Electric field dependent photocurrent generation in a thin-film organic photovoltaic device with a [70]fullerene-benzodifuranone dyad

A [70]fullerene-benzodifuranone acceptor dyad synthesized by a Ag?-mediated coupling reaction was used to construct a thin-film organic solar cell. The fullerene and the benzodifuranone dye in the dyad have close-lying LUMO levels in the range of 3.7-3.9 eV, so that energy transfer from the dye to the fullerene can take place. A p-n heterojunction photovoltaic device consisting of a tetrabenzoporphyrin and a [70]fullerene-benzodifuranone dyad showed a weak but discernible contribution from light absorption of the dyad to the photocurrent under both a positive and a negative effective bias. These results indicate that the benzodifuranone moiety attached to the acceptor contributes to light-harvesting by energy transfer.     

Wishart exponential families on cones related to tridiagonal matrices

Annals of the Institute of Statistical Mathematics - Let G be the graph corresponding to the graphical model of nearest neighbor interaction in a Gaussian character. We study Natural Exponential...     

NANOMECHANICAL MAPPING OF CARBON BLACK REINFORCED NATURAL RUBBER BY ATOMIC FORCE MICROSCOPY

Atomic force microscopy （AFM） has the advantage of obtaining mechanical properties as well as topographic information at the same time. By analyzing force-distance curves measured over two-dimensional area using Hertzian contact mechanics, Young＇s modulus mapping was obtained with nanometer-scale resolution. Furthermore, the sample deformation by the force exerted was also estimated from the force-distance curve analyses. We could thus reconstruct a real topographic image by incorporating apparent topographic image with deformation image. We applied this method to carbon black reinforced natural rubber to obtain Young＇s modulus distribution image together with reconstructed real topographic image. Then we were able to recognize three regions; rubber matrix, carbon black （or bound rubber） and intermediate regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first to report on the quantitative evaluation of the interfacial region in real space.     

Ion-exclusion chromatography with the direct UV detection of non-absorbing inorganic cations using an anion-exchange conversion column in the iodide-form

An ion-exclusion chromatographic method for the direct UV detection of non-absorbing inorganic cations such as sodium (Na⁺), ammonium (NH₄⁺) and hydrazine (N₂H₅⁺) ions was developed by connecting an anion-exchange column in the I⁻-form after the separation column. For example, NH₄⁺ is converted to a UV-absorbing molecule, NH₄I, by the anion-exchange column in the I⁻-form after the ion-exclusion separation on anion-exchange column in the OH⁻-form with water eluent. As a result, the direct UV detection of Na⁺, NH₄⁺ and N₂H₅⁺ could be successfully obtained as well as the well-resolved separation. The calibration graphs of the analyte cations detected with UV at 230 nm were linear in the range of 0.001-5.0 mM. The detection limits at S/N = 3 of the cations were below 0.1 μM. This method was applied to real water analysis, the determination of NH₄⁺ in river and rain waters, or that of N₂H₅⁺ in boiler water, with the satisfactory results. This could be applied also to low- or non-absorbing anions such as fluoride or hydrogencarbonate ions by the combination of a weakly acidic cation-exchange resin in the H⁺-form as the separation column and the anion-exchange conversion column.     

Determination of haptoglobin in human serum by high-performance gel-permeation chromatography

Summary A high-performance gel-permeation chromatographic (GPC) method is described for the determination of serum haptoglobin (Hp), based on the estimation of the haptoglobin-hemoglobin (Hp−Hb) complex. Hemoglobin (Hb) is added to the serum and the resulting Hp−Hb complex is separated by GPC and detected at 415 nm. The Hp−Hb complex separated chromatographically from serum migrated electrophoretically with the globulin fraction. It was found to be stable over a period of one week at 4°C. The total analysis time for a serum sample is approximately 20 min. The minimum detection limit is 30mg/L. Relative standard deviation values were below 1% (peak area). No interferences from bilirubin or from turbidity of samples were observed. The results of the GPC analysis correlate well with those obtained by nephelometric assay (r=0.996).     

Electromagnetic Properties of Lanthanum Manganese Oxides Doped with Iron

The mechanism of GMR effects in La(Mn_1–x Fe _x )O₃ (x=0, 0.01, 0.03) oxides has been investigated by means of magnetic measurements, resistivity measurements in magnetic field and Mössbauer spectroscopy. For the x=0.01 sample, the GMR behavior is similar to that of the conventional (La, A)MnO₃ (A: divalent cations) oxides. For the x=0.03 sample, even though the temperature dependence of the Mössbauer spectra was similar to that of the x=0.01 sample, the mechanism for the occurrence of the GMR effect seems to be different. The x=0 sample shows a similar behavior to the x=0.03 sample. A thermal stabilization of spin fluctuation is proposed for the x=0 and x=0.03 sample.     

Oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with dinuclear‐type copper(II) catalyst

The oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with the novel dinuclear‐type copper(II) catalysts successfully produced poly(2,3‐dihydroxy‐1,4‐naphthylene). For example, the MeOH‐insoluble polymer with a number average molecular weight of 4.4 × 10³ from the polymerization using the complex of CuCl₂ and N,N′‐bis(2‐morpholinoethyl)‐p‐xylylenediamine ( p ‐ 1 ) at room temperature under an O₂ atmosphere followed by acetylation of the hydroxyl groups was obtained in 63% yield. The structures of the tetraamine ligands and the counter anion of the copper(II) salts significantly influenced the catalyst activity. The polymerization of 2,2′‐dimethoxy‐1,1′‐binaphthalene‐3,3′‐diol with the 2CuCl₂‐ p ‐ 1 catalyst, however, resulted in a lower yield. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1635–1640, 2005     

Synthesis of polyester dendrimers and dendrons starting from Michael reaction of acrylates with 3-hydroxyacetophenone

A new AB₂ type building block for synthesis of dendritic compounds is made starting from Michael addition of 2 equiv of 3-hydroxyacetophenone to acrylate, followed by decarboxylation and deprotection of either carboxyl or hydroxyl protecting groups. [G1]-[G4] dendrons and [G2] dendrimer were synthesized by the reiterative [hydrogenolysis then DCC/DPTS coupling] sequence using a combination of convergent and divergent growth methods.