Photoelectrochemical oxidation of methanol on oxide nanosheets

Photoelectrochemical oxidation of alcohol on various nanosheet electrodes such as Nb6O17, Ca2Nb3O10, Ti(0.91)O2, Ti4O9, and MnO2 system host layers were measured to evaluate the photocatalysis of water photolysis with alcohol as a sacrificial agent. The nanosheet electrodes were prepared by the layer-by-layer (LBL) method, using electrostatic principles. The highest photooxidation current density was observed in methanol solution for Nb6O17 and Ca2Nb3O10 nanosheets, while the density was lower for Ti(0.91)O2, Ti4O9, and MnO2 nanosheets in decreasing order. The rank in the photocurrent density was in agreement with that in the photocatalytic activity, which means that the degree of photooxidation of the alcohol determines the activity of the alcohol in the water photolysis process. The photocurrent was independent of the number of nanosheet layers on the electrode, indicating that only the mono-nanosheet layer attached directly on a substrate acts as a photoelectrocatalyst and that the interlayer space is not important. Consequently, higher photooxidation current on the Nb6O17 mono-nanosheet layer means that the charge separation of electron and hole under illumination is very large and that the hole-capturing process by CH3OH is very quick compared with the surface recombination on the Nb6O17 nanosheet. The adsorption of a transition metal cation on the nanosheet acted as the surface recombination center, because the photocurrent decreased after the adsorption. The photocatalytic mechanism has been discussed in detail in terms of various photoelectrochemical behaviors.     

Possibility of isostructural condensed states of matter in the D phase of ANBC and the cubic mesophase of BABH: heat capacity of 4'-n-octadecyloxy-3'-nitrobiphenyl-4-carboxlic acid, ANBC(18)

Heat capacity measurements have been made on ANBC(18) at temperatures from 8 to 490 K by adiabatic calorimetry. All known phases were detected. The temperatures, enthalpies and entropies of transition were determined for the phase transitions observed. On the basis of the entropy of transition to the SmC phase from the D or cubic phases, it is pointed out that the D phase of ANBC and the cubic phase of BABH might be identical in nature. It is shown that the arrangement of 'molecular' cores has a higher degree of order in the isotropic (D and cubic) phases than in the SmC phase, whereas the terminal alkoxy chains are more disordered in the isotropic phases than in the SmC phase. The degrees of disorder in the D and cubic phases relative to the SmC phase are very similar in terms of the entropy of transition per methylene group. The inverted phase sequence in ANBC (SmC D on heating) and BABH (cubic SmC) can be accounted for in terms of the competing roles in the entropy between the molecular core and the chains.     

An elliptic quantum algebra for\widehat{s1}_2 2

An elliptic deformation of $\widehat{s1}_2 $ is proposed. Our presentation of the algebra is based on the relationRLL = LLR ^*, whereR andR ^* are eight-vertexR-matrices with the elliptic moduli chosen differently. In the trigonometric limit, this algebra reduces to a quotient of that proposed by Reshetikhin and Semenov-Tian-Shansky. Conjectures concerning highest-weight modules and vertex operators are formulated, and the physical interpretation ofR ^* is discussed.     

Magnetic phase transitions in 187-01187-01187-01

We report SR measurements of Pr₂CuO_4– and (Pr_2–xCe_x)CuO_4– single crystals in the temperature range 4.2K300K. Two spin reorientation phase transitions were observed, although neutron scattering experiment could not detect these phase transitions. These allow us to conclude that magnetic moments of the Cu atoms order in an antiferromagnetic noncollinear cross like structure including a hidden canting spin arrangement.     

Synthesis of polyamide-pyrazolones from 2,2′-disubstituted bis(4-ethoxymethylene-5-oxazolone) and aromatic dihydrazines

A new class of polyamide-pyrazolones was synthesized by the vinylogous nucleophilic substitution polymerization, which was followed by rearrangement, from 2,2′-p-phenylenebis(4-ethoxymethylene-5-oxazolone) and aromatic dihydrazines. Solution polymerization was carried out in polar aprotic solvents under mild conditions to yield polymers having inherent viscosities in the range of 0.5–1.2 quantitatively. The polymer derived from bis(4-hydrazinophenyl) sulfone was readily soluble in strongly polar solvents, while that from bis(4-hydrazinophenyl)methane was partially soluble or swelled in these solvents. The polyamide-pyrazolones which are presumed to contain some intermediate oxazolone structure showed a low level of thermal stability.     

The n-orbital sequence in 1,3 diazaadamantane

The photoelectron spectra of 1,3-diazaadamantane (1) and 1,3-diaza-6-methyleneadamantane (2) have been measured. An analysis of the spectra based on a ZDO model indicates that the ordering of the n-orbitals in 1 is b₂(n?λσ) above a₁(n₊?λσ). The splitting of b₂ and a₁ in 1 is dominated by the through space interaction. These results are confirmed by semiempirical calculations of the Extended Hückel and MINDO/3 type. An analysis of the PE spectrum of 1,3-diazaadamantanone(6) (5) indicates that in 5 the inductive effect of the CO group is dominant.     

Capillary electrophoretic separation between Fe(II) and Ni(II) precomplexed with 1,10-phenanthroline in a high concentration buffer of n-butyric acid/ n-butyrate and its application

The capillary electrophoretic separation was accomplished for Fe(II) and Ni(II) precomplexed with 1,10-phenanthroline (phen) in 2 M n-butyric acid/ n-butyrate buffer at pH 4.5 with direct UV detection at 260 nm. The applied voltage was 5 kV. The high concentration buffer of the n-butyrate resulted in a similar separation mechanism to that of ion-pair reversed-phase high-performance liquid chromatography. The separation would be due to the hydrophobic interaction between the ionic associates, [Fe(phen)(3)]( n-butyrate)(+) and [Ni(phen)(3)]( n-butyrate)(+), with the n-butyrate ion and n-butyric acid as background electrolyte. Linear calibration ranges were obtained for Fe(II) and Ni(II) from 100 to 500 ng ml(-1). The relative standard deviations ( n=10) for 3 g mL(-1) Fe(II) and Ni(II) were 0.090 and 0.086, respectively. Detection limits ( S/ N=3) for Fe(II) and Ni(II) were 20 ng mL(-1). The method was applied to the determination of nickel in aluminium and duralumin alloys.     

Combined NMR and quantum chemical studies on the interaction between trehalose and dienes relevant to the antioxidant function of trehalose

In a previous study (Oku, K.; Watanabe, H.; Kubota, M.; Fukuda, S.; Kurimoto, M.; Tujisaka, Y.; Komori, M.; Inoue, Y.; Sakurai, M. J. Am. Chem. Soc. 2003, 125, 12739), we investigated the mechanism of the antioxidant function of trehalose against unsaturated fatty acids (UFAs) and revealed that the key factor relevant to the function is the formation of OH...pi and CH...O hydrogen bonds between trehalose and the cis double bonds of the UFA. Here, we investigate whether such intriguing interactions also occur between this sugar and cis double bonds in other unsaturated compounds. For this purpose, we selected various diene compounds (1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, and 2,5-heptadiene) as interaction partners. All NMR experiments performed, including 1H-1H NOESY measurements, indicated that trehalose selectively interacts with the cis-olefin proton pair in the above diene with a 1:1 stoichiometry, and the C-3 (C-3') and C-6' (C-6) sites of the sugar are responsible for the interaction. Similar interactions were not observed for the mixtures of the diene and other saccharides (neotrehalose, kojibiose, nigerose, maltose, isomaltose, sucrose, maltitol, and sorbitol). Quantum chemical calculations revealed that the OH-3 and OH-6 groups bind to the olefin double bonds of the diene through OH...pi and CH...O types of hydrogen bonds, respectively, and the stabilization energy of the resulting complex is 5-6 kcal mol(-1). These results strongly support the above NMR results. Finally, the activation energies were calculated for the hydrogen abstraction reactions from the activated methylene group of heptadiene. In particular, when the reaction was initiated by a methyl radical, the activation energy was only 10 kcal mol(-1) for the free heptadiene, but on complexation with trehalose it drastically increased to ca. 40 kcal mol(-1). This indicates that trehalose has a significant depression effect on the oxidation of the diene compounds. These results strongly support the antioxidant mechanism deduced in the previous study and indicate that the formation of unique multiple hydrogen bonds between trehalose and cis-olefin bonds is rather a general event not confined to the case of UFA.     

Characterization of Ce@C82 and its anion

Ce@C(82) is isolated by high-performance liquid chromatography (HPLC) and the cage symmetry is determined as C(2)(v)() by measuring the (13)C NMR spectra of its anion. The (13)C NMR peaks of [Ce@C(82)](-) show temperature-dependent shifts ascribed to the f electron remaining on the Ce atom. Both Ce@C(82) and [Ce@C(82)](-) are silent in electron spin resonance spectroscopy (ESR) because of the highly anisotropic g matrix as well as of the fast relaxation process originating from the orbital angular momentum of the f electron. This is the complementary relationship to the observation of the paramagnetic shift in (13)C NMR. [Ce@C(82)](-) has lower stability in air than [La@C(82)](-).     

Photoactivity and phase stability of ZrO2-doped anatase-type TiO2 directly formed as nanometer-sized particles by hydrolysis under hydrothermal conditions

Anatase-type TiO₂ doped with 4.7 and 12.4 mol% ZrO₂ that were directly precipitated as nanometer-sized particles from acidic precursor solutions of TiOSO₄ and Zr(SO₄)₂ by simultaneous hydrolysis under hydrothermal conditions at 200°C, showed higher photocatalytic activity than pure anatase-type TiO₂ for the decomposition of methylene blue. The crystallite growth and the phase transformation from anatase-type to rutile-type structure caused by heating at high temperature were retarded by doping ZrO₂ into TiO₂. The anatase-type TiO₂ doped with ZrO₂ showed high phase stability and maintained anatase-type structure even after heating at 1000°C for 1 h.