Oxidative activation of n-butane on sulfated zirconia

Catalytic activation and conversion of light alkanes by sulfated zirconia is unequivocally shown to be initiated by producing small concentrations of olefins. This occurs via stoichiometric oxidative dehydrogenation of butane by SO3 or pyrosulfate groups to butene (present mostly as alkoxy groups), water, and SO2. Thermal desorption and in situ IR spectroscopy have been used to determine all three reaction products. The concentration of butene formed determines both the catalytic activity of sulfated zirconia as well as the deactivation via formation of oligomers. The thermodynamics of the oxidative dehydrogenation of n-butane by different SZ surface structures has been examined by density functional (DFT) calculations. The calculations show that pyrosulfate or re-adsorbed SO3 species have the highest oxidizing ability.     

Colloidal crystals of cationic spheres

Colloidal single crystals of cationic polymer spheres (198–250 nm in diameter) in deionized aqueous dispersions were formed for the first time. The spheres used were poly(styrene-co-methacryloyloxyphenyldimethylsulfonium) cations. These cations are unstable in deionized suspensions with mixed beds of cation-exchange and anion-exchange resins. This was clarified by reflection spectroscopy, pH, conductance and -potential measurements for 250 days after suspension preparation. Colloidal crystals formed over a period of 24 h for the deionized suspensions at sphere concentrations higher than 0.09 in volume fraction. The nearest-neighbor intersphere distances coincide satisfactorily with the calculated values using the diameter and the concentration of the spheres. Alloy crystals formed from binary mixtures of the cationic polymer spheres and the anionic silica spheres when the ratio of the volume fraction of cationic spheres against the sum of the both cationic and anionic spheres was smaller than 0.3.     

N‐band Hubbard models. III. Boson–fermion and interaction–boson models for high‐Tc superconductivity

In this series of articles (I, II), N‐band Hubbard models have been considered for strongly correlated electron systems, which are realized in d–p, π–d, π–R, and σ–R conjugated systems. The magnetism and superconductivity of these systems have been elucidated in terms of effective exchange integrals (J), which are calculated by first‐principle methods. In part III of this series, the BCS–BEC crossover theory, has been introduced to elucidate the physical foundation of our J and JP model for the high‐T_c superconductivity (HTSC). The boson–fermion (BF) model for this theory is found useful for a reasonable explanation of the experimental phase diagrams of HTSC. The underlying physics of the BF model is different from that of the slave boson field‐theoretical model assuming spinon–holon condensations in the low dimension. The interaction boson model (IBM) for nuclear matter is also employed to describe the cooperative mechanisms of electron–phonon (EP), spin fluctuation (SF), charge fluctuation (CF), and many‐bands (MB) effects. This phenomenological model is useful for pictorial understanding and for the theoretical explanation of the cooperative mechanisms: (EP + SF), (SF + CF), (EP + SF + MB), etc. These are also investigated in analogy to BF model of fermionic gases, where the Feshbach resonance between boson and fermion is responsible for their coupling. The implications of these theoretical results are discussed in relation to recent ALPES and STM experiments for HTSC, which suggest the contributions of SF (J) and EP (P) interactions. The recently discovered superconductivity of boron‐doped diamond is examined as an example of two‐band sigma‐radical (σ–R) conjugated systems. Finally, the bipolaron model is briefly discussed in relation to boson–fermion model via EP interaction to superconductivity. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Selective separation of flavonoids with a polyvinyl alcohol membrane

In order to develop a selective membrane separation process for flavonoids, i.e. baicalin, baicalein and flavone extracted from a crude drug, “Wogon”, we have measured the permeabilities of these flavonoids through a polyvinyl alcohol membrane, together with their aqueous solubilities. The aqueous solubilities of baicalin and baicalein increase with increasing aqueous solution pH due to the acid dissociation of the saccharic carboxyl group of baicalin or the phenolic hydroxyl group of baicalein. The mass transfer coefficients of flavonoids experimentally obtained in both systems of single and mixed constituents agreed well with the calculated values based on a solution-diffusion model together with the acid dissociation of the carboxyl or hydroxyl groups of baicalin and baicalein, respectively. The selective mutual separation of flavonoids can be achieved from mixed solution of constituents in the neutral pH region. Furthermore, a quantitative discussion of the permeation behavior of flavonoids through the PVA membrane is provided from a molecular modelling computational viewpoint.     

Basis set and electron correlation effects on the polarizability and second hyperpolarizability of model open-shell pi-conjugated systems

The basis set and electron correlation effects on the static polarizability (alpha) and second hyperpolarizability (gamma) are investigated ab initio for two model open-shell pi-conjugated systems, the C(5)H(7) radical and the C(6)H(8) radical cation in their doublet state. Basis set investigations evidence that the linear and nonlinear responses of the radical cation necessitate the use of a less extended basis set than its neutral analog. Indeed, double-zeta-type basis sets supplemented by a set of d polarization functions but no diffuse functions already provide accurate (hyper)polarizabilities for C(6)H(8) whereas diffuse functions are compulsory for C(5)H(7), in particular, p diffuse functions. In addition to the 6-31G(*)+pd basis set, basis sets resulting from removing not necessary diffuse functions from the augmented correlation consistent polarized valence double zeta basis set have been shown to provide (hyper)polarizability values of similar quality as more extended basis sets such as augmented correlation consistent polarized valence triple zeta and doubly augmented correlation consistent polarized valence double zeta. Using the selected atomic basis sets, the (hyper)polarizabilities of these two model compounds are calculated at different levels of approximation in order to assess the impact of including electron correlation. As a function of the method of calculation antiparallel and parallel variations have been demonstrated for alpha and gamma of the two model compounds, respectively. For the polarizability, the unrestricted Hartree-Fock and unrestricted second-order M?ller-Plesset methods bracket the reference value obtained at the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples level whereas the projected unrestricted second-order M?ller-Plesset results are in much closer agreement with the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples values than the projected unrestricted Hartree-Fock results. Moreover, the differences between the restricted open-shell Hartree-Fock and restricted open-shell second-order M?ller-Plesset methods are small. In what concerns the second hyperpolarizability, the unrestricted Hartree-Fock and unrestricted second-order M?ller-Plesset values remain of similar quality while using spin-projected schemes fails for the charged system but performs nicely for the neutral one. The restricted open-shell schemes, and especially the restricted open-shell second-order M?ller-Plesset method, provide for both compounds gamma values close to the results obtained at the unrestricted coupled cluster level including singles and doubles with a perturbative inclusion of the triples. Thus, to obtain well-converged alpha and gamma values at low-order electron correlation levels, the removal of spin contamination is a necessary but not a sufficient condition. Density-functional theory calculations of alpha and gamma have also been carried out using several exchange-correlation functionals. Those employing hybrid exchange-correlation functionals have been shown to reproduce fairly well the reference coupled cluster polarizability and second hyperpolarizability values. In addition, inclusion of Hartree-Fock exchange is of major importance for determining accurate polarizability whereas for the second hyperpolarizability the gradient corrections are large.     

Synthetic Studies on Selectin Ligands/Inhibitors: A Systematic Synthesis of Sulfatide and Its Higher Congeners Carrying 2-(Tetradecyl)Hexadecyl Group as a Ceramide Substitute 1

Abstract

A systematic synthesis of sulfatide (I) and novel sulfatide analogs (II-VI) carrying 2-(tetradecyl)hexadecyl group as a ceramide substitute is described. The 3-O-, 4-O- and 3,4-di-O-levulinoyl derivatives of galactopyranosyl trichloroacetimidates (1, 12, and 13) were coupled with (2S,3R,4E)-3-O-acetyl-2-octadecanamido-4-octadecene-1,3-diol or 2-(tetradecyl)hexadecan-1-ol. The resulting glycolipids (2, 4, 14, and 15) were each transformed, by selective removal of the levulinoyl group(s), and successive sulfation and de-O-acylation, into the 3-sulfates (I, II), 4-sulfate (III), and 3,4-disulfate (IV). The 6-sulfate (V) was prepared from 2-(tetradecyl)hexadecyl β-D-galactopyranoside (21) via the 6-O-t-butyldimethylsilyl derivative, while the 3′-sulfate of 2-(tetradecyl)hexadecyl β-D-lactoside (VI) was synthesized from 2-(trimethylsilyl)ethyl 3′-O-benzyl-β-D-lactoside (26). The structures of the sulfated glycolipids (I-VI) were characterized by ion-spray MS, MS/MS, and ¹H NMR spectrometry.

     

Analysis of detected signal performance in multi-tracks of optical disk memory using convex-shaped recording mark

The possibility of multi-valued optical disk memory by using a convex-shaped recording mark fabricated by two-photon absorption is investigated. We fabricate a numerical model for convex-shaped recording marks and evaluate the signal characteristics in terms of the signal-to-noise ratio (SNR). The numerical results show that 6 bit data can be realized when the acceptable average SNR is 2 and a length of the mark is 4T.     

Noncovalent wrapping of chemically modified graphene with π-conjugated disk-like molecules

A facile and scalable preparation of dispersion of isolated graphene in various organic solvents has been developed by combining between covalent and noncovalent functionalizations of the graphene surface. Covalently functionalized graphene (FRG) was prepared by the reaction of partially reduced graphene oxide with aryl diazonium salts, followed by the graphene oxide being completely reduced with hydrazine. The resulting FRG disperse readily in organic solvents such as N,N′-dimethylformamide (DMF) and N-methyl-2-pyrrolidinone and the functionalization of graphene was characterized by Fourier transform infrared spectroscopy, thermogravimetric thermogram, X-ray photoelectron spectroscopy, and Raman spectroscopy. The hydrophobic surface of FRG was noncovalently wrapped with aromatic hexakis-dodecylhexa-peri-benzocorone (HBC) by simply mixing of dispersion of FRG in DMF with toluene solution of HBC. The complexation of FRG and HBC was monitored by viewing the absorption and fluorescence spectral changes. Atomic force microscopic images confirmed that graphene was covalently and noncovalently functionalized, while keeping a two-dimensional sheet shape.     

Counting rule of Nambu–Goldstone modes for internal and spacetime symmetries: Bogoliubov theory approach

When continuous symmetry is spontaneously broken, there appear Nambu–Goldstone modes (NGMs) with linear or quadratic dispersion relation, which is called type-I or type-II, respectively. We propose a framework to count these modes including the coefficients of the dispersion relations by applying the standard Gross–Pitaevskii–Bogoliubov theory. Our method is mainly based on (i) zero-mode solutions of the Bogoliubov equation originated from spontaneous symmetry breaking and (ii) their generalized orthogonal relations, which naturally arise from well-known Bogoliubov transformations and are referred to as “σ$\sigma$-orthogonality” in this paper. Unlike previous works, our framework is applicable without any modification to the cases where there are additional zero modes, which do not have a symmetry origin, such as quasi-NGMs, and/or where spacetime symmetry is spontaneously broken in the presence of a topological soliton or a vortex. As a by-product of the formulation, we also give a compact summary for mathematics of bosonic Bogoliubov equations and Bogoliubov transformations, which becomes a foundation for any problem of Bogoliubov quasiparticles. The general results are illustrated by various examples in spinor Bose–Einstein condensates (BECs). In particular, the result on the spin-3 BECs includes new findings such as a type-I–type-II transition and an increase of the type-II dispersion coefficient caused by the presence of a linearly-independent pair of zero modes.