Hydrothermal saccharification of cotton cellulose in dilute aqueous formic acid solution

Cotton cellulose subjected to a dilute aqueous formic acid solution, at acid concentrations up to 1% (w/w), under hydrothermal conditions in a semi-batch reactor was converted into glucose and oligomers with lower degrees of polymerizations (DP). After heating at 250 °C for 60 min in 0.1% (w/w) aqueous formic acid solution, yields of glucose and total sugar with DP = 1 to 9 were 36.6 and 83.8% (100 × gC/gC of initial cotton sample), respectively, and 5-hydroxymethylfurfural was almost as low as 1%. The yields of glucose and oligomers were significantly improved by adding the acid. The reaction was represented by first-order reaction kinetics with regard to (1 ?C x) where x is the conversion based on the total sugar or glucose yield. At 250 °C, the differences in the rate constants (k ? k _water) were proportional to the square root of formic acid concentration.     

Communication: The reason why +c ZnO surface is less stable than -c ZnO surface: first-principles calculation

It has been experimentally shown that an O(-c)-polar ZnO surface is more stable than a Zn(+c)-polar surface in H(2) ambient. We applied first-principles calculations to investigating the polarity dependence on the stability at the electronic level. The calculations revealed that the -c surface terminated with H atom was stable maintaining a wurtzite structure, whereas the +c surface was unstable due to the change of coordination numbers of Zn at the topmost surface from four (wurtzite) to six (rock salt). This causes the generation of O(2) molecules, resulting in instability at the +c surface.     

Third-order nonlinear optical properties of open-shell supermolecular systems composed of acetylene linked phenalenyl radicals

The third-order nonlinear optical (NLO) properties, at the molecular level, the static second hyperpolarizabilities, γ, of supermolecular systems composed of phenalenyl and pyrene rings linked by acetylene units are investigated by employing the long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method. The phenalenyl based superethylene, superallyl, and superbutadiene in their lowest spin states have intermediate diradical characters and exhibit larger γ values than the closed-shell pyrene based superpolyene systems. The introduction of a positive charge into the phenalenyl based superallyl radical changes the sign of γ and enhances its amplitude by a factor of 35. Although such sign inversion is also observed in the allyl radical and cation systems in their ground state equilibrium geometries, the relative amplitude of γ is much different, that is, |γ(regular allyl cation)/γ(regular allyl radical)| = 0.61 versus |γ(phenalenyl based superallyl cation)/γ(phenalenyl based superallyl radical)| = 35. In contrast, the model ethylene, allyl radical/cation, and butadiene systems with stretched carbon-carbon bond lengths (2.0 ?), having intermediate diradical characters, exhibit similar γ features to those of the phenalenyl based superpolyene systems. This exemplifies that the size dependence of γ as well as its sign change by introducing a positive charge on the phenalenyl based superpolyene systems originate from their intermediate diradical characters. In addition, the change from the lowest to the highest π-electron spin states significantly reduces the γ amplitudes of the neutral phenalenyl based superpolyene systems. For phenalenyl based superallyl cation, the sign inversion of γ (from negative to positive) is observed upon switching between the singlet and triplet states, which is predicted to be associated with a modification of the balance between the positive and negative contributions to γ. The present study paves the way toward designing a variety of open-shell NLO supermolecular systems composed of phenalenyl radical building blocks.     

Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand

A copper(II)-hydroperoxo complex, [Cu(Me(6)-tren)(OOH)](+) (2), and a copper(ii)-cumylperoxo complex, [Cu(Me(6)-tren)(OOC(CH(3))(2)Ph)](+) (3), were synthesized by reacting [Cu(Me(6)-tren)(CH(3)CN)](2+) (1) with H(2)O(2) and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.     

Synthesis of the ABC ring system of Jiadifenin via Pd-catalyzed cyclizations

An efficient route toward the central ABC system of jiadifenin has been developed using two key Pd-catalyzed cyclizations. A protic solvent-activated Mizoroki-Heck reaction was used to construct the C(9) quaternary carbon and the A ring. A cascading Tsuji-Trost cyclization/lactonization sequence was employed to establish the BC ring system and the C(5,6) stereochemistry.     

Kinetics of phase separation and coarsening in dilute surfactant pentaethylene glycol monododecyl ether solutions

We investigated the phase separation phenomena in dilute surfactant pentaethylene glycol monodedecyl ether (C(12)E(5)) solutions focusing on the growth law of separated domains. The solutions confined between two glass plates were found to exhibit the phase inversion, characteristic of the viscoelastic phase separation; the majority phase (water-rich phase) nucleated as droplets and the minority phase (micelle-rich phase) formed a network temporarily, then they collapsed into an usual sea-island pattern where minority phase formed islands. We found from the real-space microscopic imaging that the dynamic scaling hypothesis did not hold throughout the coarsening process. The power law growth of the domains with the exponent close to 1/3 was observed even though the coarsening was induced mainly by hydrodynamic flow, which was explained by Darcy's law of laminar flow.     

Enhancement of second hyperpolarizabilities in open-shell singlet slipped-stack dimers composed of square planar nickel complexes involving o-semiquinonato type ligands

Using the spin-unrestricted hybrid density functional theory method, we have investigated the intermolecular interaction effects on the longitudinal static second hyperpolarizability (γ) of open-shell singlet slipped-stack dimers composed of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands, Ni(o-C(6)H(4)X(2))(2) (where X = O, NH, S, Se, PH). For comparison, we have also examined the γ values of a closed-shell singlet slipped-stack dimer composed of closed-shell monomers Ni[o-C(6)H(4)S(NH(2))](2). It is found that for interplanar distance ranging between 3.0 and 5.0 ? the slipped-stack dimers with intermediate monomer diradical characters exhibit larger γ values per monomer (γ(dimer)/2) than those with large monomer diradical characters or than the closed-shell dimer. These results extend the domain of validity of the relationship found between γ and the diradical character for individual molecules. It also turns out that the ratio R = (γ(dimer)/2)/γ(monomer) increases upon decreasing the interplanar distance and that this increase is larger for intermediate diradical character than for the other cases. These phenomena have been analyzed by considering the γ density distributions of the dimers, demonstrating a significant field-induced third-order charge transfer between the monomers in the case of intermediate diradical character. The present results indicate that open-shell singlet slipped-stack aggregates composed of monomers with intermediate diradical characters constitute another mean for achieving highly efficient and tunable third-order nonlinear optical materials.     

High-pressure and high-temperature generation using diamond/sic composite anvils prepared with hot isostatic pressing

Using a hot isostatic pressing (HIP) technique, we synthesized diamond/SiC composites from diamond and Si powders. At an HIP condition of 1450 °C and 100 MPa, a pressure much lower than that of the diamond stability field, diamond powders react with molten Si to form well-sintered diamond/SiC composites. Cubes of the composites with 15 mm edge length were thereby fabricated, and an application to the second stage anvils in a Kawai-type high-pressure apparatus was attempted. A hybrid anvils system using four cubes of the composites and four of the conventional WC was introduced and heating experiments up to 1600 °C became possible. Because the diamond/SiC composites are transparent to X-rays, the present system is applicable not only to diffraction studies but also to radiographic studies that need a larger window for an X-ray image.     

Non-symmetric calamitic liquid crystal dimers containing troponoid and benzenoid units

Five types of non-symmetric calamitic dimers were synthesized to investigate the effect of the core structure and length of the spacer on mesomorphic properties. Two non-symmetric dimers containing a troponoid and benzenoid unit showed smectic A and C phases whereas the corresponding benzenoid dimers showed no mesophase. Non-symmetric dimers with a three-ring system showed smectic A and C phases with higher transition temperatures than the two-ring system. We propose packing models for these non-symmetric dimers by considering the direction of the dipole moments of the ring structures and microsegregation between the polar units and the non-polar chains.