Enzymatic hydrolysis of cellulose I is greatly accelerated via its conversion to the cellulose II hydrate form

Cellulose II hydrate was prepared from microcrystalline cellulose (cellulose I) via its mercerization with 5 N NaOH solution over 1 h at room temperature followed by washing with water. The structure of cellulose II hydrate changed to that of cellulose II after drying. Compared with cellulose II, cellulose II hydrate exhibited a slightly (8.5%) expanded structure only along the direction. The hydrophobic stacking sheets of the cellulose II were conserved in the cellulose II hydrate, and water molecules could be incorporated in the inflated two-chain unit cell of cellulose II hydrate. Enzymatic hydrolysis of cellulose I, cellulose II hydrate, and cellulose II was carried out at 37 °C using solutions comprising a mixture of cellulase and β-glucosidase. The hydrolysis of cellulose II hydrate proceeded much faster than the hydrolysis of the other two substrates, while the saccharification ratio of cellulose II was only slightly higher than that of cellulose I. The alkaline mercerization treatment was also applied to sugarcane bagasse. After its direct mercerization, the cellulose in bagasse was converted from cellulose I to cellulose II hydrate, and then to cellulose II after drying. Similar to in the case of microcrystalline cellulose, the rate of the enzymatic hydrolysis of the mercerized bagasse without drying (cellulose II hydrate) was much faster than the enzymatic hydrolysis of the other two substrates. Thus, the wet forms of cellulose and cellulosic biomass after mercerization, and after hydrolysis with cellulolytic enzymes, afforded superior products with extremely high degradability.     

Optical properties of high-density amorphous carbon films grown by nanosecond and femtosecond pulsed laser ablation

High-density tetrahedral amorphous carbon (ta-C) films have been prepared by nanosecond (17 ns) and femtosecond (150 fs) pulsed laser deposition (PLD) using fluences and repetition rates compatible with fast and homogeneous growth over large areas. Their optical properties were measured by spectroscopic ellipsometry from 1.0 to 4.7 eV and analyzed using a multi-layer Tauc-Lorentz model. In spite of very different ablation mechanisms, both PLD techniques produce high density bulk layers as revealed by a refractive index (n at 2 eV) of 2.7±0.1 for both fs-PLD and ns-PLD. Films are covered by a few nm-thick sp²-rich top layer which is denser and thicker in femtosecond PLD as compared to nanosecond PLD. The respective roles of low and high energies in the kinetic energy distribution of the incident carbon species are discussed in terms of densification and sp³↦sp² configurational relaxation predicted by the subplantation growth model. The significantly higher optical gap found in the ns-PLD films is attributed to the larger contribution of energetic species with kinetic energies E_c≥200 eV, as revealed by time-of-flight optical studies. PACS 81.40.Tv; 81.05.Uw; 81.15.Fg     

Influence of Si doping on the optical and structural properties of InGaN films

Influence of Si doping on the optical and structural properties of InGaN epilayers with different Si concentrations was investigated in detail by means of high-resolution X-ray diffraction (HRXRD), scanning electron microscope (SEM), Cathodoluminescence (CL) and photoluminescence (PL). It was found that a small amount of Si doping in InGaN could enhance luminescence intensity, improve the crystal quality of InGaN and suppress the formation of V-defects in InGaN. Further investigation by CL showed that V-defects act as nonradiative center, which lower the luminescence efficiency of InGaN. Based on above-mentioned results, one possible mechanism of influence of Si doping on the formation of V-defects in InGaN was also proposed in this paper.     

Minute displacement and strain analysis using lensless Fourier transformed holographic interferometry

An optical system for lensless Fourier transformed holographic interferometry is constructed to enable the measurement of minute displacements from nanometers to micrometers scale and to obtain corresponding strain distributions using a CCD camera with poor spatial resolution. Since a Fourier spectrum of an object beam is recorded on a hologram in this technique, the image reconstruction is easily performed with a single pass of 2-D fast Fourier transformation. Then, the map of the phase difference over the whole field is obtained by comparing two images before and after deformation. A suitable and effective unwrapping process is, however, inevitably required since the phase difference distribution is wrapped from −π to π in this technique. For phase unwrapping, the maximum spanning tree method is adopted here, which seeks a spanning tree that maximizes overall edge weights given by the cross amplitude. In-plane and out-of-plane displacements are obtained separately from the phase difference distributions at one's request. Moreover, in-plain strain is easily calculated from the in-plane displacement distribution.     

Enantioselective Total Synthesis of (+)‐Ophiobolin A

The enantioselective total synthesis of (+)‐ophiobolin A is described. This total synthesis features the construction of the spiro CD ring of (+)‐ophiobolin A through a stereoselective intramolecular Hosomi–Sakurai cyclization reaction, the joining of the A ring to the CD ring by using a reaction reported by Utimoto, and the construction of the ophiobolin eight‐membered carbocyclic ring through ring‐closing metathesis (RCM), which was performed for the first time in this study. This successful RCM reaction required the use of a substrate that contained either a benzyloxy or a methoxymethoxy group at the C5 position and either an isopropenyl group or its hydroxylated form at the C6 position.     

Structure and dynamics of a complex of cellulose with EDA: insights into the action of amines on cellulose

The neutron structure of a complex of EDA with cellulose has been determined to reveal the location of hydrogen atoms involved in hydrogen-bonding. EDA disrupts the hydrogen-bonding pattern of naturally occurring cellulose by accepting a strong hydrogen-bond from the O6 hydroxymethyl group as the conformation of this group is rotated from tg to gt. The O3-H·O5 intrachain hydrogen-bond commonly found in cellulose allomorphs is observed to be disordered in the neutron structure, and quantum chemistry and molecular dynamics calculations show that O3 prefers to donate to EDA. The hydrogen-bonding arrangement is highly dynamic with bonds continually being formed and broken thus explaining the difficulty in locating all of the hydrogen atoms in the neutron scattering density maps. Comparison with other polysaccharide-amino complexes supports a common underlying mechanism for amine disruption of cellulose.     

Photoinduced electron transfer from polystyrene pendant tris(2,2′-bipyridyl)ruthenium (II) complex to methylviologen

The characteristics of the photoinduced electron transfer reaction from polystyrene pendant tris(2,2′-bipyridyl)ruthenium (II) complex [Ru(bpy)] to methylviologen (MV²⁺) were studied. The rate constant k₁ from the excited state of the complex, Ru(bpy), to MV²⁺ were determined for both the polymeric and monomeric complexes from the lifetime τ of Ru(bpy) and the quenching rate of Ru(bpy) by MV²⁺. The polymer pendant Ru(bpy) showed three kinds of τ components ranging from 7 to 474 ns, in contrast to the monomeric complex, which showed one component of 350 ns. The k₁ values for both complexes were almost the same, on the order of 10⁸ L/mol s. The photoinduced electron transfer from solid-phase Ru(bpy) to liquid-phase MV²⁺ was realized by utilizing the polymer complex, and the solid–liquid interphase reaction system is discussed.     

Enantioselective total synthesis of (-)-erinacine B

The first enantioselective total synthesis of (-)-erinacine B has been achieved. Our approach features convergent construction of the 5-6-7 tricyclic cyathane core system via chiral building blocks prepared using asymmetric catalysis developed by us and highly stereoselective construction of all stereogenic centers in the aglycon. [reaction: see text].