Fast and Robust Nanocellulose Width Estimation Using Turbidimetry

The dimensions of nanocelluloses are important factors in controlling their material properties. The present study reports a fast and robust method for estimating the widths of individual nanocellulose particles based on the turbidities of their water dispersions. Seven types of nanocellulose, including short and rigid cellulose nanocrystals and long and flexible cellulose nanofibers, are prepared via different processes. Their widths are calculated from the respective turbidity plots of their water dispersions, based on the theory of light scattering by thin and long particles. The turbidity‐derived widths of the seven nanocelluloses range from 2 to 10 nm, and show good correlations with the thicknesses of nanocellulose particles spread on flat mica surfaces determined using atomic force microscopy.

     

Effect of preparation process of microfibrillated cellulose-reinforced polypropylene upon dispersion and mechanical properties

Microfibrillated cellulose (MFC)-reinforced polypropylene (PP) was prepared via two engineering approaches: disintegration of the pulp by a bead mill followed by a melt-compounding process with PP (B-MFC-reinforced PP); and disintegration of the pulp mixed with PP by a twin screw extruder followed by a melt-compounding process (T-MFC-reinforced PP). The effects that the engineering process and the microfibrillation of the pulp had upon the dispersion and mechanical properties were investigated through tensile tests, rheological analysis and X-ray computed tomography. The bead-milling method enabled a uniform microfibrillation of the pulp to under 100 nm, which corresponded to a surface area of 133–146 m²/g for the pulp, found by the Brunauer–Emmett–Teller (BET) analysis. The T-MFC-reinforced PP with 30 wt% MFC content exhibited a tensile modulus of 5.3 GPa and a strength of 85 MPa, whereas the B-MFC-reinforced PP composites with the same content of MFC exhibited values of 4.1 GPa and 59.6 MPa, respectively. Rheological analysis revealed that the complex viscosity and storage modulus at 170 °C of T-MFC-reinforced PP with 30 wt% MFC content are 5–7 and 5–8 times higher than that of B-MFC-reinforced PP, respectively. This indicated that T-MFC was more dispersed in the PP than B-MFC. Therefore, T-MFC produced a more rigid interconnected network in the matrix during the melting state than B-MFC.     

Radiation in a hypersonic shock layer generated around a projectile

Radiation emitted from the shock layer generated around a hypersonic flight model is experimentally investigated by using a ballistic range (two-stage light-gas gun). A polyethylene projectile of 1.2 cm in diameter is launched in this facility at the velocity of 5 km/sec (M=15), and the emission from the induced shock layer around the projectile is observed with a spectroscope. As a result, molecular band-spectra from NO and N₂ are detected along with those from carboncontaining molecules. Total emission power is measured with a diode-type powermeter. In addition, dimension effect of the flight model is theoretically and numerically examined, and a scaling law on thermochemical structure of the shock layer is developed. It shows that the thickness of thermal boundary-layer formed on the model surface does not follow the conventional scaling law based on the reaction distance and on the energy relaxation distance. Finally, the radiative field around the projectile is numerically computed, and the total power emitted from the shock layer is estimated. From the comparison between computed and measured results, the validity of the calculation model is discussed.     

Mass,momentum and total excess energy transported by a weak planeN wave

A weakly nonlinear plane acoustic wave is emitted into an ideal gas of semi-infinite extent from an infinite plate by its sinusoidal motion of single period. The wave develops into anN wave in the far field, as long as the energy dissipation is negligible everywhere except for discontinuous shock fronts. The third-order effects at shock fronts are evaluated, i.e., the generation of reflected acoustic wave as a result of the interaction of shock and expansion wave and the production of entropy by the energy dissipation at shock fronts. Consideration of these effects enables one to estimate the whole mass, momentum and total excess energy (sum of the kinetic energy and excess of internal energy over an initial undisturbed value) transported by theN wave to the accuracy of third order of wave amplitude. It is shown that the mass and total excess energy transported by theN wave increase and the momentum decreases to asymptotic limits as the wave propagates. The result shows good agreement with a numerical result obtained by solving the Euler equations with a high-resolution TVD upwind scheme.     

Facile synthesis of platinum nanoparticle-containing porous carbons,and their application to amperometric glucose biosensing

This study describes the facile synthesis of platinum nanoparticle-containing porous carbons (Pt/C) by carbonization of freeze-dried agarose gels containing potassium tetrachloroplatinate under a nitrogen atmosphere at 800 °C. By adjusting the ratio between agarose and platinate in the freeze-dried gels, the Pt content in the final Pt/C products could be systematically varied from 0–10 wt.%. Transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray photoelectron spectroscopy, Raman spectroscopy, and nitrogen physisorption measurements revealed that the Pt/C materials obtained by this method possess high surface areas (350–500 m² g⁻¹), narrow Pt nanoparticle size distributions (6 ± 3 nm) and nanocrystalline graphite –like carbon character. By immobilization of glucose oxidase on the surface of a 4 wt.% Pt/C electrocatalyst prepared by this route, a very sensitive amperometric glucose biosensor was obtained (response time <2 min, sensitivity 1.9 mA M⁻¹; and a linear response with glucose concentration up to 10 mM). The simplicity and versatility of the described synthetic method suggests its application to the preparation of carbon supported noble metal catalysts including palladium/C and gold/C.

This study describes the facile synthesis of platinum nanoparticle-containing porous carbons (Pt/C) by carbonization of freeze-dried agarose gels containing potassium tetrachloroplatinate. The Pt/C materials exhibited excellent electrocatalytic activities, as demonstrated by their successful integration into amperometric glucose biosensor

     

Possible Involvement of a Tetrahydrobiopterin in Photoreception for UV‐B‐induced Anthocyanin Synthesis in Carrot

Our previous studies of action spectra for UV‐B‐induced anthocyanin accumulation in cultured carrot cells indicated that a reduced form of pterin, possibly tetrahydrobiopterin, contributes to UV‐B photoreception. In this report, we provide additional evidence for the involvement of pterin in UV‐B light sensing. UV‐B‐induced phenylalanine ammonia‐lyase (PAL) activity was considerably suppressed by N‐acetylserotonin (an inhibitor of tetrahydrobiopterin biosynthesis), and this suppression was partially recovered by adding biopterin or tetrahydrobiobiopterin. In addition, protein(s) specifically bound to biopterin were detected by radiolabeling experiments in N‐acetylserotonin‐treated cells. Furthermore, diphenyleneiodonium, a potent inhibitor of electron transfer, completely suppressed UV‐B‐induced PAL activity. These results suggest the occurrence of an unidentified UV‐B photoreceptor (other than UVR8, the tryptophan‐based UV‐B sensor originally identified in Arabidopsis) with reduced pterin in carrot cells. After reexamining published action spectra, we suggest that anthocyanin synthesis is coordinately regulated by these two UV‐B sensors.     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Nb2O5·nH2O as a heterogeneous catalyst with water-tolerant Lewis acid sites

Niobic acid, Nb(2)O(5)·nH(2)O, has been studied as a heterogeneous Lewis acid catalyst. NbO(4) tetrahedra, Lewis acid sites, on Nb(2)O(5)·nH(2)O surface immediately form NbO(4)-H(2)O adducts in the presence of water. However, a part of the adducts can still function as effective Lewis acid sites, catalyzing the allylation of benzaldehyde with tetraallyl tin and the conversion of glucose into 5-(hydroxymethyl)furfural in water.     

3D interconnected ionic nano-channels formed in polymer films: self-organization and polymerization of thermotropic bicontinuous cubic liquid crystals

Thermotropic bicontinuous cubic (Cub(bi)) liquid-crystalline (LC) compounds based on a polymerizable ammonium moiety complexed with a lithium salt have been designed to obtain lithium ion-conductive all solid polymeric films having 3D interconnected ionic channels. The monomer shows a Cub(bi) phase from -5 to 19 °C on heating. The complexes retain the ability to form the Cub(bi) LC phase. They also form hexagonal columnar (Col(h)) LC phases at temperatures higher than those of the Cub(bi) phases. The complex of the monomer and LiBF(4) at the molar ratio of 4:1 exhibits the Cub(bi) and Col(h) phases between -6 to 19 °C and 19 to 56 °C, respectively, on heating. The Cub(bi) LC structure formed by the complex has been successfully preserved by in situ photopolymerization through UV irradiation in the presence of a photoinitiator. The resultant nanostructured film is optically transparent and free-standing. The X-ray analysis of the film confirms the preservation of the self-assembled nanostructure. The polymer film with the Cub(bi) LC nanostructure exhibits higher ionic conductivities than the polymer films obtained by photopolymerization of the complex in the Col(h) and isotropic phases. It is found that the 3D interconnected ionic channels derived from the Cub(bi) phase function as efficient ion-conductive pathways.     

Dynamic behaviour attributed to chiral carbohydrate substituents of N-heterocyclic carbene ligands in square planar nickel complexes

Nickel complexes having acetylated glucopyranosyl group incorporated N-heterocyclic carbene (NHC) ligands with methyl or benzyl groups as an N-substituent exhibit two kinds of dynamic behaviours in solution (1)H NMR spectroscopy. One of the dynamic behaviours is attributed to the anti- and syn-rotamers, which occur by the rotation of the unsymmetrical NHC ligands around the axes of the Ni-C bonds. The other is attributed to the diastereomers of the syn-rotamers, which occur by opposite rotation of the imidazolylidene rings and the chiral carbohydrate group incorporated into the NHC ligands. Crystallographic analysis of the nickel complex having the NHC ligand with acetylated glucopyranosyl and benzyl groups as N-substituents showed CH-π interaction between the glucopyranosyl unit of each NHC ligand and the phenyl ring of the other NHC ligand in the complex in the solid state.