Solid state NMR analysis of poly(L‐lactide) random copolymer with poly(ε‐caprolactone) and its reactive extrusion process

A random copolymer based on poly(L ‐lactide) (PLA) with poly(ε‐caprolactone) (PCL) was prepared and characterized by mechanical testing and solid state NMR, compared with a polymer blend. For a monofilament sample consisting of PLA/PCL random copolymer, there were negative correlations between the CL content and the mechanical properties: tensile strength, tensile elastic modulus, flexural rigidity, and flexural hysteresis decreased with increasing CL content. In contrast, the mechanical properties of the polymer blend were only slightly changed by addition of the CL unit. For the random copolymer, the addition of a small amount of CL reduced relaxation times, T₁C and T_1ρH, gradually. The T₁C and T_1ρH values correlated closely with the tensile elastic modulus and the tensile strength, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Simulation of mechanical properties of epoxy-based chemically amplified resist by coarse-grained molecular dynamics

The mechanical properties of an epoxy-based chemically amplified resists with various cross-linking ratios were simulated using a newly developed coarse-grained molecular dynamics simulation that employs a bead–spring model. Models with the different cross-linking ratios were created in the molecular dynamics calculation step and uniaxial elongation simulations were performed. The results reveal that the simulated elastic modulus of the resist modeled by the Kremer–Grest model with an extended angle bending potential depends on the cross-linking ratio, its dependency exhibits good agreement with that determined by nanoindentation tests.     

Silver(I)-Ion-Mediated Cytosine-Containing Base Pairs: Metal Ion Specificity for Duplex Stabilization and Susceptibility toward DNA Polymerases

Spectroscopic characterization of Ag^I-ion-mediated C-Ag^I-A and C-Ag^I-T base pairs found in primer extension reactions catalyzed by DNA polymerases was conducted. UV melting experiments revealed that C-A and C-T mismatched base pairs in oligodeoxynucleotide duplexes are specifically stabilized by Ag^I ions in 1:1 stoichiometry in the same manner as a C-C mismatched base pair. Although the stability of the mismatched base pairs in the absence of Ag^I ions is in the order C-A≈C-T>C-C, the stabilizing effect of Ag^I ions follows the order C-C>C-A≈C-T. However, the comparative susceptibility of dNTPs to Ag^I-mediated enzymatic incorporation into the site opposite templating C is dATP>dTTP≫dCTP, as reported. The net charge, as well as the size and/or shape complementarity of the metal-mediated base pairs, or the stabilities of mismatched base pairs in the absence of metal ions, would be more important than the stability of the metallo-base pairs in the replicating reaction catalyzed by DNA polymerases.     

Force measurement enabling precise analysis by dynamic force spectroscopy

Dynamic force spectroscopy (DFS) makes it possible to investigate specific interactions between two molecules such as ligand-receptor pairs at the single-molecule level. In the DFS method based on the Bell-Evans model, the unbinding force applied to a molecular bond is increased at a constant rate, and the force required to rupture the molecular bond is measured. By analyzing the relationship between the modal rupture force and the logarithm of the loading rate, microscopic potential barrier landscapes and the lifetimes of bonds can be obtained. However, the results obtained, for example, in the case of streptavidin/biotin complexes, have differed among previous studies and some results have been inconsistent with theoretical predictions. In this study, using an atomic force microscopy technique that enables the precise analysis of molecular interactions on the basis of DFS, we investigated the effect of the sampling rate on DFS analysis. The shape of rupture force histograms, for example, was significantly deformed at a sampling rate of 1 kHz in comparison with that of histograms obtained at 100 kHz, indicating the fundamental importance of ensuring suitable experimental conditions for further advances in the DFS method.     

Particle velocity and solids circulation rate in a jet-spouted bed

Radial distribution of particle velocities, solids circulation rate and radial variation in bed voidage in a jet-spouted bed were investigated in a 0.2 m diameter conical-cylindrical column. The upward particle velocity is strongly dependent on gas velocity and its radial profile is the Gaussian. The solids circulation rates are of the same order of magnitude as those in a conventional spouted bed and are proportional to the gas velocity. Estimation of the variation in bed voidage in the radial direction revealed that the annulus voidage of about 0.90 was greater than the spout voidage of around 0.70. This tendency is contrary to that in a conventional spouted bed.     

Thraustochytrid as a potential source of carotenoids

Thraustochytrids, marine protists whose dominant genera are Thraustochytrium and Schizochytrium, belong to the kingdom Chromista and are known as an industrial source of DHA. We describe here that thraustochytrid strain KH105, isolated as a DHA producer, also accumulates significant levels of β-carotene and xanthophylls including canthaxanthin and astaxanthin. A4-d cultivation using a medium composed of 10% glucose and less than 0.3% of nitrogen sources in a half-concentration of seawater gave an astaxanthin production up to 6.1 mg/L, and canthaxanthin content reached more than 10 mg/L under conditions where a higher concentration of nitrogen sources (6%) was employed. It might be advantageous in mass production systems for these carotenoids to be extracted readily by simply suspending the cells with organic solvents such as acetone and chloroform. Analyses on the morphological and life history features of the KH105 strain revealed that it belongs to the genus Schizochytrium. This particular species of thraustochytrids is thus considered to be a promising source of xanthophylls as well as DHA for use in the food industry.     

A Novel KCaNi/α-Al2O3 Catalyst for CH4 Reforming with CO2

A potassium and calcium co-promoted nickel catalyst (KCaNi/-Al₂O₃) prepared by a direct impregnation method possessed a high activity, high stability and excellent coke resistance properties in CH₄ reforming with CO₂. XRD, XPS and H₂-TPR characterizations indicated that (i) Ca and K strengthened the interaction between Ni and -Al₂O₃ and promoted the formation of a unique NiAl₂O₄ phase on the surface of the catalyst and (ii) Ca and K increased the dispersion of Ni and retarded its sintering. Coking reactions (CH₄ temperature-programmed decomposition and O₂-TPO) disclosed that K reduced carbon formation via CH₄ decomposition.     

Investigation of CH4 Reforming with CO2 on Meso-Porous Al2O3-Supported Ni Catalyst

Meso-porous Al₂O₃-supported Ni catalysts exhibited the highest activity, stability and excellent coke-resistance ability for CH₄ reforming with CO₂ among several oxide-supported Ni catalysts (meso-porous Al₂O₃ (Yas1-2, Yas3-8), -Al₂O₃, -Al₂O₃, SiO₂, MgO, La₂O₃, CeO₂ and ZrO₂). The properties of deposited carbons depended on the properties of the supports, and on the meso-porous Al₂O₃-supported Ni catalyst, only the intermediate carbon of the reforming reaction formed. XRD and H₂-TPR analysis found that mainly spinel NiAl₂O₄ formed in meso-porous Al₂O₃ and -Al₂O₃-supported catalysts, while only NiO was detected in -Al₂O₃, SiO₂, CeO₂, La₂O₃ and ZrO₂ supports. The strong interaction between Ni and meso-porous Al₂O₃ improved the dispersion of Ni, retarded its sintering and improved the activated adsorption of CO₂. The coking reaction via CH₄ temperature-programed decomposition indicated that meso-porous Al₂O₃-supported Ni catalysts were less active for carbon formation by CH₄ decomposition than Ni/-Al₂O₃ and Ni/-Al₂O₃.     

Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars

The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.