Single molecule fluorescence autocorrelation measurement on anisotropic molecular diffusion in nematic liquid crystal

Diffusion kinetics of three dyes in nematic liquid crystals are studied with single-molecule fluorescence autocorrelation spectroscopy. Markedly large anisotropy was observed in the diffusion coefficient and structure of diffusion molecules showed no marked effect on the anisotropy.     

Synthesis and thermal cure of high molecular weight polybenzoxazine precursors and the properties of the thermosets

High molecular weight polybenzoxazine precursors have been synthesized from aromatic or aliphatic diamine and bisphenol-A with paraformaldehyde. The precursors were obtained as soluble white powder. Molecular weight was estimated from the size exclusion chromatography to be several thousands. The structure of the precursors was confirmed by IR, ¹H NMR and elemental analysis, indicating the presence of cyclic benzoxazine structure. The ratio of the ring-closed benzoxazine structure and the ring-opened structure in the high molecular weight precursor was estimated from ¹H NMR spectrum and also from the exotherm of DSC, showing that the ratio of the ring-closed benzoxazine structure was 77–98%. The precursor solution was cast on glass plate, giving transparent and self-standing precursor films, which was thermally cured up to 240 °C to give brown transparent polybenzoxazine films. The toughness of the crosslinked polybenzoxazine films from the high molecular weight precursors was greatly enhanced compared with the cured film from the typical low molecular weight monomer. Tensile measurement of the polybenzoxazine films revealed that polybenzoxazine from aromatic diamine exhibited the highest strength and modulus. While, polybenzoxazine from longer aliphatic diamine had higher elongation at break. The viscoelastic analyses showed that the glass transition temperature of the polybenzoxazines derived from the high molecular weight precursors were as high as 238–260 °C. Additionally, these novel polybenzoxazine thermosets showed excellent thermal stability.     

Abrupt changes in cross polarizations observed during thunder

Abrupt changes in the cross-polarization discrimination (XPD) and cross-polar phase were observed in cross-polarization measurements at 4, 6, and 11 GHz on propagation paths with low elevation angles. These abrupt changes were always observed during thunder, though exact time-to-time correspondence with lightning strokes was not clear in the measurement. In most cases, these sudden changes occurred in the direction in which the distortion of polarization ellipse increases, and the rate of change in XPD was much faster than rain-induced depolarizations by an order of magnitude. Based on the simultaneous measurement of circular and linear polarizations at 11 GHz, it was also found that the differential phase shift component suddenly increased to as large as20degto40degupon occurrence of these XPD changes, which confirms that this phenomenon is attributed to the effect of ice particles.     

Solution Property and Irradiation Effect of Random Copolypeptides Composed of Ala and Pro Residues

Summary Poly(proline) and random copolypeptide composed of Pro and Ala residues were synthesized, and their solution properties and molecular conformation were investigated. Aqueous solutions of the polypeptide were irradiated with γ-rays above the transition temperature. It was shown that the transition temperature of the aqueous solution of the copolypeptide is influenced by Ala-residue content and γ-ray irradiation.     

Water vapor solubility of poly(lactic acid) films modified the surface by vacuum ultraviolet irradiation

Surface modification of poly(lactic acid) (PLA) film is performed via 172 nm excimer lamp irradiation. Effects on water vapor solubility and physical properties via vacuum ultraviolet (VUV) irradiation are studied systematically. After VUV irradiation, water vapor solubility increases approximately 11–43% in the low‐pressure region and approximately 20–38% in the high‐pressure region as surface hydrophilicity increased. The increase is attributed to hydrogen bonding with the carboxyl groups because of VUV radiation. The modified layer is significantly swelling after water vapor sorption. The hydrophilic layer forms a thickness of 2–3 μm from the irradiated surface via VUV radiation, but no changes are observed inside the irradiated film. Therefore, PLA film solubility after irradiation is enhanced by hydrophilicity and the swelling effect of the surface. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42200.     

Absolute Configuration of β- and α-Asymmetric Carbons within β-O-4-Structures in Hardwood Lignin

In this study, we investigated the proportion of erythro- and threo-forms of β-O-4-ether structures and their enantiomeric compositions in hardwood lignin by applying the ozonation method to birch wood meal. Optical activity was not substantially observed in either the erythronic or threonic acids obtained as the ozonation products of β-O-4-structures in birch wood meal. The proportions of the four stereoisomeric forms {(αS,βR)-erythro, (αR,βR)-threo, (αS,βS)-threo, and (αR,βS)-erythro forms} were estimated to be 37-38%, 13-14%, 12-13%, and 36-37% based on the yields of erythronic and threonic acids, and on their optical activities. The proportions suggest that the entire components of β-O-4-ether structures in birch wood lignin have R- and S-configurations at the β-carbon in approximately the same quantities {(βR)-β-O-4-structure: (βS)-β-O-4-structure = 50–52:48–50}; i.e., that the β-ether structures are essentially racemic. This estimation implies that, during lignin biosynthesis, an equal number of enantiomeric forms of β-O-4-bonded quinone methides were formed by radical coupling reactions.     

Enhancement of the thermal stability and mechanical properties of a PMMA/aluminum trihydroxide composite synthesized via bead milling

The use of aluminum trihydroxide (ATH) fillers as non-halogen flame retardants for polymethylmethacrylates (PMMA) creates a conflict between the mechanical properties and heat resistance of the composites. Therefore, to ensure that the PMMA mechanical properties remain satisfactory, improvements in both the filler–polymer interactions and the ability to control the size and size distribution, morphology and dispersion of the fillers are required. Thus, in the present study, bead milling was used to control both the size distribution and dispersion of ATH fillers in MMA, which had an initial average size of 0.75 μm. The dispersion was obtained by alteration of the surface characteristics of ATH fillers using a silane-based dispersing agent, (3-acryloxypropyl) trimethoxysilane (APTMS). Bead milling successfully comminuted the ATH particles and prevented the formation of ATH agglomerates. The smallest average size of the ATH particles after bead milling was 300 nm. Highly dispersed ATH filler particles were observed in the TEM images of the PMMA/ATH composites. The filler–polymer interaction, i.e. the interaction parameter (B), was calculated. The effects of volume fraction, particle size distribution, and surface modification of the fillers on the results of dynamic mechanical analysis (DMA) are discussed. The thermal stability of the PMMA/ATH composites was also investigated using thermal gravimetric analysis (TGA).     

Effect of heating process on the formation of nanoparticles of elastin model polypeptide, (GVGVP)251, by gamma-ray crosslinking

Nanoparticles were prepared by the thermosensitive aggregation of the elastin model polypeptide, (GVGVP)₂₅₁, and gamma-ray crosslinking. Three different heating processes, “slow heating,” “fast heating,” and “heat shock,” were used for the aggregation of the peptide, followed by gamma-ray crosslinking. Only the “heat shock” process successfully yielded stable nanoparticles with diameters of less than ca. 150 nm and a narrow size distribution. Circular dichroism (CD) spectrometry showed that this polypeptide formed a type-II β-turn structure when the temperature was increased to above the cloudy point in the case of the “heat shock” process; suggesting that this structure might contribute to stable nanoparticle formation by gamma-rays. CD spectrometry also suggested that this structure would be affected during the formation of stable crosslinked particles.