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.     

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.     

Mechanism‐Based Trapping of the Quinonoid Intermediate by Using the K276R Mutant of PLP‐Dependent 3‐Aminobenzoate Synthase PctV in the Biosynthesis of Pactamycin

Mutational analysis of the pyridoxal 5′‐phosphate (PLP)‐dependent enzyme PctV was carried out to elucidate the multi‐step reaction mechanism for the formation of 3‐aminobenzoate (3‐ABA) from 3‐dehydroshikimate (3‐DSA). Introduction of mutation K276R led to the accumulation of a quinonoid intermediate with an absorption maximum at 580 nm after the reaction of pyridoxamine 5′‐phosphate (PMP) with 3‐DSA. The chemical structure of this intermediate was supported by X‐ray crystallographic analysis of the complex formed between the K276R mutant and the quinonoid intermediate. These results clearly show that a quinonoid intermediate is involved in the formation of 3‐ABA. They also indicate that Lys276 (in the active site of PctV) plays multiple roles, including acid/base catalysis during the dehydration reaction of the quinonoid intermediate.     

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).     

Cloning and Characterization of the Biosynthetic Gene Cluster of 16‐Membered Macrolide Antibiotic FD‐891: Involvement of a Dual Functional Cytochrome P450 Monooxygenase Catalyzing Epoxidation and Hydroxylation

FD‐891 is a 16‐membered cytotoxic antibiotic macrolide that is especially active against human leukemia such as HL‐60 and Jurkat cells. We identified the FD‐891 biosynthetic (gfs) gene cluster from the producer Streptomyces graminofaciens A‐8890 by using typical modular type I polyketide synthase (PKS) genes as probes. The gfs gene cluster contained five typical modular type I PKS genes (gfsA, B, C, D, and E), a cytochrome P450 gene (gfsF), a methyltransferase gene (gfsG), and a regulator gene (gfsR). The gene organization of PKSs agreed well with the basic polyketide skeleton of FD‐891 including the oxidation states and α‐alkyl substituent determined by the substrate specificities of the acyltransferase (AT) domains. To clarify the involvement of the gfs genes in the FD‐891 biosynthesis, the P450 gfsF gene was inactivated; this resulted in the loss of FD‐891 production. Instead, the gfsF gene‐disrupted mutant accumulated a novel FD‐891 analogue 25‐O‐methyl‐FD‐892, which lacked the epoxide and the hydroxyl group of FD‐891. Furthermore, the recombinant GfsF enzyme coexpressed with putidaredoxin and putidaredoxin reductase converted 25‐O‐methyl‐FD‐892 into FD‐891. In the course of the GfsF reaction, 10‐deoxy‐FD‐891 was isolated as an enzymatic reaction intermediate, which was also converted into FD‐891 by GfsF. Therefore, it was clearly found that the cytochrome P450 GfsF catalyzes epoxidation and hydroxylation in a stepwise manner in the FD‐891 biosynthesis. These results clearly confirmed that the identified gfs genes are responsible for the biosynthesis of FD‐891 in S. graminofaciens.     

Impact of fertilizer on a small watershed of Lake Biwa: use of sulfur and strontium isotopes in environmental diagnosis

Sulfur and strontium isotopes (delta(34)S and (87)Sr/(86)Sr) were determined in 39 river water samples collected over three different cultivation periods (April, May, and June), and in several materials used for comparison (fertilizers, detergents, soils, irrigation and agricultural waters), to evaluate the impact of fertilizers on a small agricultural watershed of Lake Biwa, in central Japan. delta(34)S values in river water decreased (from +5.8 to -2.0 per thousand) with increasing SO(4) concentrations (3.8 to 93.2 ppm) from upstream to downstream of the watershed. Comparison of river water S isotopes with those of possible source materials indicates that the enrichment of SO(4) can be attributed to the dissolution of two kinds of fertilizers: (1) compound fertilizers commonly used in this area and (2) ammonium sulfate which is applied on a small scale. In contrast, (87)Sr/(86)Sr values of river water decreased with time from April (avg. 0.71163), through May (avg. 0.71139), to June (avg. 0.71127). The tendency of the sample plots on the (87)Sr/(86)Sr vs. 1/Sr diagram suggests a time-dependent increase in the contribution of soil water to the river, which is partly affected by the Sr-bearing fertilizers. It is suggested that a maximum of 25% of dissolved Sr is derived from these fertilizers, while more than 75% of it is of rock origin. Mass balance calculations permitted us to evaluate the proportion of fertilizer contribution in each river. Combined use of S and Sr isotopes together with concentration data could be a new environmental diagnosis technique for rivers and soils in localized watersheds.