Studies on the effect of ball milling on lignin structure using a modified DFRC method.

The structures of milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and residual lignin (REL) from a loblolly pine were analyzed using a modified derivatization followed by reductive cleavage (DFRC) method developed to allow the quantitative determination of three different structural monomeric products originating in lignin: phenolic beta-O-4, alpha-O-4, and etherified beta-O-4 structures. Results show that MWL and CEL are structurally identical, with an increased phenolic beta-O-4 content compared to that of the original Wiley milled wood. These results indicate that the portion of lignin linked to carbohydrates and that not linked to carbohydrates are structurally the same. Modified DFRC analysis of the effect of ball milling on the structure of lignin in wood, MWL, CEL, and REL indicate that vibratory ball milling does not change the lignin structure provided certain precautions are taken. Specifically, dry vibratory ball milling under a nitrogen atmosphere causes substantial structural changes including condensation, whereas vibratory ball milling in toluene had little effect on the lignin structure. This indicates that the structural differences observed in MWL and CEL arise because of the extraction procedure, which preferentially extracts phenolic lignin structures. MWL and CEL are representative of the total lignin in wood; however, due primarily to the solvent extraction process, higher phenolic hydroxyl contents are observed. Nitrobenzene oxidation showed structural results similar to those from the modified DFRC method.     

Hydrogasification of wood for high heating-value gas production X: Effect of pretreatment of Japanese oak bark by HNO3 oxidation on subsequent iron-catalyzed hydrogasification

Japanese oak bark, which is one of the most difficult woody biomass materials for iron-catalyzed lowtemperature (<700°C) hydrogasification, was subjected to HNO₃ oxidation as the pretreatment after prewashing with water. The effect was compared with that of HCl demineralization from four points of view: (1) removal of catalyst poisons; (2) development of porosity in the cell tissue; (3) introduction of ion-exchanged iron; and (4) reduction of nitrogen and sulfur. It was found that HNO₃-oxidized oak bark char loaded with iron by the ion-exchange method gave a satisfactory reactivity in agreement with the corresponding larch bark char previously used. Also, the oak bark char contained only small amounts of nitrogen and sulfur. These situations confirmed the high suitability of oxidation pretreatment combined with water prewashing for woody biomass.     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

Annual changes in distribution depths of bighand thornyhead <Emphasis Type="Italic">Sebastolobus macrochir</Emphasis> off the Pacific coast of northern Honshu,Japan

ABSTRACT:   Body size dependent distribution patterns of bighand thornyhead Sebastolobus macrochir were examined using bottom trawl surveys in the Tohoku area, off the Pacific coast of northern Honshu, Japan. In northern and southern Tohoku, distribution depths of ≤10-cm standard length (SL) fish increased from 500–600 m in 2003 to 600–700 m in 2005 with an increase in density of 11–20-cm SL fish at depths of 500–600 m. In 2004–2005, small fish (≤10 cm SL) were distributed in deeper waters than large fish (11–20 cm SL). In ≤20-cm SL fish, the main distribution depths changed from 300–600 m in 1997–2002 to 500–600 m in 2003 in southern Tohoku, but not in northern Tohoku. Stepwise multiple regression analysis showed that negative correlations were found in biomass densities between a few demersal fish species and bighand thornyhead at depths of 300–400 and 400–500 m in southern Tohoku. These results suggest that distribution of bighand thornyhead was affected by intra- and interspecific competitions in the Tohoku area.     

Habitat and prey selection of common minke,sei, and Bryde’s whales in mesoscale during summer in the subarctic and transition regions of the western North Pacific

This study represents the first quantitative analysis of the characteristics of the distribution areas and stomach contents of common minke whale Balaenoptera acutorostrata, sei whale B. borealis, and Bryde’s whale B. edeni in relation to oceanographic and prey environments in mid summer in the western North Pacific. Common minke whales were distributed within subarctic regions and the northernmost region of the transitional domain, coinciding with the main habitat of their preferred prey, Pacific saury Cololabis saira. Sei whales were mainly found in the northernmost part of the transition zone and showed prey preference for Japanese anchovy Engraulis japonica, which was significantly more abundant in the main distribution area of the whale than in its adjacent areas. “Hot spots” of Bryde’s whales were found in several regions of the transition zone between the subarctic boundary and the Kuroshio front. This whale species preferred Japanese anchovy as prey, for which the distribution density was significantly higher in the main distribution area of the whale than in the adjacent areas. These results indicate that the summer distributions of Pacific saury and Japanese anchovy greatly influence the distributions of these whale species, suggesting that the whales’ habitat selection is closely related to their prey selection.     

Genetic homogeneity between adult and juvenile populations of <Emphasis Type="Italic">Scombrops gilberti</Emphasis> (Percoid,Scombropidae) in the Pacific Ocean off the Japanese Islands

Scombrops gilberti is a member of the percoid family Scombropidae, which includes a single genus and three to four species worldwide. Little is known about the ecology of this species. Juvenile S. gilberti have been found in the waters off northern Japan (Iwate Prefecture), whereas adults are found in the waters around the southern counterpart (Izu Islands), approximately 700 km from the northern waters. In the present study, we captured immature S. gilberti (106–248 mm standard length, SL) in the northern waters by set net at 8–80 m depth, whereas larger individuals (150–328 mm SL) were captured by trawling at 150–500 m depth. By contrast, only adult S. gilberti (422–590 mm SL) were captured in the southern waters. The genetic composition of the adult population of S. gilberti from the southern waters and of the juvenile population from the northern waters was compared using the nucleotide sequence of the mitochondrial DNA (mtDNA) cytochrome b gene. No significant differences in genetic parameters such as fixation index, neutrality test or mismatch distribution analysis were found between these geographically distinct populations of S. gilberti, showing that these populations are genetically homogeneous.     

A possible function of Nik-related kinase in the labyrinth layer of delayed delivery mouse placentas

In mice and humans, Nik-related protein kinase (Nrk) is an X-linked gene that encodes a serine/threonine kinase belonging to GCK group 4. Nrk knockout (Nrk KO) mice exhibit delayed delivery, possibly due to defective communication between the Nrk KO conceptus and its mother. However, the mechanism of delayed labor remains largely unknown. Here, we found that in pregnant mothers with the Nrk KO conceptus, the serum progesterone (P4) and placental lactogen (PL-2) concentrations in late pregnancy were higher than those in the wild type. Moreover, we demonstrated that Nrk is expressed in trophoblast giant cells (TGCs) and syncytiotrophoblast-2 (SynT-2) in the labyrinth layer of the mouse placenta. In the human placenta, NRK is also expressed in Syn-T in villi. Both human Syn-T and mouse TGCs of the labyrinth layer are present within fetal tissues that are in direct contact with the maternal blood. The labyrinth layer of the Nrk KO conceptus was gigantic, with enlarged cytoplasm and Golgi bodies in the TGCs. To investigate the function of Nrk in the labyrinth layer, a differentially expressed gene (DEG) analysis was performed. The DEG analysis revealed that labor-promoting factors, such as prostaglandins, were decreased, and pregnancy-maintaining factors, such as the prolactin family and P4 receptor, were increased. These findings suggest that the Nrk KO mice exhibit delayed delivery owing to high P4 concentrations caused by the hypersecretion of pregnancy-maintaining factors, such as PL-2, from the placenta.     

Polyphenolic constituents of Cynomorium songaricum Rupr. and antibacterial effect of polymeric proanthocyanidin on methicillin-resistant Staphylococcus aureus

Oligomeric and polymeric flavan-3-ols were obtained by chromatographic fractionation of extracts from Cynomorium songaricum Rupr. The structure of the polymeric constituent, cynomoriitannin, was characterized using spectral and chemical data. Results from acid-catalyzed degradation indicated that cynomoriitannin is a polymeric proanthocyanidin predominantly composed of epicatechin, together with low proportions of epicatechin-3-O-gallate and catechin as extension units. The terminal unit was chiefly composed of catechin, with an admixture of epicatechin. Size exclusion chromatographic analysis demonstrated a mean polymerization degree of 14. Two new phloroglucinol adducts (cynomoriitannin-phloroglucinol adducts A and B) obtained by acid-catalyzed degradation of cynomoriitannin in the presence of phloroglucinol were characterized using spectral analyses. Six oligomeric flavan-3-ols were also identified as follows: procyanidin B3, catechin-(6'-8)-catechin, catechin-(6'-6)-catechin, epicatechin-(4β-8)- epicatechin-(4β-8)-catechin, epicatechin-(4β-6)-epicatechin-(4β-8)-catechin, and arecatannin A1, respectively. These flavan-3-ols were isolated from C. songaricum. This is the first time that this procedure has been described. The antibacterial activity of the fractions and constituents was tested against methicillin-resistant Staphylococcus aureus (MRSA). The crude acetone-water (7:3) extract had moderate activity against MRSA. Cynomoriitannin was the most effective of the plant constituents against MRSA.     

Sorption Behavior of Arsenate by Mg-Bearing Minerals at Hyperalkaline Condition: Implications for Oxyanions Sequestration During the Use and Disposal of Alkaline Wastes

The utilization and disposal of alkaline waste materials such as slag and coal fly ash as cement aggregates and raw materials in cement manufacturing can pose environmental and health hazards because these waste materials usually contain elevated concentration of toxic elements. This study examined the possibility of controlling the pore water chemistry of these waste materials in order to induce the secondary mineral formation of Mg-bearing minerals as major sorbing solids for oxyanions during the utilization and disposal of alkaline wastes. The formation of Mg-bearing minerals was examined at ambient temperature and alkaline pH conditions in the Mg?CSi?CAl system. The interaction of Mg-bearing minerals with oxyanions using arsenate as an analog was examined during and after mineral formation. The results revealed that the generated Mg-bearing mineral phases were smectite and brucite in Mg?CSi system and hydrotalcite and serpentine in Mg?CSi?CAl system. Moreover, hydrotalcite, serpentine, brucite, and smectite phases formed under low Si ratio showed high sorption capacity for arsenate, but only high Al content hydrotalcite and serpentine showed substantial irreversible fraction of sorbed arsenate. Hence, the generation of these kinds of hydrotalcite and serpentine phases as scavengers for oxyanions must be considered during the utilization and disposal of alkaline wastes.