Evidence for the biosynthetic pathway from sinapic acid to syringyl lignin using labeled sinapic acid with stable isotope at both methoxy groups in Robinia pseudoacacia and Nerium indicum

A tracer experiment using synthesized labeled lignin precursors was designed to confirm the actual biosynthetic pathway for syringyl lignin. Tetradeuteroferulic acid-[8-D, 3-OCD(3)] and heptadeuterosinapic acid-[8-D, 3,5-OCD(3)] were synthesized and fed to shoots of robinia (Robinia pseudoacacia) and oleander (Nerium indicum) trees. The incorporation of each labeled precursor into lignin was traced by gas chromatography-mass spectrometry. The synthesized sinapic acid, in which both methoxy groups were labeled, was useful in monitoring the conversion of sinapic acid into syringyl lignin. When heptadeuterosinapic acid was fed, syringyl units containing seven deuterium labels were detected. The results of this study support the traditionally accepted pathway that sinapic acid is converted to sinapyl alcohol via sinapoyl-CoA in robinia and oleander.     

Seasonal and interannual variation in net ecosystem production of an evergreen needleleaf forest in Japan

Carbon dioxide (CO₂) flux was measured above the forest at the Fujiyoshida site on the northern slope of Mount Fuji in Japan in 2000?C2008 using an eddy covariance technique. The forest mainly consists of Japanese red pine (Pinus densiflora) and Japanese holly (Ilex pedunculosa). The 9-year average of monthly mean net ecosystem production (NEP) ranged from ?0.1?g?C?m^?2?day^?1 in January to 2.5?g?C?m^?2?day^?1 in May. The maximum net uptake was observed in May, although gross primary production (GPP) was highest in July. Variation in the leaf amount did not notably affect seasonal variation in GPP. This site was characterized by carbon uptake even in winter, if the meteorological conditions were conducive for photosynthesis and a resulting long period of carbon uptake. The 9-year averages of annual NEP, GPP, and ecosystem respiration (RE) were 388, 1,802, and 1,413?g?C?m^?2?year^?1, respectively. The annual NEP was lowest in 2003 and highest in 2004 over the 9?years. Year-to-year variability of NEP mainly depended on air temperature and photosynthetically active radiation in summer, and the dependence of the deviation of annual NEP on that of GPP was greater than that of RE. Long-term observational data indicated that the carbon uptake ability at the study site was at a moderate level in comparison with other temperate humid evergreen forests around the world. These data also indicated that the site had a high carbon uptake ability compared with other deciduous forests in Japan because of the duration of carbon uptake.     

Chemical modification of wood by non-formaldehyde cross-linking reagents

Summary Using sulfur dioxide (SO₂) as catalyst, wood specimens were treated with nonformaldehyde cross-linking reagents such as glyoxal, glutaraldehyde and dimethylol dihydroxy ethyleneurea (DMDHEU). The results of dimensional stability, acoustic properties, and mechanical strength tests were compared with those obtained from formaldehyde treatment. With glyoxal and glutaraldehyde treatments, antiswelling efficiency (ASE) reached around 70%, which is comparable to the values attained by formaldehyde treatment, although the accompanying weight gain was much larger than for the latter, whereas DMDHEU did not give sufficiently high ASE. None of the treatments, significantly increased specific dynamic Young's modulus (E/) with the exception of the DMDHEU treatment, loss tangent (tan ) decreased substantially, about 50 and 60% in longitudinal and radial directions respectively, which were somewhat exceeding the formaldehyde treatment. The results suggested that the improvement of the dimensional stability and acoustic properties is partly attributed to the formation of cross-links.     

Reactivity of green tea catechins with formaldehyde

In the reaction of green tea catechins with formaldehyde at room temperature (25°C), tea catechins were found to have reactivity. In particular, (-)-epicatechin gallate and (-)-epigallocatechin gallate, which have a galloyl moiety at the C-3 position, showed higher reactivity than (+)-catechin, (-)-epicatechin, or (-)-epigallocatechin. Reactivity of various kinds of simple phenolic compounds and flavonoids with formaldehyde was also examined. Among these compounds, only phloroglucinol showed reactivity to the same degree as that of nongalloylated catechins. These results suggest that factors for reactivity with formaldehyde at room temperature may be the presence of a phloroglucinolic A-ring structure and the absence of the electron-attractive group such as a carbonyl group in Cring. The comparison of the reactivity of 3-O-acylated catechins with that of 3-O-galloylated catechins indicated that only a galloyl group effectively enhanced reactivity with formaldehyde.     

Preparation of strongly acidic cation-exchange resins from gymnosperm acid hydrolysis lignin

The chemical preparation of strongly acidic cation-exchange resin from sulfuric acid lignin (Klason lignin) (SAL), a typical acid hydrolysis lignin, was investigated. Sulfonation of resinified SAL itself gave a resin with an ion-exchange capacity of 2.3 mEq/g. After resinification with formaldehyde, the phenolized SAL with a reactivep-hydroxyphenyl group yielded a resin with an ion-exchange capacity of 3.2 mEq/g. The latter capacity is superior to that of the corresponding commercial phenol-type resins (2–3 mEq/g), but did not reach the level of the corresponding commercial styrene-type resins (4-5 mEq/g).This paper was presented at the 43th Lignin Symposium, Fuchu, October 1998     

Tree-to-tree and clone-to-clone variations of monoterpenes emitted from needles of hinoki (Chamaecyparis obtusa)

Variations in the composition of low boiling point (LBP) monoterpenes emitted from needle samples of 150 hinoki (Chamaecyparis obtuse) trees (30 strains, each with five clones) native to Shimane Prefecture, Japan, were investigated using a headspace technique. The assays revealed considerable proportional variations especially in the amount of sabinene, which ranged from 24% to 78% of the total LBP monoterpenes. The proportions of α-pinene, myrcene, and limonene negatively correlated with that of sabinene overall. In particular, the proportion of limonene showed clear negative correlation with that of sabinene (r = −0.98). Differences in the proportion of sabinene among five clones in each strain were less than 15% in 22 out of 30 strains, indicating that monoterpene composition is constitutively steady in most strains. In a few strains, however, considerable variation in the composition was observed among clones.     

Pits and rocky microsites in a subalpine forest stand facilitate regeneration of spruce saplings by suppressing dwarf bamboo growth inside a deer-proof fence

We determined patterns of microsite suppression in dwarf bamboo Sasa nipponica when grazing deer were absent. This bamboo species is able to outcompete Hondo spruce (Picea jezoensis var. hondoensis) saplings under many environmental circumstances. We set up two 10 × 100 m plots inside a deer-proof fence within a subalpine forest on Mt. Ohdaigahara, central Japan, and two similarly sized plots outside the fence. Within the plots, we surveyed microsites where spruce saplings grew. We measured height and shoot elongation of all spruce saplings, and culm height and cover ratios of dwarf bamboo growing around each spruce sapling. Spruce sapling density and average height were higher inside the deer-proof fence than outside, as were bamboo height and cover. Thus, there was a negative effect of deer browsing on vegetation parameters outside the fence and a suppression of the negative effect of bamboo on spruce sapling growth inside the fence. Spruce sapling height was higher in tree-fall pits than in other microsites inside the fence, whereas both dwarf bamboo height and cover were lower in pits and rocky sites than elsewhere. In soil and collar microsites, spruce sapling shoot growth was lower and bamboo height and cover were higher than in pits and rocky sites. Inside the fence, dwarf bamboo cover was high, but pits and rocks suppressed its growth, allowing spruce saplings to flourish. To restore heavily damaged spruce forests with advanced saplings, it will be necessary to construct deer-proof fences and create and maintain microsites with pits and rocks.     

Application of cationic polymer prepared from sulfuric acid lignin as a retention aid for usual rosin sizes to neutral papermaking

Cationic polymers that acted as the retention aids for usual rosin sizes in neutral papermaking were prepared from sulfuric acid lignin (SAL), one type of acid lignin. To convert SAL to the cationic polymer (MP-SAL), SAL was phenolated and then treated by the Mannich reaction to introduce the amino groups. In the MP-SAL single system, MP-SAL exhibited high sizing effectiveness in neutral papermaking with the rosin emulsion size. However, MP-SAL showed no sizing effectiveness when soap rosin size was used. MP-SAL showed increased sizing effectiveness as the pK _a of the introduced amino group increased. From this and comparison of the sizing degrees of MP-SAL and polyethylenimine, which possesses a linear structure, it was suggested that the sizing effectiveness was not only affected by the charge density and molecular weight, but also by the basicity of the introduced amino groups and the molecular structure of the retention aid. In the alum–MP-SAL dual system, alum and MP-SAL synergistically enhanced the sizing effectiveness in the rosin emulsion sizing at neutral pH. In turn, this allowed a decrease in the MP-SAL dosage and resulted in a small decrease in brightness.Part of this report was presented at the 48th Lignin Symposium, October 2003, Fukui     

Comparison of organic matter dynamics in soil between Japanese cedar (Cryptomeria japonica) forest and adjacent Japanese red pine (Pinus densiflora) forest established on flatland

In order to clarify the effects of tree species on organic matter dynamics in soil, we investigated the amount of forest floor material, leaf litter decomposition rate, soil chemical characteristics, soil respiration rate and cellulose decomposition rate in a Japanese cedar forest (cedar plot) and an adjacent Japanese red pine forest (pine plot) established on a flatland. The amount of forest floor material in the cedar plot was 34.5 Mg ha⁻¹ which was greater than that in the pine plot. Because the leaf litter decomposition rate was higher in the pine plot than in the cedar plot, it is likely that the difference in the amount of forest floor material between the plots is caused by the difference in the leaf litter decomposition rate. The C concentrations of soil in the cedar plot were 1.2–2.1 times higher than those in the pine plot. Soil pH(H₂O)s in the cedar plot were significantly higher than those in the pine plot. The soil respiration rates and the rates of mineralized C in the cedar plot byin vitro incubation were higher than those in the pine plot. From this result, it is assumed that soil organic matter in the cedar plot was decomposed relatively faster compared with the pine plot. Furthermore, microbial activities, which were reflected as cellulose decomposition rates in the cedar plot, were higher than those in the pine plot. A part of this paper was presented at the 109th Annual Meeting of the Japanese Forestry Society (1998).