Investigation on hydrogen abstraction from methyl glucoside by active oxygen species under oxygen delignification conditions III: effects of the origin of active oxygen species

Carbohydrate model compounds methyl β-d-glucopyranoside (MGPβ), methyl α-d-glucopyranoside (MGPα), and methyl β-d-mannopyranoside (MMPβ) and the deuterium compounds of MGPβ labeled at the anomeric or C-2 positions (MGPβ-1D, MGPβ-2D) were reacted with active oxygen species (AOS) generated in situ by reactions between O₂ and a co-treated phenolic lignin model compound, 4-hydroxy-3-methoxybenzyl alcohol (VAlc), under conditions simulating oxygen delignification (0.5 mol/l NaOH, 0.36 mmol/l Fe³⁺, 1.1 MPa O₂, 95°C). MGPβ was degraded more than MGPα but less than MMPβ when the pairs MGPβ/MGPα and MGPβ/MMPβ, respectively, were treated, which indicates that the configurational differences at the anomeric and C-2 positions influence the reactivity of AOS toward these compounds. When the pairs MGPβ/MGPβ-1D and MGPβ/MGPβ-2D were treated, no clear kinetic isotope effects were observed in either case. These results contrasted with those obtained when another phenolic compound, 2,4,6-trimethylphenol (TMPh), was used as the AOS generator instead of VAlc under exactly the same conditions. Clear kinetic isotope effects were observed when using TMPh. Because it is not easily accepted that the anomeric and C-2 hydrogen abstractions are minor reaction modes only for AOS generated in the VAlc system, it is suspected that the AOS do not show any clear kinetic isotope effect even though the AOS abstract an objective hydrogen.     

Significance of benzylic hydroxymethylene group in the reaction of lignin side-chain with active oxygen species under oxygen bleaching conditions

To examine the effect of the presence of benzylic hydroxyl group on the reaction of β-O-4 type lignin moiety with active oxygen species (AOS) under oxygen bleaching conditions, a specially designed β-O-4 type model compound carrying the benzylic methoxyl group, 2-(3,5-difluorophenoxy)-3-methoxy-3-(3,4-dimethoxyphenyl)propan-1-ol (IV), was treated together with a phenolic compound, 4-hydroxy-3-methoxybenzyl alcohol (II), under oxygen bleaching conditions. In this reaction system, AOS were generated by reactions of compound II with dioxygen and attacked compound IV. Compound IV was rather stable, while an analogous model compound carrying the benzylic hydroxyl group, 2-(3,5-difluorophenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (I), was rather degraded. This result and the previous knowledge on the relatively high stability of 3,4-dimethoxybenzyl alcohol carrying only the hydroxymethyl group as side-chain under the identical reaction conditions suggested that the existence of benzylic hydroxymethylene group is essential in the extensive reaction of side-chain of β-O-4 type lignin moiety with AOS. To compare the reactivity of AOS toward different types of hydroxyl and aryloxyl carbons, 2-(3,5-difluorophenoxy)propane-1,3-diol (VI) or 3-(3,5-difluorophenoxy)propane-1,2-diol (VII) was also subjected to this reaction system. Compound VII was degraded by AOS more extensively than compound VI.     

Investigation on the hydrogen abstraction from methyl glucoside by active oxygen species under oxygen delignification conditions IV: appearance of kinetic isotope effect in the reaction between methyl glucoside and deuterated methyl glucoside

In our previous studies, a clear kinetic isotope effect was observed when a pair of carbohydrate model compounds, methyl ??-d-glucopyranoside (MGP??) and a deuterated MGP?? labeled at the anomeric (methyl ??-d-(1-²H)glucopyranoside) or C-2 position (methyl ??-d-(2-²H)glucopyranoside), was reacted with active oxygen species (AOS) generated by reactions between O₂ and a phenolic compound, 2,4,6-trimethylphenol (TMPh), under oxygen delignification conditions. These results indicate that the AOS abstract the anomeric and C-2 hydrogens of MGP??. Contrarily, no clear kinetic isotope effects were observed when AOS were generated by reactions between O₂ and another phenolic compound, 4-hydroxy-3-methoxybenzyl alcohol (vanillyl alcohol, Valc), and hence, the abstraction of the anomeric and C-2 hydrogens by the AOS was not confirmed. In this study, a pair of MGP?? and the deuterated MGP?? labeled at all the positions, (²H₃)methyl ??-d-(1,2,3,4,5,6,6-²H₇)glucopyranoside, was reacted with AOS generated from TMPh or Valc under oxygen delignification conditions to further examine the appearance of a kinetic isotope effect. A clear kinetic isotope effect was observed when either of TMPh or Valc was the origin of AOS, indicating that some AOS abstract at least a hydrogen of MGP?? in either case. The results are further discussed focusing on the type of AOS generated from TMPh and Valc.     

Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin 2: significance of oxidation reaction of lignin during oxygen delignification

The progress of lignin oxidation during oxygenalkali bleaching of pulp was evaluated by the method based on the difference between permanganate consumption of original pulp and that of the mixture of pulp and effluent after oxygen-alkali bleaching. By low-consistency oxygen bleaching of softwood kraft pulp, the permanganate consumption decreased very little. When the kappa number of the pulp was halved (from 25.4 to 13.4), the decrease in permanganate consumption of 1 g pulp was only 1.22ml of 0.02mol/l potassium permanganate. This value was smaller than that obtained for the oxygen-alkali treatment of a corresponding amount of isolated residual lignin, 6.40ml. This was not due to the slow oxidation of lignin in pulp but to the formation of permanganate-consuming substances from carbohydrates. Those newly formed substances cannot be oxidized by oxygen-alkali treatment. Taking these facts into account, lignin originally present in pulp was found to be oxidized well. Reduction of carbonyl groups in carbohydrates prevented the formation of such substances.Part of this paper was presented at the 10th ISWPC, Yokohama, June 1999; and at the 43rd Lignin Symposium, Fuchu, October 1998     

Contribution of lignin to the reactivity of wood in chemical modifications II: influence of delignification on reaction with vaporous formaldehyde

Participation of lignin in the reaction between vapor-phase formaldehyde and wood was examined by using gradually delignified wood meal. A fi rst-order rate equation was successfully applied to the weight gain data. From the estimated reaction parameters such as rate constant, k, and ultimate weight gain, a, the reactivity toward formaldehyde was discussed among wood components, and compared with that for acetylation. k decreased monotonously with progress of the elimination of lignin, suggesting that the reaction rate of lignin is dominant over that of whole wood, and the decrease in the ratio of lignin retarded the reaction of wood as a whole. On the other hand, a increased with decreasing lignin content. This may be attributable to the enhanced reactivity of the remaining lignin due to some structural changes and to the increase in the number of reactive sites in polysaccharides as a result of their exposure accompanying the elimination of lignin. The dependencies of k and a on the lignin content were not similar to the case for acetylation, probably because of the difference in the reaction phase. In vapor-phase formaldehyde treatment, the remaining lignin reacts as it is, whereas in liquid-phase acetylation it would undergo rearrangement or swelling of the structure in the reaction solution.     

Pathogenicity testing of four Bursaphelenchus species on conifer seedlings under greenhouse conditions

The pinewood nematode, Bursaphelenchus xylophilus (Steiner and Buhrer, J. Agric Res. 48, 1934, 949), Nickle (J. Nematol. 2, 1970, 375), is the causative agent of the pine wilt disease and causes serious damage to pine forests around the world. During a survey for the pinewood nematode, four other Bursaphelenchus species (Bursaphelenchus mucronatus, B. sexdentati, B. anamurius and B. vallesianus) were isolated from wilted pine trees in Turkey. To understand the effects of these Bursaphelenchus species on wilting of pine trees, a study was conducted under greenhouse conditions. Two‐year‐old seedlings of three pine species (Pinus nigra, P. brutia and P. pinea) and one cedar species (Cedrus libani) were used. Fifteen seedlings of each species were inoculated with nematodes and 10 seedlings of each species served as controls. The inoculum densities used for each seedling contained approximately 1000 (±100) nematodes of all life stages in 0.25 ml of distilled water. The first wilting symptoms were observed in the fifth week in all pine species but not in the cedar seedlings. All seeding mortality occurred between the 5th and 13th weeks of the study; no mortality was observed outside of this period. The most pathogenic nematode species was B. mucronatus, closely followed by the other species. The most susceptible seedling species was P. nigra, and C. libani was the most resistant species.     

Influence of plum gum and sodium perborate addition on spruce kraft pulp properties during oxygen delignification

The aim of this study was to investigate the effects of plum gum liquor and sodium perborate addition to oxygen delignification process on spruce kraft pulp properties. Yields and viscosity of pulp were protected against oxidative attack, when kappa number of pulp was not changed by adding plum gum to oxygen delignification process. Delignification ratio improved by 7.4% without any viscosity loss by adding only 0.25% sodium perborate as active oxygen with plum gum liquor to the oxygen delignification process. It was found that crystallinity of pulp was improved by adding plum gum and sodium perborate to oxygen delignification. It was also determined that sodium perborate had an affirmative effect on delignification ratio, when plum gum affected pulp viscosity positively.     

不同光强下pH对伊乐藻光合机能的影响

不同光照条件下,研究pH变化对伊乐藻光合机能的影响。实验在水生植物培养室中进行,水培箱水深0．5m,植物在不同光照条件和pH条件下培养40d,实验发现pH对植物的影响常常和光照的强弱有一定关联,在pH高于9．0条件下,伊乐藻的叶绿素含量、PSII活力、Rubisco活力和生物量下降,但在弱光条件下（60lx）时,高pH对植物的影响程度加强。长期的高pH水平和低光照协同作用是湖泊富营养化过程中沉水植物种群退化的重要机制之一。     

Impact of plant species on the formation of carbon and nitrogen stock in soils under semi-desert conditions

The unique forest ecosystems investigated were created on the place of natural steppe biogeocoenoses 60?years ago. The aim of the study was to elucidate the effect of plant species on the formation of organic C and N stocks in soils and to estimate nitrogen availability for artificial wood plantation. For this purpose, 290 soil samples were taken from four forest monocultures (Quercus robur L., Pinus sylvestris L., Cotinus coggygria Scop., and Acer tataricum L.) and from virgin steppe ecosystem. The amounts and stocks of organic C, total and readily nitrified N, and seasonal dynamics of NO₃ ^? and NH₄ ⁺ ions activities were determined. It was shown that the species composition of the stands influenced the stock of organic C and N in soils. The storages of C and total N differed by 74 and 4.4?Mg/ha^?1, respectively, in the litter and upper horizons (0–40-cm layer) in the stands studied. The differences in distribution of stocks of these elements in virgin steppe and artificial forest ecosystems were found. Organic C and N stocks increased 1.6–6.6 times in the forest litter compared to the steppe one, while in 5–40-cm layer, the storages of C and N decreased by 20–35% compared to the virgin soil. The impact of litter on total N content in arid climate was limited in 0–5-cm layer. The deficit of mineral N compounds was observed in autumn in soil with low stock of total N.     

Inoculation of seven pine species or hybrid seedlings with Korean isolates of pinewood nematode under greenhouse conditions

? Seedlings of seven pine species or hybrids, Pinus densiflora, Pinus thunbergii, Pinus virginiana, Pinus echinata, Pinus koraiensis, Pinus thunbergii × Pinus massoniana and Pinus × rigitaeda, were inoculated in a greenhouse with 100, 1 000 and 10 000 pathogenic nematodes, Bursaphelenchus xylophilus, to compare initial symptom development and to evaluate susceptibility to pinewood nematodes.

? Genetic types were significantly different in the starting day of needle discoloration (χ² = 43.48; P < 0.001) and the period from nematode inoculation to seedling death (χ² = 32.85; P > 0.001), but treatment groups were not statistically different in the days from inoculation to seedling death in any of the pine species.

? There was no relationship between seedling mortality and the number of nematodes recovered from infected seedlings. Only eight of the nematode-inoculated seedlings remained alive by day 83 after inoculation, including four seedlings each of P. echinata and P. × rigitaeda grown from bulked seed collections.

? Seedlings from the bulk lots were likely more genetically diverse than those from the single-source lots. A broader genetic representation of pine species or hybrids is suggested for screening for planting stocks resistant to B. xylophilus.

     

Growth and survival of seedlings of various picea species under northern climatic conditions

The main purpose of these studies was to investigate the adaptation of young seedlings of various seed lots of Picea abies (L.) Karst., P. glauca (Moench) Voss, P. x lutzii Little and P. sitchensis (Bong.) Carr. to northern climatic conditions. Effects of temperature and photoperiod on elongation growth and growth cessation were studied under controlled conditions in a phytotron. In addition, growth and survival of the seedlings outdoors at 69°39’ N lat. were followed for two years. Seed lots of /’. abies originated from northern Norway (66° N lat.), those of the other species were from Alaska (between 57°.and 66° N lat.). The critical photoperiod for budset was 19–20 h for seed lots of P. abies. In general, the critical photoperiod for budset increased with increasing latitude of the seed source, but the results indicated a significantly shorter cirtical photoperiod for seed lots from about 60° N lat., <120 m a.s.l. of P. sitchensis (between 12 and 16 h) than for comparable seed lots of P x lutzii (17–18 h) or P. glauca (18 h). The time course of budset under natural light conditions, both in the phytotron and outdoors, generally followed the pattern predicted from the critical photoperiod. However, in P. glauca the budset occurred earlier than in P. abies although the latter had a longer critical photoperiod. Due to the short critical photoperiod and consequently delayed growth cessation and hardening, all seed lots of P. sitchensis (from 58° to 60° N lat.) were severely damaged during winter. Some damage was also observed in P. x lutzii and in P. abies. The optimum temperature for elongation growth was higher for P. sitchensis than for the other species. In the phytotron experiments, seedlings of P. sitchensis grew best at temperatures between 12 and 21°C, but at 9°C the best growth was obtained in some seed lots of P. abies. After two growth seasons outdoors, all seed lots of P. abies were taller than any seed lot of the other species. Also P. glauca seed lots and one seed lot of P. x lutzii showed good growth, and their growth rhythm seemed to be well adapted to the northern conditions.     

碳水化合物作添加剂制木质刨花板的研究——Ⅰ热压工艺的制定

本研究以杨木为原料,用糖蜜、麦芽糖、啤酒废液等碳水化合物以及它们的水解产物作添加剂压制刨花板。首先从探索差热和热重变化来确定热压曲线,其次用其水解前后产物作添加剂进行压板对照试验,并对反应机理进行初步探讨。最后对添加不同化学助剂改善板材性能的效果进行了测定。结果表明,NH_4NO_3的作用较ZnCl_2的显著,用碳水化合物可以压制出高质量的耐水性刨花板。     

Spatial distributions of tropical tree species in northern Vietnam under environmentally variable site conditions

Ecological interactions of species and thus their spatial pat- terns may differ between homogeneous and heterogeneous forests. To account for this, techniques of point pattern analysis were implemented on mapped locations of tree individuals from two 1-ha tropicalforest plots in Vietnam. We analyzed the effect of environmental heterogeneity on tree distributions; spatial distribution patterns of dominant species; inter-specific associations; and conspecific associations between life stages. Our analyses showed that： environmental conditions were homo- geneous at plot 1 but heterogeneous at plot 2; in both plots, all six domi- nant species were aggregated at various scales up to 30 m, and tree spe- cies were aggregated at larger scales in the homogeneous site than in the heterogeneous site; attraction between pairs of species was remarkably higher at the homogeneous site while negative associations were more frequent in the heterogeneous site; some species, H. kurzii, T. ilicifolia （homogeneous plot） and D. sylvatica, S. wightianum （heterogeneous plot） showed a lack of early life-stage individuals near conspecific adults. Moreover, additional clustering of young individuals was independent from conspecific adults, except D. sylvatica in both sites. These findings are consistent with the Janzen-ConneU hypothesis. Overall, habitat het- erogeneity influences spatial patterns and inter-specific associations of the tree species and evidences of self-thinning are shown in most species.     

Retarded biology of the two-spotted spider miteTetranychus urticae Koch after exposure to the anti-moulting compound,flufenoxuron under laboratory conditions

Flufenoxuron displayed various effects on the two spotted spider miteTetranychus urticae Koch according to the age and the concentrations tested. Generally, younger immatures were rather susceptible than the older ones. The duration of the developmental period increased due to treatments and reproduction of the succeeding females, at the different concentrations. The number of eggs/♀/10 days was fewer than in the control. Treated females at concentrations ranged between 400–20 ppm, produced none-viable eggs and viability increased by decreasing the concentration down to 1 ppm.     

Effect of rhizobial inoculation on growth of <Emphasis Type="Italic">Calliandra</Emphasis> tree species under nursery conditions

A nursery experiment was conducted in un-sterilized soil in Senegal using six Calliandra species or provenances inoculated with a mixture of seven rhizobial strains. Plant growth was assessed periodically at 1, 2, 3, 12 and 18 months whereas nodulation, shoot and root dry weights were assessed at 12 and 18 months after planting (MAP). Un-inoculated seedlings of all the six species died at 12 months after planting. Results of growth assessments were variable with significant differences (P < 0.05) between C. calothyrsus Meissn provenances (Flores and San Ramón) and C. juzepczukii Standley in height at 1, 2 and 3 MAP. Shoot dry weights of San Ramón provenance of C. calothyrsus Meissn were also significantly different from those of C. acapulcensis (Britton and Rose) Standley and C. longepedicellata (Mc Vaugh) H. Hern and Macqueen at 18 MAP. In contrast, C. glandiflora (L’Her.) Benth grew poorly and did not nodulate. Although rhizobial inoculation improved shoot and root dry weights some differences were observed among the Calliandra species in response to the inoculation, which suggested the occurrence of interaction between the rhizobial strains and the host plant species tested.     

Effect of wood species,digester conditions,and defibrator disc distance on wettability of fiberboard

Wettability of medium density fiberboard (MDF) surface affects paint or adhesive application and is, thus, of importance in the course of furniture manufacturing. This study investigated the effects of wood species, digester conditions and defibrator disc distance on the wettability properties. It was found that the wettability of the MDF significantly decreased with increasing the defibrator disc distance and increased with the increment in the severity of the digestion conditions. The highest wettability was found for samples made of beech wood having an average contact angle value of 74.5°, followed by poplar wood (76.5°), birch wood (79.7°), the mixture (1:1) of scots pine and beech wood (82.9°), and scots pine wood (86.4°), respectively.     

Sap flow of three co-occurring Mediterranean woody species under varying atmospheric and soil water conditions

We studied the seasonal patterns of water use in three woody species co-occurring in a holm oak forest in northeastern Spain. The three species studied, Quercus ilex L., Phillyrea latifolia L. and Arbutus unedo L., constitute more than 99% of the total basal area of the forest. The study period included the dry seasons of 1999 and 2000. Water use was estimated with Granier-type sap flux sensors. Standard meteorological variables, soil water content and leaf water potentials were also monitored. All monitored individuals reduced leaf-related sap flow (Q(l)) during the summer, concurrent with an increase in soil moisture deficit (SMD). Despite similar maximum Q(l) between species, the decline in Q(l) with increasing SMD was species-dependent. The average reduction in Q(l) between early summer and the peak of the drought was 74% for A. unedo (n = 3), 58% for P. latifolia (n = 3) and 87% for Q. ilex (n = 1). The relationship between canopy stomatal conductance (G(s)) and vapor pressure deficit (D) changed during the course of the drought, with progressively lower G(s) for any given D. Summertime reductions of Q(l) and G(s) were associated with between-species differences in vulnerability to xylem embolism, and with the corresponding degree of native embolism (lowest in P. latifolia and highest in Q. ilex). Our results, combined with previous studies in the same area, outlined differences among the species studied in manner of responding to water shortage, with P. latifolia able to maintain water transport at much lower water potentials than the other two species. In an accompanying experiment, A. unedo responded to an experimental reduction in water availability by reducing Q(l) during the summer. This species also modified its water use between years according to the different seasonal patterns of precipitation. These results are discussed in relation to the possible impacts that climate change will have on Q. ilex-dominated forests.     

Effect of compaction of soils on growth of Acacia mangium Willd. under glasshouse conditions

A glasshouse study was conducted to observe the initial height and diameter growth of Acacia mangium Willd, seedlings over a period of 24 weeks in pots with soil at bulk densities of 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and 2.0 g/cm³. Height and diameter growth increased significantly with decreasing soil bulk density. Significant differences in seedling diameter appeared during the tenth to twelfth week after transplanting and continued to increase until harvesting at week 24. The interaction between site water stress and compaction is discussed. A better understanding of these processes and the influence of site/soil factors on them is essential to the development of effective stand manipulation programs.