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     

Reactivity of a condensed–type lignin model compound in the Mannich reaction and preparation of cationic surfactant from sulfuric acid lignin

 The chemical conversion of phenolized sulfuric acid lignin (P-SAL), prepared from sulfuric acid lignin (SAL) by phenolation with sulfuric acid catalyst, to novel cationic surfactant was investigated. To elucidate the chemical reactivity of the P-SAL to a Mannich reaction, 1-guaiacyl-1-p-hydroxyphenylethane (I) as a simple phenolized sulfuric acid lignin model compound was reacted with dimethylamine and formaldehyde. Quantitative analysis of the products by gas-liquid chromatography suggested that the p-hydroxyphenyl nucleus was more reactive than the guaiacyl nucleus. The Mannich reaction of SAL with dimethylamine did not yield a soluble cationic surfactant, but P-SAL produced water-soluble cationic surfactant in a quantitative yield. The Mannich reaction products (MP-SAL) of P-SAL had 1,3-dimethylaminomethyl groups/C₉-C₆. The results of the surface tension measurements showed that the decrease in surface tension of MP-SAL was much larger than that of lignosulfonate as a commercial surfactant from lignin.     

Preparation of liquid polyesterpolyols from glucose and its methyl derivative

Preparation of liquid polyols from d-(+)-glucose (Glc) and its derivative, methyl--d-glucoside (m-Glc), has been studied. Direct reaction of -caprolactone (CL) with Glc (CL:Glc = 2:1–5:1 in weight ratio) at 150°C using tin(II) 2-ethyl hexanoate (SnEht₂) (series A), in which melted Glc was suspended in CL, resulted in a dark-brown coloration of the reactants. The reaction was accompanied by formation of high molecular weight resins, a pH drop, production of water, and a considerable decrease in the hydroxyl value from the theoretically expected one. In the case of Glc/ethylene glycol (EG)/CL reaction system with SnEht₂ catalyst at 150°C (series B), in which the weight ratio of Glc to EG was fixed at 1:1, Glc dissolved in the EG/CL mixture, but the brown coloration of the reactant mixture still occurred. In this case, the formation of water was enhanced, but the other effects found in series A were suppressed to a considerable extent. In the m-Glc/CL/SnEht₂ reaction system (series C), in which m-Glc reacted with two to five times weight amounts of CL under the same conditions adopted in series A, development of the color, the production of high molecular weight materials and water, and the changes in pH and hydroxyl value were not observed. These results are discussed based on the chemical structural differences: Glc exists mostly in the hemiacetal form, but tautomerizes to the aldehyde, whereas m-Glc is an acetal and is protected from reversion to the aldehyde.     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate III: Successive treatment of acid hydrolysis lignin and a lignin model compound by phenolation and arylsulfonation*

The chemical conversion of red pine sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis lignin sample to water-soluble arylsulfonates of lignin derivation (i.e., phenolized SAL) was investigated. Treatment of phenolized SAL with chlorosulfonic acid followed by alkali hydrolysis gave water-soluble sulfonated products with a sulfonic acid group on their aromatic nuclei quantitatively. The products possess 2.0 SO₃Na/C₉ C₆. In contrast, the content of sulfuric acid group in sulfonated SAL was only 0.33C₉. Chlorosulfonation of 1-guaiacyl-l-p-hydroxyphenylethane as a phenolized guaiacyl lignin model compound revealed that the sulfonyl chloride group was introduced at thepara position of an aromatic methoxyl group, theortho position of a phenolic hydroxyl group, or both.     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin I: effects of pressing pressure and pressure holding

The deformation behavior of low molecular weight phenol formaldehyde (PF) resin-impregnated wood under compression in the radial direction was investigated for obtaining high-strength wood at low pressing pressures. Flat-sawn grain Japanese cedar (Cryptomeria japonica) blocks with a density of 0.34g/cm³ were treated with aqueous solution of 20% low molecular weight PF resin resulting in weight gain of 60.8%. Oven-dried specimens were compressed using hot plates fixed to a testing machine. The temperature was 150°C and the pressing speed was 5mm/min. The impregnation of PF resin caused significant softening of the cell walls resulting in collapse at low pressures. The cell wall collapse was strain-dependent and occurred at a strain of 0.05–0.06mm/mm regardless of whether the wood was treated with PF resin. Thus, pressure holding causing creep deformation of the cell walls was also effective in initiating cell wall collapse at low pressure. Utilizing a combination of low molecular weight PF resin impregnation and pressure holding at 2MPa resulted in a density increase of PF resin-treated wood from 0.45 to 1.1g/cm³. At the same time, the Youngs modulus and bending strength increased from 10GPa to 22GPa and 80MPa to 250MPa, respectively. It can be concluded that effective utilization of the collapse region of the cell wall is a desirable method for obtaining high-strength PF resin-impregnated wood at low pressing pressures.     

Isolation of lignin–carbohydrate bonds in wood. Model experiments and preliminary application to pine wood

A novel method for analysis of benzylic ether type lignin–carbohydrate bonds has been developed by using model compounds. Four diastereomers of model compound 3-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-3-(methyl -d-glucopyranoside-6-O-yl)-1-propanol (GGMGP), were ozonized in acetic acid/water/methanol 16:3:1 for 1h at 0°C. The product from ozonation of each diastereomer was saponified and the corresponding -etherified tetronic acid (TAMGP) was isolated using ion exchange chromatography. Minor amounts of methyl -d-glucopyranoside (MGP) and small amounts of a gluconic acid etherified with tetronic acid (TAGLCA), tetronic acid, gluconic acid, and glyceric acid were detected in the product mixture of ozonated benzylic ether type model compounds. The results suggest that a benzyl ether bond between lignin and carbohydrate is rather stable during the ozone treatment. Acid treatments with sulfuric acid or trifluoroacetic acid of the derived TAMGP led to cleavage of the glucosidic bond but only a small amount of products (tetronic acid and glucose) resulting from cleavage of the -ether bond were formed. The successful chemical treatments were used for studies of benzylic ether bonds in Japanese red pine. The results suggest the presence of benzylic ether bonds to polysaccharides in the wood.Part of this paper was presented at the 10th International Symposium of Wood and Pulping Chemistry (ISWPC), Yokohama, 1999; the 11th ISWPC, Nice, 2001; and as a rapid comunication in J Wood Sci (2000) 46:263–265     

Development of binderless particleboard from kenaf core using steam-injection pressing

Binderless particleboards were successfully developed from kenaf core using the steam-injection press. The effects of board density, steam pressure, and treatment time on the properties of the board were evaluated. The target board densities were relatively low, ranging from 0.40 to 0.70g/cm³. The properties [i.e., moduli of rupture (MOR) and elasticity (MOE) in both dry and wet conditions, internal bonding strength (IB), and water absorption (WA)] of the boards increased linearly with increasing board density. Steam pressure and treatment time also affected the board properties. The bending strength and IB were improved with increased steam pressure. A long steam treatment time contributed to low thickness swelling (TS) values and thus better dimensional stability. The appropriate steam pressure was 1.0MPa, and the treatment time was 10–15min. The properties for 0.55g/cm³ density boards under optimum conditions were MOR 12.6MPa, MOE 2.5GPa, IB 0.49MPa, TS 7.5%, and wet MOR 2.4MPa. Compared with the requirement of JIS 5908, 1994 for particleboard, kenaf binderless boards showed excellent IB strength but relatively poor durability.Part of this report was presented at the 19th Annual Meeting of the Japan Wood Technological Association, Tokyo, October 2001     

In vitro propagation of <Emphasis Type="Italic">Oroxylum indicum</Emphasis> Vent. a medicinally important forest tree

In vitro propagation of Oroxylum indicum Vent. was carried out using cotyledonary node explants. Among the different types of cytokinins used for culture establishment, 6-benzyladenine exhibited the best response with higher concentrations (8.87µM or above) for inducing multiple shoots. Inclusion of indole-3-acetic acid (2.85µM) into 6-benzyladenine-supplemented medium triggered a high frequency of response as well as a proliferation of shoots. The best medium for proliferation was Murashige-Skoog (MS) medium with 6-benzyladenine (8.87µM) and indole-3-acetic acid (2.85µM). However, incorporation of gibberellic acid (1.44µM) was mandatory to enhance shoot elongation. Repeated subculturing of cotyledonary node and in vitro developed nodal segments in MS medium with 6-benzyladenine (4.44µM) at 4-week intervals resulted in continuous mass multiplication of shoots without any evidence of decline. Root induction was best (91.6%) when MS strength was reduced to one-quarter and combined with -naphthalene acetic acid (2.69µM) and indole-3-acetic acid (5.71µM), with a high survival rate (70–72%) of plantlets hardened in either soil rite or soil:sand:soil rite (1:1:2).     

Altitudinal and longitudinal variations in Pinus brutia (Ten.) of Crete Island,Greece: some needle,cone and seed traits under natural habitats

Four populations representing the entire natural distribution range of Pinus brutia (Ten.) in Crete (Greece) were sampled to determine: (1) Altitudinal variation within populations of Lassithi, Vorizia, Koustagerako, and Samaria, and; (2) Longitudinal variation among the four populations, based on morphological and anatomical differences in cone, needle and seed characteristics. Samples were collected from 10 trees per altitude, at three altitudes in each population. A total of 12 morphological and anatomical traits from needles, cones and seeds were analyzed to assess the altitudinal and longitudinal variations of the species in the island. The number of teeth per cm showed significant (P<0.01) differences between altitudes in Samaria, Vorizia and Lassithi, while needle length, width and the number of resin canals showed significant differences (P<0.01) between altitudes in Koustagerako. Cone width showed patterns of variation along the altitudinal gradient in Koustagerako, Samaria and Vorizia. Most traits had their highest means at the middle altitudes (650masl) in all the four populations. Overall, no clear altitudinal differentiation was detected, probably due to high rate of gene flow. Longitudinal variability showed a clear pattern of differentiation along the east–west climatic gradient. Needle length, width, sheath length, number of teeth per cm and the number of resin canals were the most useful traits for determining the climatic gradient clines.     

Sediment accretion and variability of sedimentological characteristics of a tropical estuarine mangrove: Kemaman, Terengganu, Malaysia

This paper reports on a study of accretion rate and sedimentological variability in a estuarine mangrove swamp. One hundred and sixteen stations were monitored for 2 years. In addition, surface sediment samples were collected at 52 stations during the months of May, June and July (1994) to represent the nonmonsoon sediments and November, December (1994) and January (1995) to represent the monsoon sediments. Results show that the accretion rate for the first year was 1.46±0.13cm/yr and 0.66±0.04cm/yr for the second year thus making the average accretion for the 2 years period to be 1.06cm/yr. The average accretion rate for the monsoon season (0.26 ± 0.04cm/month) was found to be significantly higher than the nonmonsoon season (0.12 ± 0.03cm/month). Nevertheless, the same is not true for the surface sediment characteristics. The sedimentological characteristics between the monsoon and the nonmonsoon sediments were not significantly different.     

Effects of nitrogen and phosphorus fertilization on the growth and nutrition of hybrid poplars on Vancouver Island

The effects of nitrogen (N) and phosphorus (P) rates, P source, and method of P application were tested on growth and nutrition of four clones of hybrid poplar (Populus trichocarpa Torr. & Gray×P. deltoides Bartr. ex Marsh or P. trichocarpa×P. maximowiczii A. Henry) in a plantation on Vancouver Island. Treatments were applied shortly after planting. Nitrogen (0, 500kgNha^–1) was supplied as ammonium sulfate (AS); half of the AS was added at the start of the second growing season. Phosphorus (0, 100, 200kgPha^–1) was supplied as triple super phosphate (TSP), rock phosphate (RP), or diammonium phosphate (DAP) and banded or broadcast. Over four growing seasons, stem volumes increased with AS and P additions. The effects of AS and P each were greatest when the other was also added. Volume was greater when P was applied at 100kgha^–1 than in the P control and did not significantly increase further at 200kgPha^–1. Phosphorus additions were more effective when added as TSP or DAP than when added as RP, but only in P100 and when banded. Banding increased volume when P was applied at 200kgha^–1, but increases were significant only for DAP fertilized trees. Roto-tilling associated with the banding treatment also increased volume when AS and P were not added. Rankings of clones with respect to stem volume varied with N supply and changed over time.     

Gamma radiation sensitivity of larvae and adults of the red flour beetle, <Emphasis Type="Italic">Tribolium castaneum</Emphasis> Herbst

In this study, the susceptibility of larvae and adults of Tribolium castaneum (Herbst) to gamma radiation was investigated in the laboratory in Turkey. Gamma radiation was applied at 6 dose levels between 20 and 200Gy to 13–15day-old adults and at 5 dose levels between 20 and 180Gy to 18–20day-old larvae of T. castaneum. All experiments were performed in growth chambers maintained at 27±1°C and 70±5% r.h. The larvae proved to be the more susceptible stage, survival to the adult stage being prevented by exposure of the eggs to 100Gy; the adult stage was less susceptible. LD₅₀ and LD₉₉ values were determined as 19,75 and 42,97Gy for larvae and 33,21 and 64,50Gy for adult stage, respectively. It was concluded that 100Gy is the effective dose for both larval and adult stages.     

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     

Nitrogen use by <Emphasis Type="Italic">Pinus densiflora</Emphasis> trees growing on a Mt. Fuji lava flow

To quantify the nitrogen (N) use by Pinus densiflora trees growing on an infertile lava surface, N pools, N requirement and N uptake through fine roots and N deposition from the atmosphere were estimated. The N requirement and the N uptake of fine roots were 55.5kgNha^–1year^–1 and 39.7kgNha^–1, respectively. Thus, the ratio of N uptake to N requirement of the fine roots was 71.5%. Including fine-root contribution, the total N requirement of the P. densiflora trees was 98.6kgNha^–1year^–1, and the total N uptake was 64.2kgNha^–1year^–1. Thus, the N uptake of the P. densiflora trees was 64.1% of the N requirement, indicating that P. densiflora trees growing on an infertile lava surface obtain some of their N from below-ground organic material layers every year and the contribution of N storage in trees for their growth is not any higher than indicated in previous reports that excluded fine-roots contribution. The wet N deposition of our research forest was only 5.8% of the N requirement of the P. densiflora trees and only 8.9% of the N uptake. Movement of the below-ground organic material layer N concentrations in the F- and L-layers coincides with needle development and fine-root growth, suggesting the possibility that P. densiflora trees extract N from the organic N of those layers for growth.     

Effects of a nursery CO2 enriched atmosphere on the germination and seedling morphology of two Mediterranean oaks with contrasting leaf habit

The use of an enriched CO₂ atmosphere in tree nurseries has been envisaged as a promising technique to increase productivity and to obtain seedlings with a higher root/shoot ratio, an essential trait to respond to water stress in Mediterranean-type ecosystems. In that framework, we have analyzed the effects of three levels of atmospheric CO₂ concentration (350, 500 and 700ppm) on the germination rate, growth and morphology of seedlings of two Mediterranean oaks used in reforestation programs: the evergreen Quercus ilex L. and the deciduous Quercus cerrioides Wilk. et Costa. CO₂ enrichment increased the germination rate of Q. cerrioides (from 70±7 to 81±3%) while it decreased that of Q. ilex (from 71±10 to 41±12%). Seedlings of both species increased approximately 60% their total biomass in response to CO₂ enrichment but at two different CO₂ concentrations: 500ppm for Q. cerrioides and 700ppm for Q. ilex. This increase in seedlings biomass was entirely due to an augmentation of root biomass. Considering germination and biomass partitioning, an enriched CO₂ atmosphere might not be appropriate for growing Mediterranean evergreen oaks, such as Q. ilex, since it reduces acorn germination and the only gains in root biomass occur at a high concentration (700ppm). On the other hand, a moderate CO₂ enrichment (500ppm) appears as a promising nursery technique to stimulate the germination, growth and root/shoot ratio of deciduous oaks, such as Q. cerrioides.     

Effects of soil solarization on nematodes in Croatia

For the first time soil solarization was investigated in Croatia both in the field and in the greenhouse in 1991, 1992, 1993 and 1994. For two months (July and August), the soil was mulched with transparent polyethylene (PE) sheets of 0.015 or 0.050mm thickness. Soil temperatures at depths of 5, 10 and 20cm were recorded daily. In order to assess nematode population densities, soil samples were analysed before mulching and at the end of the mulching treatment. The results of these experiments showed that soil solarization drastically reduced the population of plant-parasitic nematodes (Meloidogyne, Pratylenchus, Paratylenchus, Tylenchus, Tylenchorhynchus spp.) by about 97–100% at a depth of 10cm and 92–97% at a depth of 20cm in the field, while in the greenhouse, the population of plant-parasitic nematodes was reduced by about 89–100% at a depth of 10cm and 98–100% at a depth of 20cm.In the same experiments, the population of saprophytic nematodes in the field was reduced by about 86–90% at a depth of 10cm and 72–89% at a depth of 20cm. In the greenhouse, the population of saprophytic nematodes was reduced by about 87–97% at a depth of 10cm and 87–93% at a depth of 20cm. This data shows that soil solarization was less effective in the control of saprophytic nematodes, which is considered to be an advantage.     

Delignification of cell walls of <Emphasis Type="Italic">Chamaecyparis obtusa</Emphasis> during alkaline nitrobenzene oxidation

To clarify the behavior of whole lignins in wood cell walls during alkaline nitrobenzene oxidation, the delignification process from cell walls in normal and compression woods of Chamaecyparis obtusa Endl. (Cupressaceae) was observed using ultraviolet and transmission electron microscopies. The lignin content conspicuously decreased to around 10% after 35min in normal wood. The lignin content in compression wood finally leveled off at aroumd 10% after 50min. In gel filtration of oxidation products in ethyl acetate, a high molecular weight fraction was prominent in extracts from the early stage of the reaction. As the oxidation progressed, the high molecular weight fraction became less prominent in both normal and compression wood. Changes in the weights of cell wall residues during reaction indicated that approximately half of the components other than lignin were also removed from the cell walls. This shows that the majority of lignin with relatively high molecular weight is removed from the cell walls together with polysaccharides in the early stage of the reaction and that further oxidative degradation occurs in solution in later stages. Only a small amount of the lignin with low molecular weight could be analyzed by gas chromatography.Parts of this report were presented at the 47th (Kochi, April 1997) and 48th (Shizuoka, April 1998) Annual Meetings of the Japan Wood Research Society, and at the Lignin Symposium, Sapporo, October 1997     

Influences of host age,sex ratio,population density,and photoperiod on parasitism by <Emphasis Type="Italic">Trichogramma evanescens</Emphasis> Westw. (Hym., Trichogrammatidae)

Moth species Ephestia kuehniella and Sitotroga cerealella are serious pests in cereal-based food processing facilities and stores in Turkey. Control of these pests is undertaken by regular space treatment of infested areas with pesticides. An alternative control method could be the release of parasitic wasps of the genus Trichogramma. In laboratory tests, we use T. evanescens as a parasitic wasp reared on the eggs of Ephestia kuehniella. Adult wasps emerging from the host were maintained in glass tubes at 27±1° C, 60–70±5% r.h and L14:D10 and fed on honey solution. Adults of T. evanescens in vials without food enclosed from host eggs and all died within 1.8days; in comparison, in vials with honey, live adults were evident for 15.2days. Fresh (6–48h) and old (72–96h) host eggs were offered to T. evanescens and fresh eggs were more accepted than old. Host acceptance of females with males in vials was better than without males. The number of females in the vials also influenced the parasitization rate and single female parasitized more eggs. Adults living in light regime (L14:D10 and L6:D18) parasitized more eggs than in total darkness. Results are discussed with relation to enhancing parasitoid effectiveness in biological control in processing facilities and mills.     

The applicability of a color acetate film for estimating photosynthetic photon flux density in a forest understory

The suitability of a color acetate film for estimating photosynthetic photon flux density (PPFD) in a forest understory was examined. The fading ratio of the film (F), the total PPFD (PPFD_total) to which the film was exposed, and the average daily maximum temperature during exposure (T) were obtained from measurements at multiple sampling points throughout an entire year within a natural secondary forest (n = 42). The ranges of the recorded values were as follows: F 35%–99%, PPFD_total 1.4–28.3molm^–2, and T 6°–32°C. PPFD_total was regressed by F and T with a high r ² (=0.94; P < 0.0001): PPFD_total = (100 – F)/(1.085 + 0.051T). The absolute error (|estimated PPFD_total – measured PPFD_total|) averaged 1.3molm^–2 with a maximum of 5.7molm^–2, indicating a good fit. These results indicated broad applicability of the film, both spatially and temporally, for estimating forest understory PPFD.