Preparation of polyols from methyl-α-d-glucoside and cyclic esters for design and fabrication of biodegradable polyurethane foams

A ring-opening polymerization of cyclic esters -caprolactone (CL) and/or l-lactide (LACD) was carried out in the presence of methyl--d-glucoside (m-Glc) as an activated substrate and tin(II) 2-ethylhexanoate (SnEht₂) as a catalyst. This led to successful synthesis of an armed polyester polyol with m-Glc as the core. These polyols were characterized through gel permeation chromatography, hydroxyl value assessment, differential scanning calorimetry, and viscosity measurements. It was clarified that the thermal properties and tractability of the synthesized polyols are closely related to the structural characteristics of the side chain polyesters, such as their length and chemical composition. Polyurethane foams were also prepared by mixing an appropriate amount of the polyols with diphenyl methane diisocyanate, a foaming agent (water), and other additives, and their mechanical properties were examined. Two polyurethane foams manufactured from polycaprolactone-polyols that were synthesized at a CL/m-Glc ratio of 2 or 5, were used in a biodegradation test in a closed system of activated sludge suspension. Evidence of their biodegradation is presented based on data showing oxygen consumption by the pulverized samples.     

Factors influencing the variability of Mg, Ca and K in waters of a mangrove creek in Bragança, North Brazil

Sodium, potassium, magnesium, calcium and physicochemical parameters were monitored for one year in a mangrove tidal creek near Bragança, North Brazil, to determine their tidally induced and seasonal variations and the main parameters controlling the concentration of these cations. On a daily basis, cation concentrations showed a strong tidal rhythm due to the mixing of estuarine and mangrove waters. Mean concentrations were highest at the end of the dry season (December 1996) and lowest (April 1997) towards the end of the rainy season. Average values over one year were: Na+ = 329± 118mM, K+ = 6.9±2.5mM, Mg++=37 ±14 mM and Ca++= 6.9±2.4mM. Dissolved oxygen concentration was higher during the dry season due to enhanced aquatic primary production, with a maximum daily average value of 8.5mg/L in July 1996, and a minimum value of 4mg/L in June 1997. Cation concentrations were transformed relating them to the respective average values in standard seawater at salinity 35. Although cation concentrations and salinity tightly correlated, this standardization showed that the concentrations of K+, Ca++ and Mg++ did not depend solely on salinity and reflected the seasonal variation in aquatic primary production. It also allowed the discrimination of their sources (marine, riverine and groundwater). Thermodynamic equilibrium calculations indicate that phytoplankton may be regulating the concentration of these cations in the water column indirectly by inducing precipitation through pH increase and directly through metabolic uptake.     

Vibrational properties of wood plastic plywood

Wood plastic plywood (WPPW), composed of veneer and styrofoam, was manufactured without special adhesives such as urea–formaldehyde or phenol–formaldehyde resins, and its vibrational properties were investigated. WPPW can be produced at 1MPa and 160°C for 9min (three-ply) and 12min (five-ply). The dynamic Youngs modulus reached its highest value when the styrofoam thickness was 30mm. The sound velocity and dynamic Youngs modulus had minimum values at a grain angle of 45°. The results for dynamic Youngs moduli measured by a longitudinal vibration method and an in-plane flexural vibration method were almost the same. Dynamic shear moduli were measured by an in-plane surface wave propagation test and an in-plane flexural vibration method. From the experimental results, the dynamic shear moduli at 0° and 90° by the two methods were relatively close, although the surface wave propagation test results were higher than those from the flexural vibration method. Dynamic shear moduli at a grain angle of 45° measured by the in-plane surface wave propagation test and calculated from theory were relatively close. The surface wave propagation test results were smaller than the results calculated from theory. The shear stress distribution factors were about 1.000–1.189 for WPPW.     

Studies on the synthesis and properties of terpene-phenol-aldehyde resin with a high softening point

Synthesis conditions of terpene-phenol-aldehyde resin with a high softening point were studied based on the reactions among-pinene, phenol, and formaldehyde. A suitable catalyst system and the best processing conditions were obtained by laboratory experiments. The influence of the raw materials ratios, reaction temperature, reaction time, and catalyst dose on the softening point, yield, and color of the synthesized resin was examined. The physical and chemical characteristics of the resin were determined: softening point 140°C (ball and ring method); color value 7 (Gardner); acid value (KOH mg/g) <1; bromine value (Br₂ mg/100g) <64; saponification value (KOH mg/g) <1; average molecular weight 830. The yield of resin was more than 85% (based on the total raw material).     

5α-Reductase inhibitory component from leaves ofArtocarpus altilis

The inhibitory effects of 17 samples prepared from Thailand plants on 5-reductase activity were examined. The acetone extract of leaves ofArtocarpus altilis showed potent 5-reductase inhibitory activity. Fractionation guided by 5-reductase inhibition led to the isolation of 2-geranyl-2,3,4,4-tetrahydroxydihydrochalcone from the acetone extract of leaves ofA. altilis. This compound showed more potent inhibitory effect (IC₅₀=38M) than-linolenic acid known as a naturally occurring potent inhibitor.     

Specific degradation ofβ-aryl ether linkage in synthetic lignin (dehydrogenative polymerizate) by bacterial enzymes ofSphingomonas paucimobilis SYK-6 produced in recombinantEscherichia coli

Sphingomonas paucimobilis SYK-6 produces unique and specific enzymes, such as-etherases,O-demethylases, and ring fission dioxygenases, for lignin degradation. Cleavage of arylglycerol--aryl ether linkage is the most important process in the lignin metabolic pathway ofS. paucimobilis SYK-6. We reported the genes (ligD, ligE, ligF) for enzymes that cleaved-aryl ether linkage of dimeric compounds in previous studies. In this study we synthesized the fluorescent high-molecular-weight lignin (UBE-DHP) by dehydrogenative polymerization. We investigated the-aryl ether cleavage ability of these enzymes produced in recombinantEscherichia coli. When UBE-DHP was incubated with LigF, 4-methylumbeliferone was released as a result of-aryl ether cleavage of O-methylumbelliferyl--hydroxypropiovanillone (compound III) incorporated in UBE-DHP. Here, we report that-etherase ofS. paucimobilis SYK-6 can be expressed inE. coli and is able to cleave the-aryl ether linkage in synthetic high-molecular-weight lignin.     

Biological activity of extracts fromCupressus lusitanica cell culture

Ethyl acetate extracts ofCupressus lusitanica suspension cell cultures were examined for their biological activities (viz., tyrosinase inhibitory, antioxidant, and antimicrobial activities). The extract from elicitor-treated cells showed all of the biological activities, whereas the extract from cultures without elicitor was not bioactive to a discernible extent. The biological activities shown by the cell culture extracts were almost solely accounted for by-thuj aplicin contained in the extracts. These results suggest that the ethyl acetate extract ofC. lusitanica cells treated with the elicitor is a valuable bioactive source without isolation or purification of-thujaplicin.     

Semi-quantitative method to evaluate the α-carbonyl content in lignin

A method to estimate the content of -carbonyl structures in lignin was developed. This method consists of two successive treatments: NaBD₄ treatment of pulp to reduce an -carbonyl structure in lignin, and nitrobenzene oxidation. NaBD₄ was used to convert an -carbonyl structure to a deuterium-labeled hydroxymethine structure. The ratio of D-vanillin [(HO)(H₃CO)C₆H₃CDO] to H-vanillin [(HO)(H₃CO)C₆H₃CHO] or that of their syringyl analogues obtained by nitrobenzene oxidation was used as the measure of the content of -carbonyl structure. Model experiments demonstrated that when sodium hydroxide was used as alkali for the nitrobenzene oxidation, the retention of deuterium at the side chain -position was very low due to the displacement of deuterium with hydrogen by an unknown reaction mechanism. In order to depress this unexpected displacement, the reaction conditions of the nitrobenzene oxidation were modified. The modified nitrobenzene oxidation employs 0.5mol/l of lithium hydroxide as a reaction medium instead of 2.0mol/l sodium hydroxide. By this modification, this method could successfully trace the formation and the degradation of the -carbonyl structure in milled wood lignins.This paper was presented in part at the 11th International Symposium on Wood and Pulping Chemistry, Nice, France, June 2001 and at the 46th Lignin Symposium, Kyoto, Japan, November 2001     

Lignans ofLinum flavum var.compactum

A new dibenzylbutyrolactone lignan 7.6-dihydroxybursehernin, together with six known lignans (pinoresinol, lariciresinol, secoisolariciresinol,-peltatin,-peltatin, 5-methoxypodophyllotoxin) were isolated from the methanol extracts ofLinum flavum var.compactum. The enantiomeric analysis of pinoresinol and lariciresinol isolated from the species, which are upstream lignans in the lignan biosynthetic pathway, indicated that they are not optically pure, which is in accordance with our recent findings on lignans occurring in other plant species.Parts of this report were presented at the 42nd Lignin Symposium, Sapporo, October 1997; and the 43rd Lignin Symposium, Fuchu, October 1998     

Antioxidative activity of tree phenolic constituents 1: Radical-capturing reaction of flavon-3-ols with radical initiator

The present work was undertaken from the standpoint of radical-capturing ability with regard to the antioxidative ability of flavonoids, especially flavonols distributed widely in woody plants. In regard to the flavonols, six methyl derivatives were initially prepared from quercetin and its litinoside. Their radical-capturing constants were determined strictly by the stopped-flow spectroscopic method. It was proved that the radical-capturing ability of quercetin mainly involves the vicinal C₃. and C₄, hydroxyl groups and the C₃ hydroxyl group. To clarify the reaction mechanism begun at the C₃ hydroxyl group of quercetin, 5,7,3,4-tetramethylquercetin (TMQ), flavon-3-ol (F30) and so on were treated with 2,2-azo-bis-(2,4-dimethylvaleronitrile) (AMVN). Six products (1–6) containing one depside and its two hydrolytic products, two valeronitrile adducts, and others were isolated from the reaction mixture of TMQ and their structures determined by instrumental analyses. Similarly, F30 gave four products, 7–10, which corresponded to the above products 1–3 and 5 (one depside, its two hydrolytic products, and one adduct), respectively. 3,5,7,3,4-Pentamethylquercetin (PMQ) and flavon-3-O-methylate (F3M) gave no products. The quantitative change of the products with reaction time was determined spectroscopically. An initial reaction pathway for the radical-capturing reaction of flavon-3-ols with AMVN was proposed based on the products and their amounts. The main route — formation of depside and its hydrolytic products via ketohydroperoxide (3) or ketohydroperoxy radical (4) - was similar to that of the oxidation reaction of quercetin with quercetinase and light.Part of this paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society, Kumamoto and Kouchi, April 1996 and 1997     

Five years of Paulownia field trials in North Carolina

Performance of Paulownia elongata, Paulownia fortunei, and Paulownia×Henan 1 was monitored at three sites in North Carolina between 1996 and 2000, and P. elongata clones were tested at an additional two sites. The primary objective was to define the potential for growing Paulownia in the state. Species and clones within species differed in survival and height and diameter growth whenever genotype was included as a treatment. P. elongata was superior at two and P. fortunei was superior at one of the three sites that included P. elongata, P. fortunei, and P.×Henan 1. Trees produced through vegetative means were more likely to survive and were taller and of greater DBH than seed produced trees. Mortality in trees produced from seed was greater for P. fortunei and P. ×Henan 1 than for P. elongata. Application of animal waste or different rates of nitrogen as inorganic fertilizer did not have a pronounced effect on tree survival and growth.     

Role of caffeic glucoside esters in defense-repair processing of trees II: Synthesis of 2-(3,4-dihydroxyphenyl)-ethyl 3-α-L-rhamnopyranosylβ-D-glucopyranoside

The reference compound (9), with a partial structure of acteoside, was synthesized to elucidate the relation between structural features and the precipitation or solubility of the oxidation products of acteoside: 2-(3,4-dihydroxyphenyl)-ethyl 3-O-(-L-rhamnopyranosyl)--D-glucopyranoside (9). The glycosyl acceptor 2-O-benzoyl-3-O-(2,3,4-tri-O-acetyl--L-rhamnopyranosyl)-4,6-O-benzylidene--D-glucopyranosyl trichloroacetimidate (7) was prepared from allyl 2-O-benzoyl-3-O-(2,3,4-tri-O-acetyl--L-rhamnopyranosyl)-4,6-O-benzylidene--D-glucopyranoside (4) via isomerization of the allyl group with an iridium complex to the 1-propenyl group and its hydrolysis with HgCl₂lHgO, followed by treatment with CCl₃CN and DBU in a 65.5% overall yield. The glycosyl acceptor 3,4-diacetoxyphenethyl alcohol (16) was prepared from homoveratric acid via demethylation with 57% HI and its acetylation with Ac₂O and 85% H₃PO₄, followed by selective reduction of the carboxyl group to the alcohol with a borane-tetrahydrofurane complex in a 61% overall yield. The glycosylation of7 with16 in dichloromethane promoted by BF₃-Et₂O gave a 74.3% yield of8. Hydrolysis of8 with 90% CF₃COOH gave the debenzylidenated product, which was treated with NaOMe to afford a 32% overall yield of the desired compound9. This compound9 was identical with the natural specimen.This study was presented in part at the 46th annual meeting of the Japan Wood Research Society, Kumamoto, April 3–5, 1996     

Gas chromatographic and mass spectrometric (GC-MS) analysis of lignin-derived products from <Emphasis Type="Italic">Cryptomeria japonica</Emphasis> treated in supercritical water

Sugi (Cryptomeria japonica D. Don) wood was treated with supercritical water (374°C, 22.1MPa), and fractionated into the water-soluble portion, the methanol-soluble portion, and the methanol-insoluble residue. The methanol-soluble portion mainly consisted of the lignin-derived products. To characterize the compounds in the methanol-soluble portion, gel permeation chromatographic (GPC) and gas chromatographic-mass spectrometric (GC-MS) analyses were performed. The GPC analysis indicated that the methanol-soluble portion contained lignin-derived monomeric and dimeric products. GC-MS analysis detected 31 products which were expected to be monomeric compounds, and 18 of these were identified to be guaiacol, methylguaiacol, ethylguaiacol, vinylguaiacol, eugenol, propylguaiacol, vanillin, cis-isoeugenol, homovanillin, trans-isoeugenol, acetoguaiacone, propioguaiacone, guaiacylacetone, 2-methoxy-4-(1-hydroxypropyl)phenol, homovanillic acid, 2-methoxy-4-(prop-1-en-3-one)phenol, coniferyl aldehyde, and ferulic acid. In addition, 22 dimeric products were detected, and 4 of these were believed to be compounds with biphenyl type (5-5), diphenylethane type (-1), stilbene type (-1), and phenylcoumaran type (-5) structures. These results clearly indicated that the methanol-soluble portion included various monomeric and dimeric compounds produced as a result of the cleavage of ether linkages and propyl chains of lignin.     

Erythro/threo ratio ofβ-O-4 structures as an important structural characteristic of lignin. I: Improvement of ozonation method for the quantitative analysis of lignin side-chain structure

Ozonation as a quantitative tool to analyze the stereo structures of arylglycerol--aryl ether linkages was examined using wood meal, milled wood lignin, and a lignin model compound, 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol (veratrylglycerol--guaiacyl ether, VG). The procedure was improved. When mild postreduction was conducted for ozonation products, the total yield of erythronic and threonic acids from this model compound was 74%, which is 15% higher than the yield without postreduction. A decrease in the recovery of these two acids under prolonged ozonation treatment was successfully suppressed by postreduction. Theerythro/threo ratio of VG determined by the ozonation method with postreduction is in good agreement with the ratio determined by¹H-nuclear magnetic resonance. Excellent reproducibility of the yield was obtained by adopting a procedure that included trimethylsilylation of ammonium salts of ozonation products using a dimethylsulfoxide-hexamethyldisilazane-trimethylchlorosilane mixture and subjecting it to gas chromatography analysis. It was concluded that arylglycerol--aryl ether structures comprise at least 35% of the C₃-C₆ structure in birch wood meal, with anerythro/threo ratio of 2.8.This paper was presented at the 43rd Lignin Symposium, Fuchu, Japan, October 1998; and at the 10th ISWPC, Yokohama, Japan, June 1999     

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).     

Length of cuttings in juvenile development of a hybrid poplar clone

The influence of length of cuttings on establishment of a short rotation plantation was investigated over a period of two years using direct field planting of unrooted Populus Rasumowskiana cuttings. The longer the cuttings, the higher were the survival and dry mass production. Survival at the end of the second growing season varied from 75% to 97%. In two years, the two longest cutting lengths (40 cm and 50 cm) produced about 100 g dry mass per living cutting; but owing to the higher survival rate of the longest cuttings, there was a difference per area unit: 360 g/m² for 40 cm and 400 g/m² for 50 cm-long cuttings. The shortest (10 cm) cuttings produced only 115 g/m².     

5<Emphasis Type="Italic">Α</Emphasis>-Reductase inhibitory tannin-related compounds isolated from <Emphasis Type="Italic">Shorea laeviforia</Emphasis>

Five tannin-related compounds – gallic acid, flavogallonic acid dilactone, valoneic acid dilactone, gallagyldilactone, ellagic acid – were isolated from the heartwood of Shorea laeviforia, and the inhibitory activity of each against rat liver 5-reductase was evaluated. Valoneic acid dilactone and gallagyldilactone exhibited positive inhibitory activity, but gallic acid and ellagic acid did not. Flavogallonic acid dilactone stimulated 5-reductase activity, even though this compound is structurally similar to valoneic acid dilactone. The kinetic study of valoneic acid dilactone and gallagyldilactone indicated that the inhibitory behavior of 5-reductase were not competitive against the substrate (testosterone) and were partially competitive against the cofactor (NADPH). Additionally, double inhibition analysis of valoneic acid dilactone and NADP⁺ showed synergetic inhibition. These results suggested that neither valoneic acid dilactone nor gallagyldilactone can affect the binding of testosterone but that either compound could interact with an enzyme–NADP⁺ complex to inhibit 5-reductase.     

Absolute configuration of arylglycerol-β-aryl ethers obtained by asymmetric reduction of the correspondingα-ketonic compound with intactFusarium solani cells

When (±)--oxo-guaiacylglycerol--(vanillic acid) ether (1) is degraded byFusarium solani M-13-1, the-ketone is initially reduced to giveerythro andthreo guaiacylglycerol--(vanillic acid) ethers (2), arylglycerol--aryl ethers, both of which are enantiomerically pure. The absolute configuration in each2 was determined by Mosher's method; the products were converted to,-di-(R)--methoxy--trifluoromethylphenylacetates (MTPA esters) (3) oferythro (-)- andthreo (+)-veratrylglycerol--(methyl vanillate) ethers (3), whose¹H nuclear magnetic resonance (NMR) spectra were examined and compared with those of four di-(R)-MTPA ester (3) diastereomers from chemically synthesizederythro (±)-3 andthreo (±)-3. To assign the- and-MTPA-OCH₃ peaks, the¹H NMR scans of several compounds that have substructures of 3 and their 3,4,5-trimethoxyphenyl analogues were examined. When a racemic alcohol reacts with (R)-MTPA to give a pair of (R)-MTPA ester diastereomers, the value was defined as the absolute value of the difference in the¹H chemical shifts of the peak between the diastereomers. It was found that the values of-MTPA-OCH₃ were larger than those of-MTPA-OCH₃ owing to a shielding effect of the veratryl ring located on the-MTPA-OCH₃, and that the-MTPA-OCH₃ peaks in the 3,4,5-trimethoxyphenyl compounds shifted downfield relative to those in the veratryl compounds. On the basis of the¹h NMR data of (R)-MTPA esters, the absolute configuration of the four chemically prepared diastereomers (3) were determined. The catabolicerythro 3 [fromerythro (-)-3] andthreo 3 [fromthreo (+)-3] were identical to (R, S, R)-erythro 3 and (R, S, S)- threo 3, respectively. An hydrogen species in the fungal reduction would attack the-ketone fromre-face of both (R)-1 and (S)-1, givingerythro (S, R)-2 andthreo (S, S)-2, respectively.Part of this paper was presented at the 33rd Lignin Symposium, Tsukuba, November 1988     

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.     

Dynamic properties of three types of wood-based composites

This study used a vibration test method to show that grain angles of face veneer have substantial effects on sound velocities and dynamic Youngs moduli of three types of wood-based composites. The sound velocity at 0° grain angle of face veneer was the highest, and it decreased with increasing grain angle in the range of 0° to 90°. This tendency was similar to that for dynamic Youngs modulus. The relationship between the grain angle of face veneer and the sound velocity of three types of wood-based composites can be expressed in the form of Hankinsons equation or a second-order parabolic equation. This study also showed that the application of orthotropic elasticity theory was valid for the three types of wood-based composites. The relationship between the grain angle of the face veneer and the Youngs modulus of three types of wood-based composites can be expressed in the form of the Jenkin equation, Hankinsons equation, or a second-order parabolic equation. Rule of mixture can also be used to predict the Youngs modulus of wood-based composite from the Youngs moduli of the two elements.Part of this study was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, Japan, March 2003 and the 15th Annual Meeting of Chugoku Shikoku Branch of the Japan Wood Research Society, Higashi-Hiroshima, Japan, September 2003