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Thermal characterization of kraft lignin (KL) prepared from mixed hardwoods was conducted to determine their thermal and thermo-oxidative stability, glass transition temperature (Tg), pyrolysis products composition, and syringyl/guaiacyl ratio. Two milled wood lignins (MWLs) from acacia (MWL-aca) and mixed hardwoods (MWL-mhw), the same hardwood species employed in the production of KL, were also characterized for comparison with KL. Thermogravimetric analysis (TGA) indicated that KL had higher thermal and thermo-oxidative stability than MWLs. Based on differential scanning calorimetry (DSC), the Tg of KL was 63.2 °C, while MWLs gave similar values near 165 °C. The syringyl (S), guaiacyl (G), p-hydroxyphenyl (H) composition of KL acquired from pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) at 675 °C was 48:44:8 (S/G ratio 1.07), while MWL-aca and MWL-mhw were 31:60:9 and 46:48:6, respectively.

This study was conducted to determine the lignin substructures, hydroxyl (phenolic + aliphatic) contents, and carboxyl contents in kraft lignin (KL) prepared from mixed hardwoods by using 2D Heteronuclear Multiple Quantum Coherence Nuclear Magnetic Resonance (HMQC NMR) and 31P NMR techniques. Based on 2D HMQC NMR analysis of KL, stilbene and vanillin substructures were present in the aromatic region, while trace amounts of β-O-4 and β-β moieties were detected in the oxygenated aliphatic region. The total hydroxyl content calculated from 31P NMR was 5.24 mmol/g KL. The aliphatic hydroxyl content was 1.04 mmol/g KL, and phenolic hydroxyl content was 4.20 mmol/g KL. Of the phenolic hydroxyl groups, the contribution of syringyl (S) and guaiacyl (G) was 1.02 and 0.97 mmol/g KL, respectively. The S/G molar ratio of KL calculated from 31P NMR was 1.05. The carboxyl content was 0.44 mmol/g KL.

This preliminary study aimed to realize the potential use of titanium dioxide–carbonized medium-density fiberboard (TiO2–cMDF) as a biomaterial for dye wastewater treatment. TiO2–cMDF, which was prepared by carbonizing MDF treated with titanium tetraisopropoxide in isopropyl alcohol, was investigated for adsorption and then photodegradation of methylene blue (MB) under UV-A (390 nm, 19 W) and UV-C (280 nm, 12 W) light emitting diodes (LEDs). After two full cycles of adsorption, four successive cycles of photodegradation were conducted under UV-A LED. For every adsorption or photodegradation cycle, TiO2–cMDF practically removed MB. Both adsorption and photodegradation followed pseudo-first-order kinetics. The rate constants for adsorption decreased by half. The rate constants for photodegradation were similar. This finding suggests that UV-A LED is a robust and steady source of UV light. Photodegradation under UV-C LED was also performed. However, due to its high-energy output, the UV-C LED module overheated even though a cooling fan was present. Although the results indicate a slow photodegradation under UV LEDs, because of the limited number of specimens, increasing the number of specimens and UV LED modules will improve its performance.

TiO2-carbonized medium-density fiberboard (TiO2-cMDF), prepared by carbonization of MDF treated with 50% (v/v) titanium tetraisopropoxide (Ti-tip) in isopropyl alcohol (IPA) as a precursor, was investigated for adsorption and photodegradation in aqueous methylene blue (MB) solution under UV-C (254 nm) irradiation. After full adsorption of MB, four successive cycles of photodegradation were conducted. After the second cycle, the TiO2-cMDF was rinsed with water, dried, and subjected to photodegradation again. For every photodegradation cycle, the TiO2-cMDF practically removed MB. The photodegradation results of the second (unrinsed) and third (rinsed) cycle were similar, however, the result of the fourth (rinsed) cycle was lower than the third cycle. The rate constant of adsorption was 3.3 × 10–3/h and followed pseudo-first-order kinetics. The rate constant of photodegradation decreased from 11.0 × 10–3/h (first cycle) to 5.9 × 10–3/h (fourth cycle) and likewise followed pseudo-first-order kinetics. A reduction in Ti content on the surface of TiO2-cMDF was observed after photodegradation based on scanning electron microscope-energy dispersive X-ray spectrometer (SEM–EDS) analysis; nonetheless, photodegradation of MB was still accomplished. Although TiO2-cMDF in aqueous system exhibited slow photodegradation, it is due to the limited number of TiO2-cMDF slabs. The number of slabs must be increased to improve the photocatalytic performance.

The use of polyphenol extracts from radiata pine (Pinus radiata) bark as raw materials for bio-foams was investigated along with the optimal NaOH extraction conditions. The targeted yield of alkaline extracts was 60%, and the targeted pH was 11 to 12. The radiata pine bark was composed of 70% of a 1% NaOH extract, which contained mainly polyphenols, such as proanthocyanidin (PA). As the particle size of the bark decreased, the yield of the 1% NaOH extracts increased from 57 to 87%. A range of NaOH concentrations, liquor ratios, and extraction times were explored to establish an economic polyphenol extraction method. More than 60% of the alkaline extract was extracted, and the pH of the extract was approximately 12 when the optimum extraction conditions were employed, i.e., a liquor to bark ratio of 5:1, a NaOH dosage of 17 to 18% based on the bark weight, and a 1 h extraction time. Following neutralization of the alkaline extract, structural analysis indicated severe structural changes in the PA during the alkaline extraction. Because the alkaline extract was barely soluble in the solvent used for the structural analyses, it is assumed that chemical modification is required to increase the solubility of the alkaline extract for the production of bio-foams.

A visible-light-responsive TiO2 with carbonized medium-density fiberboard (c-MDF) was prepared by a one-step preparation method, and its application as an interior building material for decomposition of harmful aromatic volatile organic compounds was evaluated by investigating its toluene decomposition performance. Titanium tetraisopropoxide, cobalt nitrate, and iron nitrate were used as precursor materials for synthesizing metal-doped TiO2, which was then treated on MDF followed by carbonization. After carbonization at 800 °C for 2 h, the crystal structure of metal-doped TiO2 was similar to that of rutile TiO2. Further, a toluene decomposition test was conducted using a modified 20-L chamber system with a commercial fluorescent lamp as the light source. The results revealed that 0.1 mol% metal-doped TiO2/c-MDF completely decomposed toluene in 15 h under visible-light irradiation.

A solution-type TiO2-based photocatalyst for the decomposition of volatile organic compounds was synthesized using a modified sol-gel method under either alcohol (ethanol or isopropanol) or aqueous conditions. Anatase-type TiO2 was successfully synthesized with additional hydrothermal treatment using either type of medium. However, the aqueous condition for TiO2 synthesis was more convenient for the formation of anatase-type TiO2. Based on X-ray diffraction analysis data, the optimal hydrothermal treatment temperature was 80 °C for anatase-type TiO2 formation; at temperatures below 80 °C or above 90 °C, mostly rutile-type TiO2 was formed. The synthesized anatase-type TiO2 solution was applied to the surface of carbonized medium-density fiberboard (c-MDF). The anatase-type TiO2 on c-MDF showed good maintenance of toluene decomposition performance even after repeated use for 14 weeks.

Photocatalytic carbonized medium density fiberboard (MDF) was prepared by one-step carbonization with titanium tetraisopropoxide (Ti-tip) as a TiO2 precursor. Anatase TiO2 was formed at carbonizing temperatures of 600 to 800 °C. However, at > 900 °C, most crystalline TiO2 was rutile. Ti-tip-treated carbonized MDF (c-MDF) showed outstanding formaldehyde reduction performance with complete removal of formaldehyde from the chamber in 1 to 3 days. However, with non Ti-tip-treated c-MDF, formaldehyde remained after 20 days. No toluene was detected after 3 h on 50% Ti-tip-treated c-MDF, while toluene was continuously detected with other samples (10% and 5% Ti-tip-treated c-MDF, and untreated c-MDF). After 9 h ultraviolet exposure, toluene was completely reduced on 10% and 50% Ti-tip-treated c-MDF; reduction was only 20% on untreated c-MDF. In addition, c-MDF/TiO2 prepared at 800 and 900 °C had significantly higher photocatalytic performances compared to those obtained at lower carbonization temperatures. Based on the results, the combination of 10% Ti-tip treatment and carbonizing at 800 °C provided the optimum photodegradation capacity for formaldehyde and toluene.

Rennet-free Gouda (RFG) cheese was prepared to investigate the influence of rennet on the non-volatile and volatile profiles of cheese and was characterized by HPLC and GC/MS analyses. Chymosin, a major protease in rennet, was immobilized onto oxidized and chemically modified carbon cloth. The chymosin immobilization efficiency was 60.4%, and the milk-clotting activity used as an index of the stability of the immobilized chymosin decreased by around 20% in 2 weeks. However, the activity was maintained at 70–80% from 2 weeks to 32 weeks and was more stable than that of chymosin solution alone. Non-volatile (organic acids) and volatile profiles of the RFG cheese and rennet-containing normal Gouda cheese were not significantly different during ripening with a few exceptions. Therefore, it can be concluded that cheese flavor is developed by lactic acid fermentation, irrespective of the presence of rennet.

In the present study, we investigated the anticancer activity of Pinus radiata bark extract (PRE) against MCF-7 human breast cancer cells. First, we observed that PRE induces potent cytotoxic effects in MCF-7 cells. The cell death had features of cytoplasmic vacuolation, plasma membrane permeabilization, chromatin condensation, phosphatidylserine externalization, absence of executioner caspase activation, insensitivity to z-VAD-fmk (caspase inhibitor), increased accumulation of autophagic markers, and lysosomal membrane permeabilization (LMP). Both the inhibition of early stage autophagy flux and lysosomal cathepsins did not improve cell viability. The antioxidant, n-acetylcysteine, and the iron chelator, deferoxamine, failed to restore the lysosomal integrity indicating that PRE-induced LMP is independent of oxidative stress. This was corroborated with the absence of enhanced ROS production in PRE-treated cells. Chelation of both intracellular calcium and zinc promotes PRE-induced LMP. Geranylgeranylacetone, an inducer of Hsp70 expression, also had no significant protective effect on PRE-induced LMP. Moreover, we found that PRE induces endoplasmic reticulum (ER) stress and mitochondrial membrane depolarization in MCF-7 cells. The ER stress inhibitor, 4-PBA, did not restore the mitochondrial membrane integrity, whereas cathepsin inhibitors demonstrated significant protective effects. Collectively, our results suggest that PRE induces an autophagic block, LMP, ER stress, and mitochondrial dysfunction in MCF-7 cells. However, further studies are clearly warranted to explore the exact mechanism behind the anticancer activity of PRE in MCF-7 human breast cancer cells.

The change in chemical compositions of leachate and medium density fiberboard (MDF) from a labo-ratory-scale simulated landfill which constructed in a plastic container containing alternating layers of soil and MDF was investigated to evaluate decomposing of MDF in soil. Four treatments were conducted: 1) MDFin soil, 2) MDF only, 3) cured UF resin in soil, and 4) soil only. Molecular weight (MW) distribution ofcompounds in leachate from soil only treatment did not change over time. In UF resin in soil treatment, the MW distribution shifted to a lower MW distribution over time, while the peak shifted to the left indicated changing to higher MW distribution in leachate from treatment 1 and 2 contained MDF. Higher percentnitrogen in leachate was observed in MDF containing treatments due to the UF resin in the MDF. The percentcarbon slightly increased in MDF only while that greatly decreased in MDF in soil treatment maybe due to bacterial activity. The percent of extractable materials from the MDF decreased greatly on day 35 compare to day 0, and subsequently did not change much on day 77. In contrast, percent holocellulose and lignin did not change much over time. No structural change of the wood fiber in MDF occurs during the study. Water-solublematerials from MDF in soil contributed the change in chemical composition of leachate.Keywords : simulated landfill, leachate, medium density fiberboard, urea-formaldehyde resin, chemical analysis, elemental analysis

This study investigated environmental assessments of leachate containing formaldehyde from medium density fiberboard (MDF) disposed in laboratory-scale simulated landfills. Environmental impact assessment of leachate was conducted by measuring formaldehyde, toxicity, biochemical oxygen demand (BOD), chemical oxygen demand (COD), bacterial enumeration, and pH. Amount of formaldehyde in leachate from MDF in soil decreased to the level of soil only treatment by 28 days, and toxicity decreased as the amount of formaldehyde decreased. BOD and COD levels in leachate from the treatments containing MDF exceeded permissible discharge levels of BOD or COD throughout the experimental period. The pH levels of all treatment were within permissible discharge range except on day 0. Fewer bacteria were observed in leachate from MDF in soil treatment than other treatments (MDF only, cured UF resin in soil, and soil only). Consequently, the leachate from disposal of MDF in soil detrimentally affect on environment. However, soil buffered formaldehyde leaching and pH on leachate in this study. Waste MDF may be required the pre-water soaking treatment for leaching formaldehyde to reclaim on land.

The mountain pine beetle-killed lodgepole pine ( Pinus contorta ) wood treated with iron (III) nitrate solution was used for the preparation of Fe-cored carbon nanomaterials (Fe-CNs) under various carbonization temperatures. The carbonization yield of Fe-treated sample (5% as Fe) was always 1–3% higher (after ash compensation) than that of the non-treated samples heated at the same condition. The lowest carbonization temperature required to produce Fe-CNs was 700 °C. The carbon shell was composed of 30–40 well-aligned layers of graphitic carbon nanostructure. The iron captured by graphitic layers was assumed to be iron carbides and/or α-Fe and γ-Fe. This study indicates that at least 700 °C of carbonization temperature is needed for the production of Fe-CNs and the mountain pine beetle-killed pine wood can be a carbon source for the production of Fe-CNs.

This study was carried out to investigate the feasibility and usefulness of a commercial synthetic adsorbent, Diaion HP 20, for the isolation of proanthocyanidins (PAs) from hot water extract (HWE) prepared from Pinus radiata bark. Most ultraviolet (UV) absorbing materials in HWE were adsorbed onto Diaion HP 20 and easily recovered by simple ethanol (EtOH) washing. More than 50% of the UV absorbing materials were adsorbed within 20 minutes, and the adsorption equilibrium was reached within 3 h. The recovered materials from Diaion HP 20 were mostly composed of PAs, but some monomeric flavonoids such as taxifolin and unidentified hydrophobic materials were also adsorbed. The impurities such as carbohydrates and inorganic materials contained in HWE were mostly removed by Diaion HP 20. The adsorption ability of the UV absorbing materials onto Diaion HP 20 was almost the same as the first cycle even after 14 times of repeating cycles of adsorption and desorption. The radical scavenging ability of the recovered materials from the ad-sorbentwas slightly higher than that of thepure PAs prepared by Sephadex LH 20 from the same HWE.

Sodium lignosulfonate (LS) from sulfite pulping processing was used as a carbon source to synthesize graphene. LS was mixed with Fe nanoparticles (FeNPs) as a catalyst and thermally treated at 1000 °C for 1 h. The Raman spectrum and X-ray diffraction pattern suggested that graphene sheets were formed in LS thermally treated with FeNPs (Fe-HTLS). Scanning electron microscopy image of Fe-HTLS showed clusters of thin graphene sheets appearing in the form of nanoflowers. High-resolution transmission electron microscopy and electron reflection images provided further evidence of the formation of graphene in LS thermally treated in the presence of Fe catalyst.

Mast cells play a critical role in the effector phase of immediate hypersensitivity and allergic reactions. Pinus radiata bark extract exerts multiple biological effects and exhibits immunomodulatory and antioxidant properties. However, its role in mast cell-mediated anaphylactic reactions has not been thoroughly investigated. In this study, we examined the effects of proanthocyanidin-rich water extract (PAWE) isolated from P. radiata bark on compound 48/80-induced or antidinitrophenyl (DNP) immunoglobulin E (IgE)-mediated anaphylaxis-like reactions in vivo. In addition, we evaluated the mechanism underlying the inhibitory effect of PAWE on mast cell activation, with a specific focus on histamine release, using rat peritoneal mast cells. PAWE attenuated compound 48/80-induced or anti-DNP IgE-mediated passive cutaneous anaphylaxis-like reactions in mice, and it inhibited histamine release triggered by compound 48/80, ionophore A23187, or anti-DNP IgE in rat peritoneal mast cells in vitro. Moreover, PAWE suppressed compound 48/80-elicited calcium uptake in a concentration-dependent manner and promoted a transient increase in intracellular cyclic adenosine-3',5'-monophosphate levels. Together, these results suggest that proanthocyanidin-rich P. radiata bark extract effectively inhibits anaphylaxis-like reactions.

Southern yellow pine (Pinus taeda) wood char powder was thermally treated at 1,000°C in the presence of a 25-nm-size Fe nanoparticle catalyst. The thermally treated carbon materials were analyzed by Raman spectroscopy and high-resolution transmission electron microscopy. Well-aligned graphitic carbon structures with 15 to 17 layers on average were observed. These graphitic carbon structures were similar to those of graphite with an average interplanar distance of 0.34 nm. The Raman spectra results showed that the full-width half-maximum values of Raman G and D bands, and the peak intensity ratio, ID″/IG, of thermally treated pine char after an acid purification treatment were 69 cm−1, 126 cm−1, and 0.16, respectively.

5,5'-Dithiobis(2-nitrobenzoic acid) (DTNB) was selected as an electron transfer mediator and was covalently immobilized onto high porosity carbon cloth to employ as a working electrode in an electrochemical NAD(+)-regeneration process, which was coupled to an enzymatic reaction. The voltammetric behavior of DTNB attached to carbon cloth resembled that of DTNB in buffered aqueous solution, and the electrocatalytic anodic current grew continuously upon addition of NADH at different concentrations, indicating that DTNB is immobilized to carbon cloth effectively and the immobilized DTNB is active as a soluble one. The bioelectrocatalytic NAD+ regeneration was coupled to the conversion of L-glutamate into alpha-ketoglutarate by L-glutamate dehydrogenase within the same microreactor. The conversion at 3 mM monosodium glutamate was very rapid, up to 12 h, to result in 90%, and then slow up to 24 h, showing 94%, followed by slight decrease. Low conversion was shown when substrate concentration exceeding 4 mM was tested, suggesting that L-glutamate dehydrogenase is inhibited by alpha-ketoglutarate. However, our electrochemical NAD+ regeneration procedure looks advantageous over the enzymatic procedure using NADH oxidase, from the viewpoint of reaction time to completion.

The influence of Pinus radiata bark polyphenol components in the phenol liquefaction of P. radiata bark was investigated using p-toluene sulfonic acid (PTSA) and sulfuric acid (SA) as acid catalysts. A series of the phenol liquefaction reactions were carried out using mixtures of pure cellulose with increasing amounts of hot-water extract (HWE) of P. radiata bark—the polyphenol-rich component of bark. The yields of liquefied product reactions and combined phenol amounts in them were determined, and the liquefaction residues were also analyzed for determination of acid-soluble and insoluble polyphenols and residual cellulose fractions. The yield of cellulose liquefaction decreased linearly with increasing amounts of HWE with the effect being more pronounced for SA than for PTSA. The combined phenol amount increased with liquefaction yield increases for both SA and PTSA catalysts, but at liquefaction yield levels above 83 percent, more phenol was combined for SA catalyst than for PTSA catalyst. The...

Hot water extract (HWE) of Pinus radiata bark was separated into monomeric polyphenol (MPP), oligomeric proanthocyanidin (OPA), and polymeric proanthocyanidin (PPA) fractions by monitored chromatography using a Sephadex LH 20 column and an UV detector at 250 nm. The effects of these fractions on NIH/3T3 fibroblasts and B16 melanoma cells were examined by evaluating cell viability, melanogenesis (melanin content), morphological changes, and tyrosinase inhibitory activity. The polyphenolic fractions had a proliferation effect on fibroblasts, with cell growth increasing significantly (P < 0.01) even at the high concentration of 1250 μg/ml. At 125 μg/ml, HWE, MPP, and OPA had no effect on melanogenesis, whereas PPA significantly upregulated melanogenesis (P < 0.05). Melanogenesis was significantly upregulated in melanoma cells treated with these fractions at the high concentration of 600 μg/ml (P < 0.01). B16 melanoma cells cultured with the proanthocyanidin (PA)-rich fractions (HWE, OPA, and PPA) showed marked dendrite retraction, leading to significant morphological transformation. OPA in particular showed colored adhesion on the surface of melanoma cells. All four fractions significantly inhibited mushroom tyrosinase activity when compared to arbutin and ascorbic acid 2-glucoside (P < 0.05). The tyrosinase inhibitory activity of OPA and PPA did not differ significantly (P = 0.11), indicating that the inhibitory effects had a low correlation with molecular weight distribution. The inhibition kinetics of PPA determined using a Lineweaver-Burk plot indicated that PPA is a noncompetitive inhibitor of l-3,4-dihydroxyphenylalanine oxidation by mushroom tyrosinase.

Easter red cedar (Juniperus virginiana) is a valuable source of heartwood extractives that provide decay resistance against termites and wood decay fungi. This study sought to determine the antifungal activity of heartwood extracts obtained using solvents with increasing polarity (hexane, chloroform, ethyl acetate, and methanol) against two wood decay fungi. The heartwood was extracted with methanol, and the methanol extract was sequentially extracted with hexane, chloroform, and ethyl acetate. The yield of the methanol extractives was 5.26 percent based on dry wood and the percentages of the hexane, chloroform, and ethyl acetate soluble fractions from the methanol extract were 46.4, 8.3, and 28.7 percent, respectively. Hexane and chloroform soluble fractions showed a high inhibitory effect on the growth of the wood decay fungi Trametes versicolor and Gloeophyllum trabeum. Gas chromatography–mass spectrometry analysis identified skeletons of sesquiterpenes and sesquiterpene alcohols in both extracts and t...

Pinus radiata bark is a rich source of proanthocyanidins (PAs), a potent and valuable plant antioxidant. This study was performed to evaluate PA extraction conditions with water at various temperatures ranging from 25°C to 120°C. The properties of the water extract (WE) obtained at each temperature were investigated in terms of PA content, molecular weight (MW) distribution, and antioxidant activity. The WE yield was significantly dependent on temperature. The PA yield and the absorbance at 280 nm (an indicator of PA concentration) of WE reached maximum values at 80°C, implying increased extraction of monomeric polyphenols. Gel permeation chromatography results suggested that water extraction above 100°C caused depolymerization of extracted PAs, thereby noticeably reducing MW. It was found that more monomeric polyphenols can be extracted by increasing temperature. The WE antioxidant activity was maximized at 80°C and was dependent to some extent on the degree of polymerization.

Proantocyanidins are naturally occurring compounds that are widely found in fruits, vegetables, nuts, seeds, flowers and bark. In part I, we evaluated the immunomodulatory effects of proanthocyanidin-rich extract (PAE) from Pinus radiata bark in specific pathogen free (SPF) White Leghorn chickens. Proliferation of peripheral blood mononuclear cells was significantly enhanced in chickens treated for 2 weeks with 20 ㎎/㎏ PAE. Proliferation of splenocytes and bursal cells was significantly enhanced in chickens treated for 5 weeks with 5, 10, and 20 ㎎/㎏ PAE. Thymocyte proliferation was significantly enhanced in chickens treated for 5 weeks with 5 and 10 ㎎/㎏ PAE. These effects were markedly enhanced by the presence of lipopolysaccharide, which actedon B cells responsible for humoral immunity, and concanvalin A, which acteddirectly on T cells involved in cell mediated immunity. PAE significantly promoted the expression of Th1 cytokine (interferon-gamma) and decreased the expression of Th2 cytokine (interleukin-6). In part Ⅱ, we evaluated the immunomodulatory effects of proanthocyanidin-rich extract (PAE) from Pinus radiata bark in broiler. Proliferation of peripheral blood mononuclear cells and thymocytes was significantly enhanced in 2.5, 5, 10 ㎎/㎏ PAE-treated broiler chickens. Proliferation of splenocytes was significantly enhanced in 1.25, 2.5, 5, 10 ㎎/㎏ PAE-treated broiler chickens. These effects were markedly enhanced by the presence of LPS, which acts on B cells responsible for humoral immunity, and Con A, which acts directly on T cells involved in cell mediated immunity. PAE significantly promoted the expression of interleukin-18 and interleukin-1 β. In part Ⅲ, We evaluated the immunomodulatory effects of proanthocyanidin-rich extract (PAE) from Pinus radiata bark in Korean native chickens. In experiment 1, proliferation of peripheral blood mononuclear cells (PBMCs) was significantly enhanced in chickens administered for 2 weeks with 1.25, 2.5, 5 and 10 ㎎/㎏ PAE. Proliferation of splenocytes and thymocytes cells was significantly enhanced in chickens administered for 5 weeks with 1.25, 2.5, 5 and 10 ㎎/㎏ PAE. In experiment 2, proliferation of PBMCs, splenocytes and thymocytes in the PAE-administered chickens for 6 weeks were continuously higher than other groups and significantly promoted the expression of Th1 cytokines (IL-2, IL-12, and IFN- γ). Also, the CD4+CD8? (Th1 cell) and Bu-1+ (B cell) cell population significantly upregulated after 4 weeks in PAE-administered chickens.

Lack of data especially pertaining to the chemistry of mangrove wood species makes it difficult to prepare successful plans for their conservation and to use mangroves as a source of wood fiber. In this paper, chemical characterizations of the six main mangrove species of Bangladesh [namely Keora (Sonneratia apetala), Geoa (Excoecaria agallocha), Bine (Avicennia alba), Sundari (Heritiera fomes) Pashur (Xyloccarpous mekongests), and Kakra (Bruguiera gymnorhiza)] were investigated. The chemical results revealed that these species contain high percentages of dichloromethane followed by methanol extractives. Methanol extracts in Pashur, Sundari, and Bine were higher than 10%, which indicates high percentage of tannin material. The total lignin content in these species was higher than 25%, except for Gewa (23.6%) and Pashur (21.3%), which is higher than that of the normal range of hardwood. The pentosan content in these six species was within the range of 19.4–22.8%. The α-cellulose content in Keora and Gewa was acceptable for pulp production, but the others were lower than the normal range of hardwood. Alkaline nitrobenzene oxidation showed that all these species had a very high syringaldehyde to vanillin (2.6–5.0) ratio except Keora (1.6). Surprisingly, rhamnose is the main constituent with xylose of hemicelluloses of these six mangrove species. The ash content in these six mangrove wood species was also higher than that in normal hardwood.

Dioxane and milled wood lignins (MWL) were isolated from tropical hardwood, Nalita (Trema orientalis ) and temperate hardwood, aspen. These lignins were characterized by UV, FTIR, 1 H-NMR and 13 C-NMR spectroscopy, alkaline nitrobenzene oxidation, molecular weight determination, elemental and methoxyl analysis. The structural analysis revealed that Nalita and aspen lignin is syringyl-guaiacyl type. Aspen lignin had higher syringyl unit than Nalita lignin. The β-O-4 type linkages are the main interunit linkages and more abundant in aspen than Nalita. Dioxane lignin showed higher free phenolic hydroxyl group than MWL in both species. The weight average molecular weight of aspen lignin was lower than that of Nalita lignin. Nalita and aspen lignins contained both erythro and threo configuration, but erythro proton gave stronger peak. A UV absorption maximum of aspen lignin was at 274 nm, whereas it was shifted to 280 nm for Nalita lignin. Keywords: Trema orientalis , Aspen, Dioxane lignin, Milled wood lignin, Syringyl-guaiacyl, β-O-4 linkages DOI: 10.3329/bjsir.v44i3.4399 Bangladesh J. Sci. Ind. Res. 44(3) , 271-280, 2009

The chemical composition of natural powder dye manufactured from Pinus radiata bark and dyeability of dyed silk fabrics with were examined. It is made up of the optimum dyeing condition of silk fabric according to the dyeing concentration, dyeing time, and dyeing temperature. Also, we examined the colorfastness and antibiosis of dyed silk fabrics to washing, rubbing, perspiration and light. For the analysis of the chemical composition of , the total contents of phenolic compound, proanthocyanidin(PA) and anti-oxidative activities of the dye were analyzed. As a result, it was found that the main components of the manufactured from Pinus radiata bark is proanthocyanidin, mostly a flavonoid containing a procyanidin structure, and it consists of approximately 63% phenol. As a result of examining the dyeability of silk fabrics with , it showed that the dyeability was best under the conditions of the concentration of dye (wt/v%), dyeing time of 90 minutes, and dyeing temperature at . It was found that the colorfastness of dyed silk fabrics, colorfastness to washing, perspiration for acidic and rubbing were as good as grade 4 or 4-5. However, the colorfastness to light was low at grade 1, the same as the results of other natural dyed fabrics. As a result of the antibiosis measurement for the -dyed silk fabrics, it showed high antibacterial properties to Staphylococcus sureus at 99.6%.

The structural feature of macromolecular component of dhaincha, cotton stalks, jute fiber, rice straw and wheat straw, which are commonly used in paper pulp production in forest deficient countries, was thoroughly studied. Lignin was isolated by classical Bjorkman method and characterized by elemental and methoxyl analysis, alkaline nitrobenzene oxidation, FTIR and 1H NMR spectroscopy. The C9 formulas for cotton stalks, jute fiber, dhaincha, rice straw and wheat straw were C9H8.95O3.53(OCH3)1.00, C9H8.12O4.03(OCH3)1.65, C9H8.10O4.65(OCH3)1.32, C9H8.58O3.74(OCH3)1.23 and C9H8.31O3.54(OCH3)1.23, respectively. The alkaline nitrobenzene oxidation products showed that syringyl to vanilin ratio of these nonwood varied from 1.1 to 2.9. Jute fiber showed the highest syringyl to vanilin ratio that are consistent with C9 formula. The β-O-4 units in these nonwood lignins had predominately erythro stereochemistry type. The crystalline structure of these nonwood cellulose was also studied using X-ray diffraction and FTIR spectroscopy. The proportions of crystallinity, crystal size were varied from plant to plant. Jute fiber showed the highest proportion of crystallinity (73.4%) and crystal size (4.2 nm). The degree of polymerization of these nonwoods cellulose has also been studied. Degree of polymerization of jute cellulose was also the highest (3875). FTIR spectroscopy showed that these nonwoods cellulose was monoclinic unit cell structure (Iβ). Carbohydrate analysis showed that the main sugar component in the hydrolyzates of these nonwoods were xylose apart from glucose.

Constituents of tars formed during the aging of bamboo (Phyllostachys pubescens), oak (Quercus serrata), and pine (Pinus densiflora) wood crude vinegars were analyzed by pyrolysis-gas chromatography (Py-GC) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) to investigate their origination. The pyrolysate of tars obtained from the wood and bamboo crude vinegars were almost identical and were primarily composed of phenolic compounds and aromatic hydrocarbons. In addition, during the aging of model wood vinegar that was prepared for comparison with the wood and bamboo vinegars, a marked decrease was observed in the levels of phenolic compounds (phenol; o-, p-, and m-cresol; and syringol). Furthermore, the Py-GC-MS results of the tars produced during the aging of the model wood vinegar revealed that phenolic compounds were primarily responsible for the formation of tar during the aging of wood and bamboo crude vinegars. Pyrroles, which may be derived from the primary pyrolysate of amino acids, nitrogen-containing extracts, or both, were also partially involved in the formation of tar during the aging period.

The kinetics of p -toluene sulfonic acid (PTSA)-catalyzed cellulose liquefaction in the presence of phenol were investigated at 130, 140 and 150 °C. The resulting liquefied products were also analyzed to evaluate the effectiveness of PTSA as a catalyst during the phenol liquefaction. The liquefaction rate of PTSA was slightly lower than that of sulfuric acid (SA), which was used as a reference catalyst, at each liquefaction temperature. The activation energies of the PTSA and SA catalysts during the phenol liquefaction of cellulose calculated using the Arrhenius equation were 34.5 and 35.5 kcal/mol, respectively. The chemical compositions of the ether extracts in the liquefied products were very similar to both catalysts. Methylene bisphenol and its isomers, which were the primary components in the ether extracts, comprise approximately 30% of the ether extract. The GPC curves of the 80% dioxane-soluble part of the liquefied product indicated that it consists of a remarkable amount of phenol-based trimers to hexomers. The average molecular weight and the polydispersity of the liquefied products were very similar after liquefaction using both catalysts; therefore, differences in the products produced using both catalysts used were not recognized. However the level of combined phenol in the liquefied product produced using the PTSA catalyst was approximately 50% lower than that of the SA catalyst. Although it is believed that this difference may cause retardation of the rate of liquefaction, further experiments are necessary to explain differences in the effectiveness of organic sulfonic acid catalysts during the phenol liquefaction of lignocellulosic biomass.

Pine (Pinus densiflora) bark was chemically modified by grafting with acrylonitrile (AN) through Fenton reaction and conversion of the cyano group to an amidoxime group by reaction with hydroxylamine. Treatments of pine bark with 160 mM H2O2 at 40°C yielded ~70% grafting in 6-h reaction. After alkali hydrolysis of amidoximated pine bark (AOPB), its adsorption capacity (q e) for copper ions was largely increased from 0.5 to 1.8 mmol/g. Adsorption of the hydrolyzed AOPB (HAOPB) followed the pseudo-second-order kinetic model. Among the metal ions tested, the order of adsorption capacity (q e) predicted by the kinetic model at equilibrium time was Hg2+ > UO2 2+ > Cd2+ > Cu2+ > Zn2+ > Ni2+. The adsorption process was pH-dependent, and the adsorption equilibrium was observed in the pH range of 6–7 for all the metal ions. Even though pine bark is a good adsorbent for Hg2+ and UO2 2+ ions, it had a poor affinity for the other ions tested. It was obviously found that HAOPB had very high adsorption abilities for heavy metal and uranyl ions.

Cellulosic superabsorbents are prepared by pretreating the wood pulp (WP) with Ce4+ initiator, followed by the graft copolymerization of acrylamide (AM) monomer onto Ce4+-pretreated WP (Ce4+ · WP) in acidic medium and in the presence of N,N′-methylenebisacrylamide (MBAM) cross-linker. The rate of AM copolymerization of Ce4+ · WP is significantly faster than that of the untreated WP. The obtained polyAM (PAM)-grafted cellulosic copolymers (PAM-g-Ce4+ · WP copolymers) are alkaline-hydrolyzed to produce the water-absorbents. As PAM grafting yield increases, the absorbency increases rapidly and reaches the maximum value at a yield of 210–240%. The maximum water and saline absorbencies are around 2500 and 50 g g−1, respectively. The optimum feed concentration of Ce4+ pretreatment on the maximum water and saline absorbencies is 5.0 × 10−3 mol L−1. The water and saline absorbencies of the PAM-g-Ce4+ · WP water-absorbents are remarkably higher in comparison with that of the untreated WP (with a similar grafting yield) due to uniform PAM-grafting onto Ce4+ · WP specimen. In addition, as the amount of cross-linker increases, the grafting yield is not changed whereas the water and saline absorbencies are remarkably decreased. Copyright © 2008 John Wiley & Sons, Ltd.

The differences in morphological and chemical characteristics and pulpability of core and bark fiber of jute at different position, top, middle and bottom were studied. The fiber length at the middle part of both bark and core was longer than the top and bottom part. With increasing height from bottom to top lignin content is decreased and α-cellulose content increased. The bark had higher α-cellulose and lower lignin than core. The bark produced nitrobenzene oxidation products with larger syringaldehyde/vanillin (S/V) ratios than the core. The yields of nitrobenzene oxidation products in bark were higher than core. The analysis of neutral sugars suggested that xylose is the predominant sugar of hemicellulose in both bark and core. The bark had higher glucose and lower xylose as compared to core. Under identical conditions of pulping, bark gave higher pulp yield and lower kappa number than core. The bark pulp showed better bleachability than core pulp. The higher tensile index in core pulp and higher tear index in bark pulp were observed.

This study was performed to evaluate stabilization of extracellular matrix (ECM) proteins by polyphenolic fractions in hot water extract (HWE) from Pinus radiata bark against enzymatic degradation and radicals. To obtain polyphenolic fractions with different molecular weight (MW) distribution, HWE was fractionated into monomeric polyphenols (MPP), oligomeric proanthocyanidin (OPA), and polymeric proanthocyanidin (PPA) fractions by monitoring the UV–visible spectrum of the eluted fractions. For HWE, MPP, OPA, and PPA, the collagen (15 mg)-stabilizing capacities at 192 μg/mL were 86, 64, 76, and 88%, respectively, while the elastin-stabilizing capacities at 45.5 μg/mL were 37.6, 1.5, 10.8, and 41.8%, respectively. Among these fractions with different MW distribution, PPA played a significant role in the ECM (collagen and elastin) stabilization in a dose-dependent manner. It could be considered that adsorption of PPA onto the ECM is a significant mechanism of polyphenols for collagen protection. 1,1-Diphenyl-2-picrylhydrazyl (DPPH) free radical- and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate) (ABTS •+)-scavenging activity of PPA adsorbed onto collagen showed a dose-dependent increase.

The phenolic composition of pine bark from a variety of Pinus species was estimated by measuring Klason lignin, acid-soluble lignin, and a 1% NaOH extract. Polyphenol contents of hot water extracts from pine bark were determined by the Folin-Ciocalteu assay and the vanillin-H2SO4 assay. Among the pine bark varieties investigated, Pinus radiata bark showed the highest polyphenol content and potent antioxidant activity. Pinus rigida bark was also a usable polyphenol-rich source, whereas Pinus densiflora bark had a low yield (5.1%) of hot water extract, although it showed potent antioxidant activity. Correlations between proanthocyanidin content in pine bark and antioxidant activity were observed. The results suggested that proanthocyanidin was the crucial contributor to potent antioxidant activity in pine bark.

Nalita (Trema orientalis) is one of the fastest growing trees in the tropical countries. The structural characteristics of lignin isolated at different ages of Nalita wood (Trema orientalis) by acidolytic dioxane method were examined by UV, FTIR, 1H‐NMR and 13C‐NMR spectroscopy, alkaline nitrobenzene oxidation, molecular weight determination, elemental and methoxyl analysis. The data were compared with aspen lignin. The structural analysis revealed that Nalita wood lignin is syringyl‐guaiacyl type. The methoxyl content in Nalita wood lignin was lower than aspen lignin. The C9 formulas for 30‐months‐old Nalita was C9H9.31O3.13(OCH3)1.27, whereas that of aspen was C9H8.94O3.15(OCH3)1.47. The weight average molecular weight of Nalita wood lignin was decreased from 36,500 to 25,500 with increasing tree age from 12 to 30 months, whereas weight average molecular weight of aspen was 20,000. Both alcoholic and phenolic hydroxyl group in Nalita wood lignin is lower than aspen lignin.

Hot water extract (HWE) from Pinus radiata bark was fractionated into monomeric polyphenol (MPP), oligomeric proanthocyanidin (OPA), and polymeric proanthocyanidin (PPA) fractions by monitoring the UV-visible spectrum of the eluted fractions. Nine polyphenols were identified in MPP: three phenolic acids and six flavonoids. The major compounds of MPP were taxifolin (456 μg/mg), catechins (240 μg/mg), and protocatechuic acid (46.2 μg/mg). The OPA components ranged from dimers to hexamers. PPA comprised procyanidin (PC, 94%), a small amount of prodelphinidin (PD, 6%), and also the higher trans configuration, rather than the cis configuration, of C2-C3. The average molecular weight (Mw, Mn), polydispersity (Mw/Mn), and DP of PPA were 3,800 (Mw), 1,200 (Mn), 3.2 and 13, respectively. The potential antioxidant activities of HWE and the three fractions were estimated using proton- or electron-donating assays containing 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) radical cation, superoxide anion (O2•−), hydrogen peroxide (H2O2), reducing power and lipid peroxidation. All the bark fractions exhibited potent quenching abilities against both commercially available radicals (DPPH•, ABTS•+) and chemically induced radicals (H2O2, O2•−), as well as strong reducing power and inhibitory activity of lipid peroxidation. Particularly, OPA showed a hydrogen peroxide scavenging activity significantly higher (p < 0.05) than that of the other fractions. From 2-thiobarbituric acid reactive substances and ferric thiocyanate assays, PPA was suspected to act by essentially delaying the formation of hydroperoxide by quenching free oxygen radicals that operates in oil-in-water emulsion.

Batch biosorption experiments were carried out for the removal of Congo red from aqueous solution using native and pretreated mycelial pellets/biomass of Trametes versicolor. The effect of process parameters such as contact time, dye concentration, and pH on the extent of Congo red biosorption has been investigated. Higher dye concentrations resulted in lower biosorption. Increases in biomass dosage led to increases in the levels of biosorption. Biosorption kinetics and equilibrium data are essential basic requirements to develop an effective and accurate design model for the removal of the dye. A kinetic study showed that the biosorption of the dye on fungal biomass was a gradual process. Pseudo-first-order, pseudo-second-order, and Bangham's model were used to fit the experimental data. The results of the kinetic studies showed that the second-order kinetic model fitted well for the present experimental data. Equilibrium isotherms were analyzed by Langmuir, Freundlich, Dubnin-Radushkevich, and Temkin isotherms. The biosorption equilibrium data obeyed the Langmuir and Temkin isotherms well. Acidic pH was favorable for the biosorption of the dye. Studies on the pH effect and desorption show that chemisorption seems to play a major role in the biosorption process. Among the native and pretreated biomass studied, autoclaved biomass showed a better biosorption capacity.

Saw dust-reinforced linear low density polyethylene (LLDPE) (1:1) composites were prepared by using ethylene-vinyl alcohol copolymer (EVAL) as adhesion promoter to improve mechanical strength. To evaluate the optimum vinylalcohol (VA) content in EVAL, various EVAL samples containing different contents of VA were used. The tensile properties of saw dust-LLDPE composites were improved by using EVAL as adhesion promoter in place of ethylene-vinyl acetate copolymer (EVAc). The saw dust-LLDPE composites prepared with EVAL containing 15 mol% VA showed the maximum yield stress and modulus. The tensile stress increased with addition of EVAL up to 3wt% on the wood filler, and then leveled off in the range of 3-10 wt%. However, the elongation was decreased with increasing VA content. Hydrogen bonding interaction between saw dust and EVAL was detected by FT-IR spectra. When EVAL consisting with 15 mol% VA was used, good adhesion between saw dust and LLDPE matrix was confirmed by SEM fractography.

The change of crystalline structure of Nalita cellulose with tree age has been studied using X-ray diffraction and FT-IR spectroscopy. The proportion of crystallinity and crystal size were increased with tree age. FT-IR spectroscopy showed that the Nalita cellulose was a monoclinic unit cell structure (Iβ). The proportion of crystallinity and crystal size of the 30-month-old Nalita wood was higher as compared to aspen wood. The degree of polymerization (DP) of Nalita cellulose of different ages has also been studied. The DP of cellulose increased with tree age. The DP of Nalita cellulose was lower than that of aspen cellulose. The percentage of glucose in Nalita wood increased with tree age.

Wood char, a by-product from the fast-pyrolysis process of southern yellow pine wood for bio-oil production, was carbonized with Fe nanoparticles (FeNPs) as a catalyst to prepare carbon-encapsulated Fe nanoparticles. A magnetic separation method was tested to isolate carbon-encapsulated Fe nanoparticles from the carbonized char. X-ray diffraction pattern clearly shows that Fe-containing materials were completely separated from the carbonized wood char mixture using a magnet. The amorphous carbon in the material which adhered to the magnetic bar was significantly decreased in comparison with the non-adhered material. Carbon graphitic layers encapsulated FeNPs were observed in the adhered material through high-resolution transmission electron microscopy. In addition, many long and tangled-multi-layered graphitic carbon structures grew from the surface of carbon-encapsulated Fe nanoparticles.

A high molecular weight lignin fraction, alcohol bisulfite lignin, was isolated from the spent liquor of alcohol bisulfite pulping of Japanese cedar (Cryptomeria japonica D. Don) wood and subjected to analytical pyrolysis. The resulting products were compared with those from the original wood, its milled wood lignin and a synthetic lignin. The alcohol bisulfite lignin yielded several characteristic pyrolysis products compared with the other samples: a large yield of 4-propylguaiacol and small amounts of methylated compounds. Furthermore, analytical pyrolysis of the alcohol bisulfite lignin gave a much smaller yield of coniferyl alcohol than that from Japanese cedar wood. These differences are due to the chemical change in the lignin structure as a result of the alcohol bisulfite treatment.

The content of phenolic hydroxyl groups in the unbleached kraft pulp residual lignin was determined in situ by periodate oxidation method. This functional group has been shown to increase steadily with the extent of kraft delignification throughout the entire pulping process.

A high porosity carbon cloth with immobilized FAD was employed as working electrode in electrochemical NADH-regeneration procedure. Carbon cloth was oxidized with hot acids to create surface carboxyl group and then coupled by adenine amino group of FAD with carbodiimide in the presence of N-hydroxysulfosuccinimide. The bioelectrocatalytic NADH-regeneration was coupled to the conversion of achiral substrate pyruvate into chiral product l-lactate by l-lactate dehydrogenase (l-LDH) within the same reactor. The conversion was completed at 96h in bioreactor with FAD-modified carbon cloth, resulting in about 6mM of l-lactate from 10mM of pyruvate. While with bare carbon cloth, the yield at 120h was around 5mM. Immobilized FAD on the surface of carbon cloth electrode facilitated it to carry electrons from electrode to electron transfer enzymes; thereby NADH-regeneration was accelerated to drive the enzymatic reaction efficiently.