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Some species of Diospyros form the black wood that is known as ebony. Infrequently, D. kaki forms wood with black patterning that is called “kurogaki” in Japan and is highly valued. To understand the mechanism of formation of the blackened xylem, we attempted to clarify the pathways of diffusion of colored substances from the site of their biosynthesis to their deposition in secondary xylem. We observed colored substances in pits and intercellular spaces and we recorded the deposition of colored substances in the cell walls of wood fibers. In gray and black regions, we found colored substances in the pits between xylem cells, in blind pits and in intercellular spaces. At the boundary between whitish and black regions, areas of coloration in the cell walls of wood fibers gradually increased in size from the whitish to the black regions. Heavy deposition of colored substances was observed in the inner region of the secondary walls of wood fibers. Furthermore, coloration of the outer region of the secondary walls and compound middle lamella (CML) of wood fibers gradually became stronger toward the black regions. Our observations suggest that pit-pairs and intercellular spaces might provide the pathways for inter- and extracellular diffusion of colored substances, respectively. In addition, colored substances might penetrate the cell walls of wood fibers, moving from the lumen into the cell wall.

Glycol lignin possessing thermoplastic and fusible properties can be a biorefinery platform material; however, glycol lignin is obtained as very small particles in suspension and the low dewatering efficiency is a major difficulty for the mass production. To improve the productivity of glycol lignin in the refinery plant, glycol lignin-based flocculants were prepared and their flocculation performance was examined. The flocculants (cationized glycol lignins) were synthesized by a reaction with glycidyltrimethylammonium chloride (GTA) in various reaction conditions. The prepared flocculants exhibited high flocculation performance and successfully economized the production cost of glycol lignin. Their flocculation efficiency was affected by the precipitation temperature, the length of the glycol chain, the molecular weight and the functional group of the glycol lignin. The flocculation behavior was interpreted by phase separation theory at a lower critical solution temperature (LCST).

Bamboos are among the largest woody grasses and grow very rapidly. Although lignin is a crucial factor for the utilization of bamboo biomass, the lignification mechanism of bamboo shoots is poorly understood. We studied lignification in the bamboo Sinobambusa tootsik during culm development. Elongation growth began in May and ended in late-June, when the lignin content was approximately half that in mature culms. Thioacidolysis analysis indicated that p-hydroxyphenyl units in lignin formed even at late stages of lignification. The syringyl/guaiacyl ratio varied during culm development. Various lignin precursors were detected in developing culms by liquid chromatography–mass spectrometry. The ferulic acid content decreased from May to June, indicating that ferulic acid was utilized in early stages of cell wall formation. Monolignol glucosides were detected at early stages of lignification, whereas the contents of monolignols, coniferaldehyde, sinapaldehyde, p-coumaric acid, and ferulic acid peaked at later stages of lignification. Therefore, lignin precursors may be supplied differentially during the lignification process. In August, the rate of lignification decreased, although the contents of various lignin precursors peaked, implying that the rate-limiting step in the cessation of lignification in bamboo is transport or polymerization of lignin precursors, rather than their biosynthesis.

To investigate the possibility of decontaminating 137Cs-contaminated Cryptomeria japonica wood, kraft pulping was conducted and the Cs behavior in the reaction process was examined. 133Cs-treated or 137Cs-contaminated bark, sapwood, and heartwood chips of Cryptomeria japonica were digested using an aqueous solution of NaOH and Na2S. The pulp was washed with ultrapure water and filtered, after which the filtrate (black liquor) was collected. The black liquor was acidified to separate the supernatant and precipitation. The Cs (133Cs and 137Cs) concentrations in the chip and reaction products were measured. As for wood samples, the majority of Cs was present in black liquor, while only a minor amount of Cs was retained in the pulp (

In order to understand the kraft pulp decolouring mechanism on using a nonionic detergent, the pulp washing process and the resulting pulp handsheets were investigated by examining the brightness, kappa number, thioacidolysis product yield, and dewatering efficiency in the pressing sheet making process. The pulp decolouring could be attributed to a decrease in the lignin content and an improvement in the dewatering efficiency. Furthermore, the detergent distribution in the aqueous pulp suspension obtained during the pulp washing process was visualised using cryo-time-of-flight secondary ion mass spectrometry/scanning electron microscopy (cryo-TOF-SIMS/SEM). The detergent was clearly observed at the transverse surface of the pulp fibre cell wall and was also detected in the lumen of the fibres, suggesting the permeation of the detergent into the pulp fibre cell wall. Based on these results, the pulp decolouring mechanism can be proposed as follows: the detergent permeates into the pulp fibre cell wall and promotes the solution-exchange between the inside and the outside parts of the fibre cell wall, finally washing away the chromophoric substances such as lignin and its degradation products owing to the enhanced dewatering efficiency.

Lignin is a biopolymer consisted of monolignols but the growth mechanism of lignin has not yet been elucidated. In this study, enzymatic dehydrogenative polymerization of dilignols, guaiacylglycerol-β-coniferyl ether (I), dehydrodiconiferyl alcohol (II), and pinoresinol (III), was conducted using crude enzyme obtained from Japanese cypress (Chamaecyparis obtusa) in order to investigate the step following the initial radical coupling between monolignols. The results suggested the occurrence of radical transfer during the reaction, similar to the reaction using horseradish peroxidase (HRP). The behavior of erythro and threo of I during the reaction was analyzed, and it was found that the crude enzyme has a substrate specificity toward erythro rather than threo forms, but HRP shows negligible specificity. And that erythro of I shows a slightly greater tendency to form a radical by radical transfer from II or III than the threo form.

Sulfuric acid lignin (SAL) is a byproduct of the acid saccharification of lignocellulosic materials for bio-fuel generation. The recalcitrant and highly complex structure of SAL significantly limits its industrial use, making it a useless industrial waste. In a previous study, we proposed a hydrothermal reaction for SAL that can convert it into water-soluble compounds (HSALs), which considerably expanded its industrial use scenario. In this study, we converted this water-soluble HSAL into two ionic modifications with applications as flocculants and dispersants. Firstly, the introduction of a carboxy group was carried out with bromoacetic acid. In the carboxymethylated HSAL (C-HSAL), the carboxymethyl groups content was as high as 3.66 mmol/g. Dispersibility tests using gypsum paste showed that C-HSAL exhibited a dispersibility almost equivalent to that of commercial lignosulfonate. Furthermore, another investigation was conducted synthesizing cationized HSAL derivatives by the reaction with glycidyl trimethylammonium chloride (GTA). Dye removal tests were performed with the obtained lignin-based flocculants using three organic dyes. The results showed ideal dye removal ratios for the GTA-HSALs (higher than 90% for all dyes tested), thereby suggesting that they have a huge potential as core molecules to develop high-efficient dye flocculants.

The structure and biosynthesis of lignin are not yet fully understood, especially the step following the initial dimerization of monolignol. Liquid chromatograph mass spectrometer (LC–MS) was used to analyze the consumption rates of monolignol dimers formed by β-O-4, β-5, and β-β couplings between coniferyl alcohols in efforts to understand the activity of monolignol dimers in enzymatic dehydrogenative polymerization. We investigated the reaction kinetics in single-component and mixed-component reaction systems containing one and two species of the dimers, respectively. A difference was observed between the consumption rates of the three dimers we tested, and the consumption rate of one dimer in the single-component reaction was different from that in a mixed-component reaction. In qualitative LC–MS analyses, coniferyl alcohol oligomers were detected in the reaction products. Some monolignol tetramers were formed by 5-5 and 5-O-4 coupling between the dimers. The results of this work suggested that monolignol dimers with β-5 and β-β linkages could function as radical mediators in enzyme-catalyzed polymerization.

In this study, polyesters were prepared from sulfuric acid lignin (SAL) that was generated as a by-product during the production of bioethanol from lignocellulosic materials using ɛ-caprolactone (CL). Carboxylic groups were introduced into SAL by a hydrothermal reaction under alkali conditions. The acid form (-COOH) of the obtained polymer (HSAL) was dissolved into ɛ-caprolactone and the mixture was heated at 150°C for 12 h with ZnCl2 as a catalyst. The structure of the obtained polymer (PCL-HSAL) was proposed based on results of differential scanning calorimetric analysis, swelling tests, and dynamic mechanical thermal analysis. The hydroxyl group in HSAL participated in the ring-opening polymerization of CL. PCL-HSAL with a high HSAL content formed a three-dimensional network that did not dissolve in organic solvents and did not melt at high temperature. PCL-HSAL showed a high swelling property for a suitable ratio of CL to HSAL.

4,8-Dihydroxy-5-methoxy-2-naphthaldehyde (Compound I) was isolated from blackened heartwood of Diospyros kaki and was methylated with diazomethane. Antioxidant and cytotoxic activities of Compound I and two methylated derivatives [4-hydroxy-5,8-dimethoxy-2-(2-oxopropyl)-naphthalene (D-1) and 2-glycidyl-4-hydroxy-5,8-dimethoxy naphthalene (D-2)] were evaluated. Compound I showed higher 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity and reducing power than D-1 and D-2. However, D-1 and D-2 exhibited slightly stronger 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)+ (ABTS+) radical scavenging activity than Compound I. Compound I also exhibited stronger cytotoxic activity than D-1 and D-2 against the growth of HT-29 colon cancer cells. The results supported the hypothesis that methylation of naphthalene derivatives slightly increased ABTS+ radical scavenging activity, but significantly decreased DPPH radical scavenging activity, reducing power, and cytotoxic activity.

A detailed chemical investigation of the extractives of the blackened heartwood of Diospyros kaki was carried out to understand their chemical characteristics and to obtain chemotaxonomic information. Three novel naphthalene derivatives were isolated, i.e., 4-hydroxy-5,6-dimethoxy-2-naphthaldehyde (1), 5,6,8-trimethoxy-3-methyl-1-naphthol (2), and 4,8-dihydroxy-5-methoxy-2-naphthaldehyde (3), in addition to two previously reported 2-naphthaldehydes: 4-hydroxy-5,8-dimethoxy-2-naphthaldehyde (4) and 4-hydroxy-5-methoxy-2-naphthaldehyde (5) Their structures were identified by 1D and 2D nuclear magnetic resonance spectroscopy, as well as by high-resolution mass spectrometry.

Electropolymerization of coniferyl alcohol was carried out in an aqueous system (0.2 M NaOH) and in an organic solvent system [CH2Cl2/methanol (4:1 v/v) in the presence of 0.2 M LiClO4] to produce a dehydrogenation polymer (DHP) - artificial lignin. In both systems, the polymerization of coniferyl alcohol was visually confi rmed. In the aqueous system, no dimer was detected in the reaction medium after electropolymerization, suggesting that endwise polymerization occurred on the electrode surface. Thioacidolysis degradation revealed that the obtained polymers had numerous 8-O-4′ linkages. The electropolymerization products obtained in the organic solvent system also had numerous 8-O-4′ linkages; in particular, the polymers obtained in the initial polymerization stage. This was probably because of the limited area available for reaction and the orientation of coniferyl alcohol on the electrode surface controlled the polymerization.

Heartwood extracts from Amazonian trees cumaru-ferro (Dipteryx odorata), jatoba (Hymenaea courbaril), and guarita (Astronium lecointei) exhibit antioxidant activities comparable with that of α-tocopherol, a well-known antioxidant. This article reports the characterization of the antioxidant compounds in the extracts of the three heartwoods. Silica gel column chromatography of the cumaru-ferro EtOAc extract yielded (−)-(3R)-7,2′,3′-trihydroxy-4′-methoxyisoflavan and (+)-(3R)-8,2′,3′-trihydroxy-7,4′-dimethoxyisoflavan. Silica gel column chromatography followed by preparative high-performance liquid chromatography of the jatoba EtOAc extract yielded (−)-fisetinidol and (+)-trans-taxifolin. Chemical structures were assigned using electron-ionization mass spectrometry, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy including nuclear Overhauser effect spectroscopy (NOESY), as well as optical rotation and circular dichroism. Gas chromatography-mass spectrometry demonstrated that the isolated compounds were predominant in the EtOAc extracts. In the guarita EtOAc extract, catechin and gallic acid were identified by comparing their retention times and mass fragmentation patterns with those of authentic samples. Antioxidant activity determined by the 1,1-diphenyl-2-picrylhydrazyl assay demonstrated that all these compounds had activities comparable with that of α-tocopherol.

The heartwood and sapwood characteristics of 11 Amazonian trees were investigated. Whereas 7 of the specimens had densities greater than 0.7 g/cm3, the heartwood density of ipe amarelo (Tabebuia serratifolia), macaranduba (Manilkara huberi), cumaru-ferro (Dipteryx odorata), and guarita (Astronium lecointei) exceeded 1.0 g/cm3. Jatoba contained small amounts of Klason lignin and α-cellulose, and large amounts of holocellulose and alkali extract, suggesting that it has a high polysaccharide content that can be dissolved in an alkaline medium. The difference in the syringyl/guaiacyl (S/G) ratios of the samples before and after alkali extraction suggests that alkali extracts contain syringyl-type polyphenols. In all of the samples, the heart-wood methanol extracts were larger in volume than the sapwood methanol extracts, and the sapwood alkali extracts were larger in volume than the heartwood alkali extracts. The antioxidant activities of the methanol and alkali extracts were assayed by measuring the levels of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity and super oxide dismutase (SOD)-like activity, respectively. The heart-wood methanol extract of jatoba (Hymenaea courbaril) exhibited the highest level of activity (EC50 = 44 mg/l), which exceeded that of α-tocopherol (EC50 = 48 mg/l), and the heartwood alkali extracts of jatoba and ipe amarelo had high SOD-like activity comparable with red wine.

To study the behavior of hardwood sulfuric acid lignin (SAL) during phenolization, we compared the product yield, average molecular weight, methoxy content, and reactions of simple model compounds with those of softwood SAL, focusing on the difference between syringyl and guaiacyl units. The beech SAL reacted with phenol more readily than red pine SAL and yielded a larger soluble fraction of phenolized SAL. To investigate the difference in the phenolization activity of the syringyl and guaiacyl units in beech lignin, we prepared syringyl-nucleus-rich sulfuric acid lignin (S-rich-SAL) and guaiacyl-nucleus-rich sulfuric acid lignin (G-rich-SAL) from beech, which were subjected to phenolization. The results suggest that the syringyl unit in SAL had greater phenolization activity and its phenolized products were more soluble in acidic aqueous medium and introduced less phenol than the guaiacyl unit. Using model compounds, the study also showed that the syringyl unit had higher phenolization reactivity than the guaiacyl unit.

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.

To utilize acid hydrolysis lignin effectively, chemical conversion to anion-exchange resin was investigated by two methods. Sulfuric acid lignin (SAL) was selected as a typical acid hydrolysis lignin in this experiment. Because it is less reactive, SAL was phenolated with sulfuric acid catalyst to yield reactive phenolized SAL (P-SAL) with p-hydroxyphenyl nuclei. One method was the restricted resinification of P-SAL followed by the Mannich reaction with formaldehyde and dimethylamine to yield a weakly basic anion-exchange resin with an ion-exchange capacity of 2.4 mEq/g. Another method was to react resinified P-SAL with glycidyltrimethylammonium chloride to yield a strongly basic anion-exchange resin with an ion-exchange capacity of 2.0 mEq/g. The reaction of a simple P-SAL model compound with an epoxide suggested that the phenolic hydroxyl group of the p-hydroxyphenyl nucleus had slightly higher reactivity than that of the guaiacyl nucleus.

To isolate and identify the cement-hardening inhibitory components of keyaki (Japanese zelkova, Zelkova serrata Makino), methanol extractives containing inhibitory components were fractionated by successive organic solvent extraction and column chromatography, and the inhibition of these fractions was determined. Spectroscopic analysis of one isolated compound identified it to be keyakinin with the C-glucoside structure of a flavonol. According to the inhibitory indices, the compound was found to be the main cement-hardening inhibitory component of keyaki. Extraction of keyaki with hot water or a blend of keyaki with up to 30% hinoki as a suitable species diminished the cement-hardening inhibition of wood-cement board to a great extent, suggesting that such treatments are economical countermeasures to this inhibition.

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.

Highly condensed lignin can be transformed by three reactions — phenolation, hydroxymethylation, and neutral sulfonation — to water-soluble lignosulfonate. To elucidate reactivities and products in the latter two reactions, simple compounds were selected as lignin model compounds. With hydroxymethylation of creosol at 60°C, the yield of a condensed-type product with the diarylmethane structure was less than 10%. Hydroxymethylation of 1-guaiacyl-1-p-hydroxy-phenylethane (compound VI) as a phenolized guaiacyl lignin model compound gave four compounds. The initial reaction introduced the hydroxymethyl group mainly in the guaiacyl nucleus, and the additional reaction created two hydroxymethyl groups in the p-hydroxyphenyl nucleus. Contrary to our estimation, treatment of the models with 13C-labeled formaldehyde (H13CIIO) did not form any diarylmethane structure. Neutral sulfite treatment of hydroxymethylated products gave corresponding sulfonates in high yields. Phenolized guaiacylglycerol-β-aryl ether (compound XVI) showed a reactivity similar to that of compound VI.

A significant amount of technical lignins is produced in the pulp and paper industries. However, most technical lignins are burned for thermal recycling and a few percent are used as materials, such as lignosulfonate as a dispersant. Native lignin has a highly complex structure and is susceptible to structural variations depending on the pulping process, thus hindering the effective utilization of lignins. The procedures used to convert lignins into functional materials include depolymerization to monomeric fragments followed by re-building to functional materials, and chemical modifications to generate functional polymers with retained polymeric properties. In this paper, the latter is disserted. The characteristics of technical lignins, which include kraft lignin, lignosulfonate, and organosolv lignin, and their conversion to functional materials such as polyesters, polyethers, polyurethanes, etc. and the applications of lignin-based materials in some fields are discussed.