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     

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

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

Chemical structures and thermochemical properties of bagasse lignin

1 Introduction Agricultural residues are an important renewable bio- mass resource. The annual production is more than 600 million tons in China. With the reduction of fossil fuel resources, the new trend is to acquire chemicals and energy from renewable resources. To produce green chemicals and clean fuels by developing bio- mass, biorefinery technology is one of the more promising technologies and objectives. Bagasse consists of cellulose, hemicellulose and lignin. Earlier studies have sho…     

The mechanism of the Mäule colour reaction introduction of methylated syringyl nuclei into softwood lignin

Summary Ezo spruce (Picea jezoensis) wood meal and milled wood lignin were successively reduced with sodium borohydride, methylated with methanol-HCl, oxidized with Fremy's salt, reduced with sodium dithionite, and methylated with diazomethane. Permanganate oxidation of the treated milled wood lignin showed that 0.08–0.1/C9 units of 3,4,5-trimethoxyphenyl groups were introduced into the softwood lignin. Although hardwood meal (beech, Fagus crenata) methylated with diazomethane gave a purple-red colour with the Mäule test, the treated softwood meal gave only a dark brown colour. The aromatic nuclei of lignin were broken down by the Mäule treatment. The consumption of permanganate by treated softwood lignin was higher than by hardwood lignin, which suggests that the guaiacyl nuclei were broken down severely. It is proposed that the purple-red colour obtained from methylated hardwood lignin with the Mäule colour test is generated by reaction of syringyl groups which were liberated by -ether cleavage under the permanganate oxidation conditions.     

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     

Rapid assessment of coniferous biomass lignin–carbohydrates with near-infrared spectroscopy

The main objective of this research was to construct accurate near-infrared reflectance (NIR) models of wood chemistry. Wet chemistry procedures and high-performance liquid chromatography methods were employed to analyze the chemical composition of southern pine. The NIR spectra were collected from 21 wood samples, which were milled down to different particle size classes. NIR calibration and prediction models were established using two modeling methods with different pretreatments. Furthermore, the spectrum range used in the NIR models was refined to achieve higher prediction accuracy. Results showed that NIR model precision could be improved considerably by decreasing the particle size to a very fine powder coupled with a targeted spectrum range. Superior prediction models for lignin and holocellulose content were constructed, while models for extractives and cellulose contents were also strong.     

Can the structure of dormant cambium and the widths of phloem and xylem increments be used as indicators for tree vitality?

We investigated the structure and width of the dormant cambium and of the increments of phloem and xylem of Quercus robur to estimate their potential as indicators for tree vitality. The samples were taken from three woodlands, two in Slovenia [Krakovo forest (KRA) and Murska Suma (MUS)] and one in Croatia [Kobiljak (KOB)], with reported tree decline. The number of dormant cells seems to reflect the initial capacity of the cambium to accomplish cell division. With the exception of two trees at KRA, cell production was always higher on the xylem side than on the phloem side. The annual phloem increments were narrower, less variable among trees and with clear lower and upper limits. With increased cambial cell productivity, the share of the xylem in the total annual radial increment increased following a curvilinear function. In trees with an annual radial increment >3.5 mm, the xylem size represented more than 90 % of the total radial growth. The anatomical variables analyzed show that the most limiting environmental conditions seem to prevail at KRA, whereas the conditions at MUS seem to be most favorable in terms of radial growth. Analysis of the width and structure of xylem and phloem increments, the number of dormant cambial cells and their inter-relationships can provide additional information on the vitality of oaks.     

Revisiting the mechanism of <Emphasis Type="Italic">β-O</Emphasis>-4 bond cleavage during acidolysis of lignin IV: dependence of acidolysis reaction on the type of acid

The dependence of the acidolysis reaction of a C₆-C₃ dimeric nonphenolic β-O-4 type lignin model compound, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl) propane-1,3-diol (veratrylglycerol-β-guaiacyl ether, VG), on the type of acid applied was examined using three different acids [0.2 mol/l HCl, 0.2 mol/l HBr, and 0.1 mol/l (0.2 N) H₂SO₄ in 82% aqueous 1,4-dioxane at 85°C]. In the HCl system, the major reaction modes of the corresponding benzyl cation-type intermediate (BC), which is produced by protonation of the α-hydroxyl group of VG and successive release of the water molecule, are the abstraction of the β-proton and hydride transfer from the β-to the α-position. The liberation of formaldehyde from the γ-hydroxymethyl group of BC is the predominant reaction mode in the H₂SO₄ system. Apparently, an unknown reaction mode or modes is operative in the early stage of the HBr system that causes rapid disappearance of VG accompanied by the quantitative formation of 2-methoxyphenol without affording the common counterpart of a Hibbert’s ketone, 1-hydroxy-3-(3,4-dimethoxyphenyl) propan-2-one. The reaction mode in the HBr system changes with the progress of the reaction and is the same as that in the HCl system after the early stage.     

Synergistic contribution of hydrosulfide and carbonate anions to the β-O-4 bond cleavage of lignin model compounds in a green liquor pretreatment for enzymatic hydrolysis of lignocellulosic materials

To examine why green liquor (GL) pretreatment of lignocellulosic materials effectively facilitates enzymatic saccharification under conditions milder than those of a common alkaline cooking process, dimeric β-O-4 type lignin model compounds with and without free phenolic hydroxyl group were reacted in several alkaline solutions including a model solution of GL, which mainly contains Na₂CO₃ and Na₂S. The β-O-4 bond of the phenolic model compound was cleaved with a sufficient rate in the model solution of GL. The β-O-4 bond cleavage of the non-phenolic model compound was more frequent in the model solution of GL than in other alkaline solutions. These results suggest that β-O-4 bonds present in lignocellulosic materials are effectively cleaved in a GL pretreatment. It was also suggested that HS^? and CO₃ ^2? synergistically contribute to the β-O-4 bond cleavage of the non-phenolic model compound under GL pretreatment conditions.     

The relative importance of climatic gradient versus human disturbance in determining population structure of Afzelia africana in the Republic of Benin§

The study aimed to investigate the relative significance of effects of climatic variability and human disturbance on the population structure of the threatened species Afzelia africana Sm. ex Pers. in the Republic of Benin in West Africa. Forest inventory data such as regeneration density, tree diameter and total height were compiled from A. africana forest stands under different disturbance regimes in the three climatic zones of Benin. Multiple generalised linear models and non-linear diameter–height equations were fitted to contrast the individual effects of categorical variables, such as climatic zone and disturbance level. Results revealed significantly higher scaling coefficients in less drier regions and low-disturbance stands. The diameter–height relationship was more controlled by the climatic zone than by the disturbance level. Accordingly, the disturbance level contributed only to the intercept of the diameter–height model, whereas the climatic zone significantly influenced both intercept and slope. In addition, when climatic zone and disturbance level were considered as sources of variation in the diameter–height model, the former explained the greater marginal variance. It was concluded that climate has the greater effect on population structure of A. africana in natural stands.     

Relationship between structure and function of mammalian vibrissa

MaterialsandmethodsMaterialsThevibrissaeinthisexperimentweresampledfromHarbinZooandtheSpecimenRoomofNortheastForestryUniversity.Thesesamplescover4families,Carnivora,Perissodactyla,RodentiaandPrim8ts.MethodsThewholevibrissawithhairrootwassampIedinvarioussitsofmammaIbodySuchasmouth,eyelid,face,neckandjaw.Bycomparison,theauthordidnotfindsignificantdifferencesinvibrissastruCtureofdifferentpartsofbody,SothevibrissaofcheekisusedfOrobservationandcomparison-SampIeswereobservedwithIightmicrosc…     

Characterization of Brauns’ lignin from fresh and vacuum-dried birch (Betula pendula) wood

Brauns’ lignins present in the methanol extracts of fresh birch (Betula pendula) xylem and of sawn birch board subjected to vacuum drying were characterized by ¹H and ¹³C NMR spectroscopy (1D and 2D), IR spectroscopy, gel permeation chromatography (GPC) and colour measurements (CIELab) in order to find out whether Brauns’ lignin could contribute to the colour change of sawn timber that occurred during vacuum drying. The two Brauns’ lignin samples contained about equal amounts of syringylpropane and guaiacylpropane units linked with β-O-4 and β–β side-chain structures. Molecular weight of the Brauns’ lignin of vacuum-dried birch board (acetylated: 5,200 g mol⁻¹) was higher than that of the Brauns’ lignin of fresh birch wood (acetylated: 4,400 g mol⁻¹). The Brauns’ lignin of vacuum-dried wood was also clearly darker and more prominently yellow and red; between the Brauns’ lignin samples was 23.59. The differences in the molecular weights and colours suggest that the Brauns’ lignin underwent a chemical change during vacuum drying of the wood and that this change may have affected the colour of the wood.     

Effects of selection cutting on the forest structure and species diversity of evergreen broa-leaved forest in northern Fujian, southern China

The short-term effects of selection cutting of different intensities on the forest structure and species diversity of evergreen broad-leaved forest in northern Fujian Province were investigated and analyzed. The results showed that selection cutting of low and medium intensities caused little variation in the forest structure. After cutting, the dominant species retained their leading status in the community. However, the community structure changed significantly following selection cutting of high and extra-high intensities; the status of the dominant species of the community declined dramatically. Some tree species began to disappear from the sampling plots. Except for extra-high intensity cutting, the diversity of tree species did not change significantly for the other three cutting intensities. However, the evenness of the stands was very different among the four kinds of cutting plots. For low and medium intensity selection cutting, the evenness declined slightly. For extra-high intensity selection cutting, the evenness increased to some extent, which might be due to a more even distribution of tree species after cutting. Cutting operations resulted in some adverse reactions to development of arborous species diversity of evergreen broad-leaved forest, particularly serious damage to the forest canopy. But the rational selection cuttings, which may benefit the restoration and maintenance of species diversity over a long period and may come about from the variations in environmental factors such as sunlight, temperature and humidity.     

A preliminary study on the genetic structure of Northern European pinus sylvestris L. by means of neutral nuclear microsatellite markers

This paper aimed to investigate the genetic structure (GS) of Scots pine in the northern area of its distribution range by means of seven neutral nuclear microsatellite markers. In particular, the postglacial recolonization of these areas and possible different adaptation patterns in distinct refugia were studied. The GS and diversity were assessed with seven pairs of neutral nuclear microsatellite primers. A high genetic diversity was found in the Scots pine material tested, along with a shallow GS. This pattern is typical for recolonized areas and species with large population sizes, which are connected by pollen-mediated gene flow. A STRUCTURE analysis found two genetic groups to be the most likely, one south-eastern and one north-western group that meet in Fennoscandia. This indicates that Scots pine recolonization of Fennoscandia might have taken place from two different directions (south-west and north-east). Scots pine that recolonized the area originated in at least two different refugia during the last glacial maximum. The glacial survival in distinct refugia can have led to different adaptation patterns and growth optima in the different groups as reflected in the formation of latewood content, where lineage was a significant influencing factor.     

Age structure and dynamics of Zoysia japonica module population

The age structure of the natural Zoysia japonica clonal population at Qipan Mountain in Huishan Scenic Spot of Shenyang,Liaoning Province, China was studied using the morphological method in 2003 and 2004. The dynamics of leaves were recorded and the dynamics of tiller and rhizome in the growing season were observed. The results indicated that the rhizomes formed in different years changed in color and rigidity. Its internodes produced in autumn became shorter. The number of naked nodes changed with the tiller age.Rhizome and tiller characters were used as a foundation for judging the ages of modules in this study. The longevity of tiller and rhizome was 3 years at most. At the beginning of the growing season, 2-year-old tillers and rhizomes predominated. Then I -year-old tillers and rhizomes increased rapidly and became dominant in July. The proportion of buds to tillers on quantity was stable at about 30% in the mid-phase of the growing season and rose to about 50% in autumn. The seasonal dynamics of tiller, rhizome and bud was very important to guarantee the sustained existence of the Zoysia japonica population. The turnover of modules was the mechanism of sustaining the rejuvenation of the Zoysia japonica clonal population.     

Status quo of the Life Network of the Changjiang River

Alongthe6300-kmfulllengthoftheChangjiangRiver,agroupoflakesthatstretchesgreenandvastconstitutesauniquelifesystemofitsvalley.Here,thereusedtobesomuchvitality:howlingmonkeys,flyingbirdsandcountlessaquaticorgasmsinbluewaterandwhitesand,givingrisetothemostpro…