Formation and chemical structures of acid-soluble lignin I: sulfuric acid treatment time and acid-soluble lignin content of hardwood

To elucidate the formation mechanism of acidsoluble lignin (ASL) formed in the Klason lignin determination, beech wood meals were treated with sulfuric acid (SA) under various conditions, and the ASL solution was extracted with CHC1₃. The results indicated the following: (1) wood components yielding ASL are dissolved in 72% SA during the initial stage; (2) the quantity of ASL is highest during the initial stage, then decreases with prolonged time of 72% SA treatment and finally reaches a constant value; (3) soluble lignin prepared by 72% SA treatment and subsequent standing in 3% SA again yield insoluble Klason lignin and ASL after boiling in 3% SA; and (4) about half the amount of ASL is dissolved in CHC1₃. The foregoing suggest that wood components yielding ASL are dissolved in 72% SA at the beginning and finally change to ASL after being subjected to depolymerization, hydrolysis, and other reactions. ASL may thus be composed of low-molecular-weight degradation products and hydrophilic derivatives of lignin.     

Analysis of the structure of lignin-carbohydrate complexes by the specific13C tracer method

In the present study the specifically¹³C-enriched lignin precursors of biosynthesis (i.e., coniferin-[side chain–¹³C], coniferin-[side chain-–¹³C] and coniferin-[side chain-–¹³C]) were synthesized and administered exogeneously to ginkgo shoots (Ginkgo biloba L.) to obtain¹³C-enriched lignin-carbohydrate complexes (LCCs). The specifically¹³C-enriched LCCs were isolated from the newly formed xylem of ginkgo shoots administered with the¹³C-enriched precursors and degraded by enzymes. Lignin-rich fractions, so called enzyme-degraded LCCs (EDLCCs), were obtained. By determining their¹³C-NMR spectra, information related to the chemical structure of lignin building units and linkages between phenylpropane units of lignin and carbohydrates were obtained. It was found that these precursors were incorporated in natural lignin successfully. Three lignin-carbohydrates linkages (i.e., ether type, ester type, ketal type) were found at the C -position of the side chain of phenylpropane units in ginkgo LCC. No lignin-carbohydrate bond at the C- or C-position of the lignin side chain was observed in the¹³C-NMR spectra of the¹³C-enriched LCCs. This fact indicates that a specific¹³C tracer technique can be useful in NMR study of the chemical structure of LCCs.Part of this paper was presented at the 5th Pacific Polymer Conference, Kyongju, Korea, October 1997     

Application of cationic polymer prepared from sulfuric acid lignin as a retention aid for usual rosin sizes to neutral papermaking

Cationic polymers that acted as the retention aids for usual rosin sizes in neutral papermaking were prepared from sulfuric acid lignin (SAL), one type of acid lignin. To convert SAL to the cationic polymer (MP-SAL), SAL was phenolated and then treated by the Mannich reaction to introduce the amino groups. In the MP-SAL single system, MP-SAL exhibited high sizing effectiveness in neutral papermaking with the rosin emulsion size. However, MP-SAL showed no sizing effectiveness when soap rosin size was used. MP-SAL showed increased sizing effectiveness as the pK _a of the introduced amino group increased. From this and comparison of the sizing degrees of MP-SAL and polyethylenimine, which possesses a linear structure, it was suggested that the sizing effectiveness was not only affected by the charge density and molecular weight, but also by the basicity of the introduced amino groups and the molecular structure of the retention aid. In the alum–MP-SAL dual system, alum and MP-SAL synergistically enhanced the sizing effectiveness in the rosin emulsion sizing at neutral pH. In turn, this allowed a decrease in the MP-SAL dosage and resulted in a small decrease in brightness.Part of this report was presented at the 48th Lignin Symposium, October 2003, Fukui     

Chemical modification of wood by non-formaldehyde cross-linking reagents

Summary Using sulfur dioxide (SO₂) as catalyst, wood specimens were treated with nonformaldehyde cross-linking reagents such as glyoxal, glutaraldehyde and dimethylol dihydroxy ethyleneurea (DMDHEU). The results of dimensional stability, acoustic properties, and mechanical strength tests were compared with those obtained from formaldehyde treatment. With glyoxal and glutaraldehyde treatments, antiswelling efficiency (ASE) reached around 70%, which is comparable to the values attained by formaldehyde treatment, although the accompanying weight gain was much larger than for the latter, whereas DMDHEU did not give sufficiently high ASE. None of the treatments, significantly increased specific dynamic Young's modulus (E/) with the exception of the DMDHEU treatment, loss tangent (tan ) decreased substantially, about 50 and 60% in longitudinal and radial directions respectively, which were somewhat exceeding the formaldehyde treatment. The results suggested that the improvement of the dimensional stability and acoustic properties is partly attributed to the formation of cross-links.     

A Mixed-Integer Optimization Technique for Developing a Sulfur Emission Control Strategy for China

The economical development and increasing population of China and other East Asian countries is expected to be accompanied by an increase in the emission of air pollutants. The objective of this study is to develop an effective and economical emission control strategy for sulfur in East Asia. There are existing methods for controlling sulfur emission, such as changing to lower sulfur content fuel, introducing desulfurization devices for emission sources, and promoting efficient energy use. The applicability of such measures is restricted by both energy supply and control cost, amongst other concerns. As a case study, an optimal control strategy based on the estimated sulfur emission for China in 2010, is simulated using a Mixed-Integer Linear Programming technique with several restrictions that satisfies, among other constraints, the atmospheric environment requirements for SO₂ and the soil load limit for SO₄ deposition.     

Use of electrical conductivity to estimate effects of competing ions on radionuclide distribution coefficients

The distribution coefficient (K _d) between the soil solid phase and the liquid phase is a commonly used parameter to evaluate radionuclide behavior in soil. For reliable evaluation, the variability of the K _ddue to changes of environmental conditions should be clarified. In the present study, applicability of electrical conductivity (EC) to estimate effects of competing ions on K _dwas examined in batch experiments. The K _dof five radionuclides (⁶⁰Co, ⁵⁴Mn, ⁸⁵Sr, ¹³⁷Cs, ⁶⁵Zn) were found to be in inverse proportion to the supernatant EC. The K _dof ⁶⁰Co and ⁵⁴Mn were increasing at 7 days and no stable K _dcould be determined. For ⁸⁵Sr, ¹³⁷Cs, and ⁶³Zn, the regression equations obtained between the K _dof the equilibrium state and the supernatant EC were validated in another experiment; it is expected that their K _ds can be determined accurately using the EC. Because of its simplicity in measurements, using EC should be very practical for estimating effects of competing ions on K _dof selected radionuclides.     

Evidence for the biosynthetic pathway from sinapic acid to syringyl lignin using labeled sinapic acid with stable isotope at both methoxy groups in Robinia pseudoacacia and Nerium indicum

A tracer experiment using synthesized labeled lignin precursors was designed to confirm the actual biosynthetic pathway for syringyl lignin. Tetradeuteroferulic acid-[8-D, 3-OCD(3)] and heptadeuterosinapic acid-[8-D, 3,5-OCD(3)] were synthesized and fed to shoots of robinia (Robinia pseudoacacia) and oleander (Nerium indicum) trees. The incorporation of each labeled precursor into lignin was traced by gas chromatography-mass spectrometry. The synthesized sinapic acid, in which both methoxy groups were labeled, was useful in monitoring the conversion of sinapic acid into syringyl lignin. When heptadeuterosinapic acid was fed, syringyl units containing seven deuterium labels were detected. The results of this study support the traditionally accepted pathway that sinapic acid is converted to sinapyl alcohol via sinapoyl-CoA in robinia and oleander.     

Identification of the core rumen bacterial taxa and their population dynamics during the fattening period in Japanese Black cattle

The rumen microbiota comprises a vast range of bacterial taxa, which may affect the production of high-quality meat in Japanese Black cattle. The aim of this study was to identify core rumen microbiota in rumen fluid samples collected from 74 Japanese Black cattle raised under different dietary conditions using 16S rRNA gene amplicon sequencing. In the rumen of fattening Japanese Black cattle, 10 bacterial taxa, showing >1% average relative abundance and >95% prevalence, irrespective of the dietary conditions and the fattening periods, were identified as the core rumen bacterial taxa, which accounted for approximately 80% of the rumen microbiota in Japanese Black cattle. Additionally, population dynamics of the core rumen bacterial taxa revealed two distinct patterns: Prevotella spp. and unclassified Bacteroidales decreased in the mid-fattening period, whereas unclassified Clostridiales, unclassified Ruminococcaceae, Ruminococcus spp., and unclassified Christensenellaceae increased during the same period. Therefore, the present study reports the wide distribution of the core rumen bacterial taxa in Japanese Black cattle, and the complementary nature of the population dynamics of these core taxa, which may ensure stable rumen fermentation during the fattening period.