Revisiting the Mechanism of β-O-4 Bond Cleavage During Acidolysis of Lignin. Part 6: A Review

ABSTRACT

This paper reviews our results on the acidolysis of dimeric non-phenolic β-O-4-type lignin model compounds in aqueous 82% 1,4-dioxane containing an acid at 85°C. It was shown that the mechanism of a C₆-C₂-type model compound, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)ethanol IX, is fairly different from that of a C₆-C₃ analogue, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol XX, suggesting the significance of the presence of the γ-hydroxymethyl group. It was confirmed that the hydride transfer mechanism exists as a reaction route of the benzyl-cation-type intermediates derived from both compounds, and the contribution of this mechanism is greater than expected in the acidolysis of compound XX. An enol ether compound, 2-(2-methoxyphenoxy)-3-(3,4-dimethoxyphenyl)prop-2-en-1-ol, was first detected in the acidolysis of compound XX using the DBr/D₂O/1,4-dioxane system. It was confirmed in the acidolysis of compound XX using HBr that the mechanism is different from that in the system using either HCl or H₂SO₄ and an unknown mechanism contributes to the reaction. This unknown mechanism surprisingly contributed more with decreasing concentration of HBr or Br^?, provided that Br^? still existed in the system.     

Characteristics and Reactivity of Lignin in Acacia and Eucalyptus Woods

The chemical characteristics of lignin, including the Klason lignin content, acid-soluble lignin content, proportion of the aromatic ring types [syringyl ratio = syringyl/(syringyl + guaiacyl)], and proportion of the diastereomeric forms for the β-O-4 structure [erythro ratio = erythro/(erythro + threo)], and pulpability were investigated for 28 wood samples belonging to the genera Acacia and Eucalyptus. Although the lignin characteristics of these 28 woods varied widely, the chemical characteristics of the two genera could be categorized in two clearly distinguished groups on the basis of the syringyl ratio. Clear negative correlations were observed between both the syringyl and erythro ratios and the total lignin content (sum of the Klason and acid-soluble lignin contents) within each genus. In addition, the syringyl ratio correlated positively with the erythro ratio and acid-soluble lignin content, regardless of the genus. The existence of a clear, high correlation between the syringyl and erythro ratios supports the hypothesis that the aromatic ring type (syringyl ratio) is a decisive factor for controlling the diastereomeric forms of the β-O-4 structure (erythro ratio). Each of the wood samples was also subjected to Kraft pulping, and it was demonstrated that the woods with higher syringyl ratios were easier to delignify. This tendency is reasonably attributed to the high reactivity of the erythro-rich and syringyl-rich β-O-4 structures, and the low lignin content of these syringyl-rich woods.     

Structure–Property Relationship in BT-Based Dielectrics for Ni-MLCC: Modification of Grain Boundary

Structure–property relationship in BaTiO₃ (BT)-based dielectrics for multi-layer ceramic capacitors with nickel internal electrode was investigated using samples having various HoO_3/2 concentrations by measuring temperature characteristics of capacitance, voltage–current characteristics, lifetime at highly accelerated life test, high-resolution analytical electron microscope, and frequency response at elevated temperature and ultra-low frequency. It was concluded that the addition of Ho affected the shell and grain boundary (GB) characteristics. Incorporation of Ho into BT perovskite lattice and the change in GB characteristics along with the doped concentration of HoO_3/2 were discussed to better understand the role of doped Ho₂O₃.     

Osteoinduction by Functionally Graded Apatites of Bovine Origin Loaded with Bone Morphogenetic Protein-2

Bioresorbable and functionally graded apatites (fg-HAp) ceramics, which are characterized by gradations in crystallinity and the grain size of hydroxyapatite (HAp:Ca₁₀(PO₄)₆(OH)₂), were designed using bovine bone by the calcination and partial dissolution–precipitation method. The fg-HAp ceramics had macropores of 100–600 μm originated from spongy bone, and micropores of 10–160 nm. Fg-HAp ceramics loaded with recombinant human bone morphogenetic protein-2 (rhBMP-2/fg-HAp) were implanted into the subcutaneous tissue of rats. Eight weeks after the implantation, the surface and bulk degradations of the fg-HAp-containing body fluid occured, and small pieces of fg-HAp were incorporated into the induced bone and fatty marrow, suggesting that osteoinduction occurred in conjunction with bone remodeling. The rhBMP-2/fg-HAp ceramics developed could become a resorbable biomimetic material with fast bioresorption and osteoinduction characteristics.     

Ozonation of C.I. Reactive Yellow 3 and Further Decrease in Dissolved Organic Carbon Concentration by Post-Biodegradation

Using C.I. Reactive Yellow 3 as the target compound, the effect of the combined use of ozonation and post-biodegradation on the decrease in dissolved organic carbon (DOC) concentration was investigated, and the synergistic effect (the difference in the amounts of DOC removed by the biological process between solutions with and without ozonation) was estimated. A decrease in DOC concentration was observed during ozonation and ΔO₃/ΔDOC was decreased from 16.0 to 5.2 with increasing ozonation time. Moreover, an enhancement of biodegradability was shown. A further decrease in DOC concentration was observed during the biodegradation after ozonation. The total amount of DOC removed by the combined method was increased from 73.6 mg at 30 min to 159.9 mg at 4 h. The synergistic effect was in the range of 22.7 to 39.2 mg. BOD₅ was a better indicator of the synergistic effect than BOD₅/DOC.     

Hemicellulose Composition in Different Cell Wall Fractions Obtained using a DMSO/LiCl Wood Solvent System and Enzyme Hydrolysis

In our previous studies on the relationships between lignin structure and hemicellulose composition in a wide range of hardwood species, we showed that the higher the syringyl ratio, the higher the xylan/mannan ratio. In this study, the relationship of the syringyl ratio and xylan/mannan ratio was further studied using fractions obtained by stepwise extraction of finely milled beech wood by use of aqueous dioxane and subsequent dimethyl sulfoxide (DMSO)/LiCl solvents with increasing LiCl concentration. Each soluble fraction obtained with a different LiCl concentration was compared with the corresponding insoluble residue, and it was shown that both the syringyl ratio and xylan/mannan ratio were always higher in the insoluble fraction. To analyze polysaccharides closely located with lignin, milled wood lignin (MWL), and cellulolytic enzyme lignin (CEL) obtained by enzyme treatment after DMSO/LiCl swelling were investigated. Although the xylan/mannan ratio of MWL was higher, that of CEL with more than 80% lignin yield was lower.     

Separation of Ru(III), Rh(III) and Pd(II) from nitric acid solutions using ion-exchange resins bearing carboxylic betaine

To understand the adsorption properties of a styrene–divinylbenzene copolymer functionalized with N,N,N-trimethylglycine, AMP03, the adsorption behaviours for platinoid ions (Ru(III), Rh(III) and Pd(II)) were examined. Furthermore, we performed adsorption experiments using sample solutions by adding triethylamine, thiourea and N,N,N-trimethylglycine. Based on the adsorption data obtained in this study, we performed chromatographic experiments. The results indicated that all platinoid ions in the feed solution completely adsorbed on AMP03, and almost 80% of the adsorbed platinoid ions were recovered. These results show that AMP03 has the potential to recover Ru(III), Rh(III) and Pd(II) from high-level liquid waste.     

Statistical Analysis of Surface Reconstruction Domains on InAs Wetting Layer Preceding Quantum Dot Formation

Surface of an InAs wetting layer on GaAs(001) preceding InAs quantum dot (QD) formation was observed at 300°C with in situ scanning tunneling microscopy (STM). Domains of (1 × 3)/(2 × 3) and (2 × 4) surface reconstructions were located in the STM image. The density of each surface reconstruction domain was comparable to that of subsequently nucleated QD precursors. The distribution of the domains was statistically investigated in terms of spatial point patterns. It was found that the domains were distributed in an ordered pattern rather than a random pattern. It implied the possibility that QD nucleation sites are related to the surface reconstruction domains.     

Preparation of 1 1 1-textured BaTiO3 ceramics by templated grain growth method using novel template particles

Dense BaTiO₃ ceramics with 1 1 1-texture were prepared by the TGG process. Platelike BaTiO₃ particles with their 1 1 1 direction perpendicular to the plate face were prepared by the reaction of platelike Ba₆Ti₁₇O₄₀ particles with BaCO₃ particles in molten NaCl. A green compact was composed of the aligned, platelike BaTiO₃ template particles dispersed in the matrix of small, equiaxed BaTiO₃ particles. Sintering caused densification and also the growth of template particles at the expense of matrix particles, resulting in texture development. Densification prior to grain growth was found to be necessary to obtain highly textured ceramics, and the effect of pre-sintering conditions on texture development was examined.