|Budget Amount *help
¥3,500,000 (Direct Cost : ¥3,500,000)
Fiscal Year 2003 : ¥1,000,000 (Direct Cost : ¥1,000,000)
Fiscal Year 2002 : ¥2,500,000 (Direct Cost : ¥2,500,000)
The incorporation of soil-pollutant organic substances into lignin was investigated using both a bulk dehydrogenation copolymer of p-chloroaniline and coniferyl alcohol (Cl-DHP) and a bulk dehydrogenation polymer of coniferyl alcohol alone (G-DHP). Although the yield of Cl-DHP was very low (4.4%) compared to that of G-DHP (74%), the elemental analysis of Cl-DHP (Cl 3.44% ; N 1.47%) demonstrated that Cl-DHP incorporates p-chloroaniline with the 5:1 ratio of coniferyl alcohol-to-p-chloroaniline.
Integrated ^<13>C-NMR signal intensities between 70-90 ppm showed that acetylated G-DHP revealed the signal intensities attributable to the side chain carbons of β-O-4, β-β and β-5 linkages. Although acetylated Cl-DHP also showed the signal intensities attributable to the side chain carbons of the latter two linkages, it lacked the signal intensities attributable to the Cα of the Cα-O-Ac of β-O-4 subunits, contrary to acetylated G-DHP showing the intense Cα signal intensities. Instead, signal inte
nsities attributable to the Cβ of β-O-4 linkages with the Cα-NH were newly observed. Two-dimensional ^1H-^<13>C chemical shift correlation NMR studies of the DHPs also supported these findings. These NMR results suggest that the incorporated p-chloroaniline is linked at the Cα position of β-O-4 subunits.
Tetramethylammonium hydroxide (TMAH) thermochemolysis-gas chromatography-mass spectrometry (GC-MS) of G-DHP and Cl-DHP revealed a considerable level of isomeric stilbene products stemming from dehydrodiconiferyl alcohol type subunits, coniferyl alcohol dimethyl ether stemming from coniferyl alcohol-end groups, and a large level of pinoresinol dimethyl ether, along with a large level of 1-(3,4-dimethoxyphenyl)-1,2,3-trimethoxypropane whose pyrolytic origins are guaiacylglycerol moieties involved in β-O-4 type linkages. TMAH thermochemolysis-GC-MS of Cl-DHP showed a large level of p-chloroanilines, and a small level of (4-chlorophenyl)-[1-(3,4-dimethoxyphenyl)-2,3-dimethoxypropyl]amine whose pyrolytic origins are β-O-4 type subunits having p-chloroaniline at the Cα position via a benzylamine linkage, and a trace level of 1-(3,4-dimethoxyphenyl)-1,2,3-trimethoxypropane, although pinoresinol dimethyl ether and coniferyl alcohol dimethyl ether were observed in a similar level to those from G-DHP. Less