Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer
To elucidate the chemical linkages between lignin and carbohydrates in ginkgo cell walls, <sup>13</sup>C-<sup>2</sup>H-enriched cell wall-dehydrogenation polymers (CW-DHP) were selectively prepared with cambial tissue from <i>Ginkgo biloba</i> L. by feeding D-gluc...
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MDPI AG
2021-09-01
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| Online Access: | https://www.mdpi.com/1420-3049/26/19/5740 |
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| author | Kai Zhang Yanchao Liu Sheng Cui Yimin Xie |
| author_facet | Kai Zhang Yanchao Liu Sheng Cui Yimin Xie |
| author_sort | Kai Zhang |
| collection | DOAJ |
| description | To elucidate the chemical linkages between lignin and carbohydrates in ginkgo cell walls, <sup>13</sup>C-<sup>2</sup>H-enriched cell wall-dehydrogenation polymers (CW-DHP) were selectively prepared with cambial tissue from <i>Ginkgo biloba</i> L. by feeding D-glucose-[6-<sup>2</sup>H<sub>2</sub>], coniferin-[α-<sup>13</sup>C], and phenylalanine ammonia-lyase (PAL) inhibitor. The abundant detection of <sup>13</sup>C and <sup>2</sup>H confirmed that D-glucose-[6-<sup>2</sup>H<sub>2</sub>] and coniferin-[α-<sup>13</sup>C] were involved in the normal metabolism of ginkgo cambial cells that had been effectively labelled with dual isotopes. In the ginkgo CW-DHP, ketal and ether linkages were formed between the C-α of lignin side chains and carbohydrates, as revealed by solid state CP/MAS <sup>13</sup>C-NMR differential spectroscopy. Furthermore, the DMSO/TBAH ionic liquids system was used to fractionate the ball-milled CW-DHP into three lignin-carbohydrate complex (LCC) fractions: glucan–lignin complex (GL), glucomannan–lignin complex (GML), and xylan–lignin complex (XL). The XRD determination indicated that the cellulose type I of the GL was converted into cellulose type II during the separation process. The molecular weight was in the order of Ac-GL > Ac-GML > XL. The <sup>13</sup>C-NMR and <sup>1</sup>H-NMR differential spectroscopy of <sup>13</sup>C-<sup>2</sup>H-enriched GL fraction indicated that lignin was linked with cellulose C-6 by benzyl ether linkages. It was also found that there were benzyl ether linkages between the lignin side chain C-α and glucomannan C-6 in the <sup>13</sup>C-<sup>2</sup>H-enriched GML fraction. The formation of ketal linkages between the C-α of lignin and xylan was confirmed in the <sup>13</sup>C-<sup>2</sup>H-enriched XL fraction. |
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| spelling | doaj.art-a963a1f6e51f4f34bbfa952d5f9e7c342023-11-22T16:31:56ZengMDPI AGMolecules1420-30492021-09-012619574010.3390/molecules26195740Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope TracerKai Zhang0Yanchao Liu1Sheng Cui2Yimin Xie3Research Institute of Pulp & Paper Engineering, Hubei University of Technology, Wuhan 430068, ChinaResearch Institute of Pulp & Paper Engineering, Hubei University of Technology, Wuhan 430068, ChinaResearch Institute of Pulp & Paper Engineering, Hubei University of Technology, Wuhan 430068, ChinaResearch Institute of Pulp & Paper Engineering, Hubei University of Technology, Wuhan 430068, ChinaTo elucidate the chemical linkages between lignin and carbohydrates in ginkgo cell walls, <sup>13</sup>C-<sup>2</sup>H-enriched cell wall-dehydrogenation polymers (CW-DHP) were selectively prepared with cambial tissue from <i>Ginkgo biloba</i> L. by feeding D-glucose-[6-<sup>2</sup>H<sub>2</sub>], coniferin-[α-<sup>13</sup>C], and phenylalanine ammonia-lyase (PAL) inhibitor. The abundant detection of <sup>13</sup>C and <sup>2</sup>H confirmed that D-glucose-[6-<sup>2</sup>H<sub>2</sub>] and coniferin-[α-<sup>13</sup>C] were involved in the normal metabolism of ginkgo cambial cells that had been effectively labelled with dual isotopes. In the ginkgo CW-DHP, ketal and ether linkages were formed between the C-α of lignin side chains and carbohydrates, as revealed by solid state CP/MAS <sup>13</sup>C-NMR differential spectroscopy. Furthermore, the DMSO/TBAH ionic liquids system was used to fractionate the ball-milled CW-DHP into three lignin-carbohydrate complex (LCC) fractions: glucan–lignin complex (GL), glucomannan–lignin complex (GML), and xylan–lignin complex (XL). The XRD determination indicated that the cellulose type I of the GL was converted into cellulose type II during the separation process. The molecular weight was in the order of Ac-GL > Ac-GML > XL. The <sup>13</sup>C-NMR and <sup>1</sup>H-NMR differential spectroscopy of <sup>13</sup>C-<sup>2</sup>H-enriched GL fraction indicated that lignin was linked with cellulose C-6 by benzyl ether linkages. It was also found that there were benzyl ether linkages between the lignin side chain C-α and glucomannan C-6 in the <sup>13</sup>C-<sup>2</sup>H-enriched GML fraction. The formation of ketal linkages between the C-α of lignin and xylan was confirmed in the <sup>13</sup>C-<sup>2</sup>H-enriched XL fraction.https://www.mdpi.com/1420-3049/26/19/5740lignin–carbohydrate complexesCW-DHPisotope labellingginkgoNMR |
| spellingShingle | Kai Zhang Yanchao Liu Sheng Cui Yimin Xie Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer Molecules lignin–carbohydrate complexes CW-DHP isotope labelling ginkgo NMR |
| title | Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer |
| title_full | Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer |
| title_fullStr | Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer |
| title_full_unstemmed | Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer |
| title_short | Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by <sup>13</sup>C-<sup>2</sup>H Dual Isotope Tracer |
| title_sort | elucidation of the structure of lignin carbohydrate complexes in ginkgo cw dhp by sup 13 sup c sup 2 sup h dual isotope tracer |
| topic | lignin–carbohydrate complexes CW-DHP isotope labelling ginkgo NMR |
| url | https://www.mdpi.com/1420-3049/26/19/5740 |
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