Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study

Elder, Thomas; del Río, José C.; Ralph, John; Rencoret, Jorge; Kim, Hoon; Beckham, Gregg T.; Crowley, Michael F.

doi:10.1021/acssuschemeng.0c02880

Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study

Journal Article · Thu Jul 09 00:00:00 EDT 2020 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.0c02880· OSTI ID:1660142

^[1]; ^[2]; ^[3]; ^[2]; ^[3]; ^[4]; ^[4]

US Dept. of Agriculture (USDA), Auburn, Alabama (United States)
Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS) (Spain)
Univ. of Wisconsin, Madison, WI (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

This perspective summarizes and compares computational results for the thermodynamics of bond dissociation, coupling, and rearomatization for a number of noncanonical lignin monomer–lignol combinations that have been found to occur experimentally. The noncanonical lignin monomers discussed are tricin, caffeyl alcohol, 5-hydroxyconiferyl alcohol, and piceatannol. Among dimeric combinations, the results for bond dissociation are generally similar, but in cases for which trimers have been reported (tricin-lignol adducts), this value can be quite variable, with stereochemical and structural preferences. Among the adducts examined thus far, the energies associated with quinone methide formation and rearomatization are not dissimilar and would not impede subsequent polymerization. These fundamental studies may help to elucidate how lignin monomers are incorporated into the lignin polymer, provide leads for targeted genetic modification, and be of use in deconstruction for the production of commodity chemicals.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1660142

Report Number(s):: NREL/JA--2800-77352; MainId:26298; UUID:43ce9ffd-6f2e-411b-8db0-064ae15c74f0; MainAdminID:15196

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 30 Vol. 8; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Distribution oferythro andthreo forms of different types of β-O-4 structures in aspen lignin by13C NMR using the 2D INADEQUATE experiment Bardet, Michel; Robert, Danielle; Lundquist, Knut Magnetic Resonance in Chemistry, Vol. 36, Issue 8 https://doi.org/10.1002/(SICI)1097-458X(199808)36:8<597::AID-OMR345>3.0.CO;2-G	journal	August 1998
Lignification: are Lignins Biosynthesized via simple Combinatorial Chemistry or via Proteinaceous Control and Template Replication? Ralph, John; Brunow, Gösta; Harris, Philip J. Recent Advances in Polyphenol Research, Vol. 1 https://doi.org/10.1002/9781444302400.ch2	book	July 2008
Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T. Angewandte Chemie International Edition, Vol. 55, Issue 29 https://doi.org/10.1002/anie.201510351	journal	June 2016
Hydroxycinnamate Conjugates as Potential Monolignol Replacements: In vitro Lignification and Cell Wall Studies with Rosmarinic Acid Tobimatsu, Yuki; Elumalai, Sasikumar; Grabber, John H. ChemSusChem, Vol. 5, Issue 4 https://doi.org/10.1002/cssc.201100573	journal	February 2012
Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates Regner, Matt; Bartuce, Allison; Padmakshan, Dharshana ChemSusChem, Vol. 11, Issue 10 https://doi.org/10.1002/cssc.201800617	journal	May 2018
Assessing the Viability of Recovery of Hydroxycinnamic Acids from Lignocellulosic Biorefinery Alkaline Pretreatment Waste Streams Karlen, Steven D.; Fasahati, Peyman; Mazaheri, Mona ChemSusChem, Vol. 13, Issue 8 https://doi.org/10.1002/cssc.201903345	journal	March 2020
On the distribution of the diastereomers of the structural elements in lignins: the steric course of reactions mimicking lignin biosynthesis Brunow, G.; Karlsson, O.; Lundquist, K. Wood Science and Technology, Vol. 27, Issue 4 https://doi.org/10.1007/BF00195305	journal	May 1993
Hydroxycinnamates in lignification Ralph, John Phytochemistry Reviews, Vol. 9, Issue 1, p. 65-83 https://doi.org/10.1007/s11101-009-9141-9	journal	August 2009
Lignin-ferulate cross-links in grasses: active incorporation of ferulate polysaccharide esters into ryegrass lignins Ralph, John; Grabber, John H.; Hatfield, Ronald D. Carbohydrate Research, Vol. 275, Issue 1, p. 167-178 https://doi.org/10.1016/0008-6215(95)00237-N	journal	September 1995
13C NMR of flavonolignans from Hydnocarpus wightiana Parthasarathy, M. R.; Ranganathan, K. R.; Sharma, D. K. Phytochemistry, Vol. 18, Issue 3 https://doi.org/10.1016/S0031-9422(00)81905-6	journal	January 1979
Reassignment of relative stereochemistry at C-7 and C-8 in arylcoumaran neolignans Li, Shiming; Iliefski, Tommy; Lundquist, Knut Phytochemistry, Vol. 46, Issue 5 https://doi.org/10.1016/S0031-9422(97)00360-9	journal	November 1997
Designer lignins: harnessing the plasticity of lignification Mottiar, Yaseen; Vanholme, Ruben; Boerjan, Wout Current Opinion in Biotechnology, Vol. 37 https://doi.org/10.1016/j.copbio.2015.10.009	journal	February 2016
Lignin biosynthesis and its integration into metabolism Vanholme, Ruben; De Meester, Barbara; Ralph, John Current Opinion in Biotechnology, Vol. 56 https://doi.org/10.1016/j.copbio.2019.02.018	journal	April 2019
Lignin structure and its engineering Ralph, John; Lapierre, Catherine; Boerjan, Wout Current Opinion in Biotechnology, Vol. 56 https://doi.org/10.1016/j.copbio.2019.02.019	journal	April 2019
Computational study of bond dissociation enthalpies for lignin model compounds: β-5 Arylcoumaran Younker, Jarod M.; Beste, Ariana; Buchanan, A. C. Chemical Physics Letters, Vol. 545 https://doi.org/10.1016/j.cplett.2012.07.017	journal	August 2012
Lignin engineering Vanholme, R.; Morreel, K.; Ralph, J. Current Opinion in Plant Biology, Vol. 11, Issue 3, p. 278-285 https://doi.org/10.1016/j.pbi.2008.03.005	journal	June 2008
Radical coupling reactions of piceatannol and monolignols: A density functional theory study Elder, Thomas; Carlos del Río, José; Ralph, John Phytochemistry, Vol. 164 https://doi.org/10.1016/j.phytochem.2019.04.003	journal	August 2019
Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation Elder, Thomas; Berstis, Laura; Beckham, Gregg T. Journal of Agricultural and Food Chemistry, Vol. 64, Issue 23 https://doi.org/10.1021/acs.jafc.6b02234	journal	June 2016
Variability in Lignin Composition and Structure in Cell Walls of Different Parts of Macaúba ( Acrocomia aculeata ) Palm Fruit Rencoret, Jorge; Kim, Hoon; Evaristo, Anderson B. Journal of Agricultural and Food Chemistry, Vol. 66, Issue 1 https://doi.org/10.1021/acs.jafc.7b04638	journal	December 2017
Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels del Río, José C.; Rencoret, Jorge; Gutiérrez, Ana Journal of Agricultural and Food Chemistry, Vol. 66, Issue 17 https://doi.org/10.1021/acs.jafc.8b00880	journal	April 2018
Effect of C _α –C _β Bond Type on the Radical Scavenging Activity of Hydroxy Stilbenes: Theoretical Insights in the Gas and Liquid Phase Nenadis, Nikolaos; Stavra, Katholiki The Journal of Physical Chemistry A, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpca.6b11814	journal	February 2017
Lignin Monomers from beyond the Canonical Monolignol Biosynthetic Pathway: Another Brick in the Wall del Río, José C.; Rencoret, Jorge; Gutiérrez, Ana ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 13 https://doi.org/10.1021/acssuschemeng.0c01109	journal	March 2020
Radical Nature of C-Lignin Berstis, Laura; Elder, Thomas; Crowley, Michael ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 10 https://doi.org/10.1021/acssuschemeng.6b00520	journal	May 2016
Density Functional Theory Study of Spirodienone Stereoisomers in Lignin Elder, Thomas; Berstis, Laura; Beckham, Gregg T. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 8 https://doi.org/10.1021/acssuschemeng.7b01373	journal	July 2017
Computational Evidence for Kinetically Controlled Radical Coupling during Lignification Gani, Terry Z. H.; Orella, Michael J.; Anderson, Eric M. ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 15 https://doi.org/10.1021/acssuschemeng.9b02506	journal	July 2019
Bond Dissociation Enthalpies of a Dibenzodioxocin Lignin Model Compound Elder, Thomas Energy & Fuels, Vol. 27, Issue 8 https://doi.org/10.1021/ef401026g	journal	July 2013
Bond Dissociation Enthalpies of a Pinoresinol Lignin Model Compound Elder, Thomas Energy & Fuels, Vol. 28, Issue 2 https://doi.org/10.1021/ef402310h	journal	January 2014
NMR Evidence for Benzodioxane Structures Resulting from Incorporation of 5-Hydroxyconiferyl Alcohol into Lignins of O-Methyltransferase-Deficient Poplars Ralph, John; Lapierre, Catherine; Lu, Fachuang Journal of Agricultural and Food Chemistry, Vol. 49, Issue 1 https://doi.org/10.1021/jf001042+	journal	November 2000
Structural Characterization of Wheat Straw Lignin as Revealed by Analytical Pyrolysis, 2D-NMR, and Reductive Cleavage Methods del Río, José C.; Rencoret, Jorge; Prinsen, Pepijn Journal of Agricultural and Food Chemistry, Vol. 60, Issue 23 https://doi.org/10.1021/jf301002n	journal	December 2011
Computational Study of Bond Dissociation Enthalpies for Lignin Model Compounds. Substituent Effects in Phenethyl Phenyl Ethers Beste, Ariana; Buchanan, A. C. The Journal of Organic Chemistry, Vol. 74, Issue 7 https://doi.org/10.1021/jo9001307	journal	April 2009
Computational Study of Bond Dissociation Enthalpies for a Large Range of Native and Modified Lignins Kim, Seonah; Chmely, Stephen C.; Nimlos, Mark R. The Journal of Physical Chemistry Letters, Vol. 2, Issue 22 https://doi.org/10.1021/jz201182w	journal	October 2011
Theoretical Study of the Remarkably Diverse Linkages in Lignin Parthasarathi, R.; Romero, Raymond A.; Redondo, Antonio The Journal of Physical Chemistry Letters, Vol. 2, Issue 20 https://doi.org/10.1021/jz201201q	journal	October 2011
Flavonolignans from Avena s ativa Wenzig, Eva; Kunert, Olaf; Ferreira, Daneel Journal of Natural Products, Vol. 68, Issue 2 https://doi.org/10.1021/np049636k	journal	February 2005
Lignins: Natural polymers from oxidative coupling of 4-hydroxyphenyl- propanoids Ralph, John; Lundquist, Knut; Brunow, Gösta Phytochemistry Reviews, Vol. 3, Issue 1-2, p. 29-60 https://doi.org/10.1023/B:PHYT.0000047809.65444.a4	journal	January 2004
The occurrence of tricin and its derivatives in plants Li, Mi; Pu, Yunqiao; Yoo, Chang Geun Green Chemistry, Vol. 18, Issue 6 https://doi.org/10.1039/C5GC03062E	journal	January 2016
A polymer of caffeyl alcohol in plant seeds Chen, F.; Tobimatsu, Y.; Havkin-Frenkel, D. Proceedings of the National Academy of Sciences, Vol. 109, Issue 5 https://doi.org/10.1073/pnas.1120992109	journal	January 2012
Phenolic Profiling of Caffeic Acid O -Methyltransferase-Deficient Poplar Reveals Novel Benzodioxane Oligolignols Morreel, Kris; Ralph, John; Lu, Fachuang Plant Physiology, Vol. 136, Issue 4 https://doi.org/10.1104/pp.104.049312	journal	November 2004
Sequencing around 5-Hydroxyconiferyl Alcohol-Derived Units in Caffeic Acid O -Methyltransferase-Deficient Poplar Lignins Lu, Fachuang; Marita, Jane M.; Lapierre, Catherine Plant Physiology, Vol. 153, Issue 2 https://doi.org/10.1104/pp.110.154278	journal	April 2010
Lignin Biosynthesis and Structure Vanholme, R.; Demedts, B.; Morreel, K. Plant Physiology, Vol. 153, Issue 3, p. 895-905 https://doi.org/10.1104/pp.110.155119	journal	May 2010
Tricin, a Flavonoid Monomer in Monocot Lignification Lan, Wu; Lu, Fachuang; Regner, Matthew Plant Physiology, Vol. 167, Issue 4 https://doi.org/10.1104/pp.114.253757	journal	February 2015
Maize Tricin-Oligolignol Metabolites and their Implications for Monocot Lignification Lan, Wu; Morreel, Kris; Lu, Fachuang Plant Physiology https://doi.org/10.1104/pp.16.02012	journal	April 2016
Hydroxystilbenes Are Monomers in Palm Fruit Endocarp Lignins Carlos del Río, José; Rencoret, Jorge; Gutiérrez, Ana Plant Physiology, Vol. 174, Issue 4 https://doi.org/10.1104/pp.17.00362	journal	June 2017
Hydroxystilbene Glucosides Are Incorporated into Norway Spruce Bark Lignin Rencoret, Jorge; Neiva, Duarte; Marques, Gisela Plant Physiology, Vol. 180, Issue 3 https://doi.org/10.1104/pp.19.00344	journal	April 2019
Coexistence but Independent Biosynthesis of Catechyl and Guaiacyl/Syringyl Lignin Polymers in Seed Coats Tobimatsu, Y.; Chen, F.; Nakashima, J. The Plant Cell, Vol. 25, Issue 7 https://doi.org/10.1105/tpc.113.113142	journal	July 2013
CCoAOMT suppression modifies lignin composition in Pinus radiata Wagner, Armin; Tobimatsu, Yuki; Phillips, Lorelle The Plant Journal, Vol. 67, Issue 1, p. 119-129 https://doi.org/10.1111/j.1365-313X.2011.04580.x	journal	April 2011
Metabolic engineering of novel lignin in biomass crops Vanholme, Ruben; Morreel, Kris; Darrah, Chiarina New Phytologist, Vol. 196, Issue 4 https://doi.org/10.1111/j.1469-8137.2012.04337.x	journal	October 2012
Novel seed coat lignins in the Cactaceae: structure, distribution and implications for the evolution of lignin diversity Chen, Fang; Tobimatsu, Yuki; Jackson, Lisa The Plant Journal, Vol. 73, Issue 2 https://doi.org/10.1111/tpj.12012	journal	November 2012
Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny Lan, Wu; Rencoret, Jorge; Lu, Fachuang The Plant Journal, Vol. 88, Issue 6 https://doi.org/10.1111/tpj.13315	journal	November 2016
Abnormal Lignin in a Loblolly Pine Mutant Ralph, J. Science, Vol. 277, Issue 5323 https://doi.org/10.1126/science.277.5323.235	journal	July 1997
Lignin Biosynthesis Boerjan, Wout; Ralph, John; Baucher, Marie Annual Review of Plant Biology, Vol. 54, Issue 1, p. 519-546 https://doi.org/10.1146/annurev.arplant.54.031902.134938	journal	June 2003
Lignin and Lignans Heitner, Cyril; Dimmel, Don; Schmidt, John https://doi.org/10.1201/EBK1574444865	book	August 2010
Indonesian Medicinal Plants. XVIII. Kompasinol A, a New Stilbeno-Phenylpropanoid from the Bark of Koompassia malaccensis (Fabaceae). Kobayashi, Motomasa; Mahmud, Taifo; Yoshioka, Naoki CHEMICAL & PHARMACEUTICAL BULLETIN, Vol. 44, Issue 12 https://doi.org/10.1248/cpb.44.2249	journal	January 1996
A Density Functional Theory Study of Coniferyl Alcohol Intermonomeric Cross Linkages in Lignin - Three-Dimensional Structures, Stabilities and the Thermodynamic Control Hypothesis Durbeej, B.; Eriksson, L. A. Holzforschung, Vol. 57, Issue 2 https://doi.org/10.1515/HF.2003.024	journal	February 2003
Formation of β-O-4 Lignin Models -A Theoretical Study Durbeej, B.; Eriksson, L. A. Holzforschung, Vol. 57, Issue 5 https://doi.org/10.1515/HF.2003.070	journal	August 2003
Erythro/threo ratio of β-O-4-5 structures as an important structural characteristic of lignin. Part 4: Variation in the erythro/threo ratio in softwood and hardwood lignins and its relation to syringyl/guaiacyl ratio Akiyama, Takuya; Goto, Hitoshi; Nawawi, Deded S. Holzforschung, Vol. 59, Issue 3 https://doi.org/10.1515/HF.2005.045	journal	May 2005
A computational study of pyrolysis reactions of lignin model compounds Elder, Thomas Holzforschung, Vol. 64, Issue 4 https://doi.org/10.1515/hf.2010.086	journal	June 2010
Elucidating Tricin-Lignin Structures: Assigning Correlations in HSQC Spectra of Monocot Lignins Lan, Wu; Yue, Fengxia; Rencoret, Jorge Polymers, Vol. 10, Issue 8 https://doi.org/10.3390/polym10080916	journal	August 2018

Similar Records

Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

Journal Article · Fri May 27 20:00:00 EDT 2016 · Journal of Agricultural and Food Chemistry · OSTI ID:1259259

Unconventional lignin monomers—Extension of the lignin paradigm

Journal Article · Mon Mar 14 20:00:00 EDT 2022 · Advances in Botanical Research · OSTI ID:1863567

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
5-hydroxyconiferyl alcohol
caffeyl alcohol
lignin
piceatannol
tricin

Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study

Citation Formats

References (57)

Similar Records

Related Subjects