Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer

Elder, Thomas; del Río, José C.; Ralph, John; Rencoret, Jorge; Kim, Hoon

doi:10.1016/j.phytochem.2022.113122

Title: Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer

Journal Article · 04 February 2022 · Phytochemistry

DOI: https://doi.org/10.1016/j.phytochem.2022.113122 · OSTI ID:1845445

^[1];

^[2];

^[3];

^[2];

^[3]

USDA-Forest Service, Auburn, AL (United States); United States Department of Agriculture
Inst. de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Seville (Spain)
Univ. of Wisconsin, Madison, WI (United States)

Diferuloylputrescine has been found in a variety of plant species, and recent work has provided evidence of its covalent bonding into lignin. Results from nuclear magnetic resonance spectroscopy revealed the presence of bonding patterns consistent with homo-coupling of diferuloylputrescine and the possibility of cross-coupling with lignin. In the present work, density functional theory calculations have been applied to assess the energetics associated with radical coupling, rearomatization, and dehydrogenation for possible homo-coupled dimers of diferuloylputrescine and cross-coupled dimers of diferuloylputrescine and coniferyl alcohol. Furthermore, the values obtained for these reaction energetics are consistent with those reported for monolignols and other novel lignin monomers. As such, this study shows that there would be no thermodynamic impediment to the incorporation of diferuloylputrescine into the lignin polymer and its addition to the growing list of non-canonical lignin monomers.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0018409

OSTI ID:: 1845445

Journal Information:: Phytochemistry, Journal Name: Phytochemistry Vol. 197; ISSN 0031-9422

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Ferulate–coniferyl alcohol cross-coupled products formed by radical coupling reactions Zhang, Aiping; Lu, Fachuang; Sun, Runcang Planta, Vol. 229, Issue 5 https://doi.org/10.1007/s00425-009-0894-6	journal	February 2009
Diferuloylputrescine and p-coumaroyl-feruloylputrescine, abundant polyamine conjugates in lipid extracts of maize kernels Moreau, Robert A.; Nuñez, Alberto; Singh, Vijay Lipids, Vol. 36, Issue 8 https://doi.org/10.1007/s11745-001-0793-6	journal	August 2001
The composition of corn oil obtained by the alcohol extraction of ground corn Moreau, Robert A.; Hicks, Kevin B. Journal of the American Oil Chemists' Society, Vol. 82, Issue 11 https://doi.org/10.1007/s11746-005-1148-4	journal	November 2005
Naturally p-Hydroxybenzoylated Lignins in Palms Lu, Fachuang; Karlen, Steven D.; Regner, Matt BioEnergy Research, Vol. 8, Issue 3 https://doi.org/10.1007/s12155-015-9583-4	journal	February 2015
Ether-linked ferulic acid amides in natural and wound periderms of potato tuber Negrel, Jonathan; Pollet, Brigitte; Lapierre, Catherine Phytochemistry, Vol. 43, Issue 6 https://doi.org/10.1016/S0031-9422(96)00500-6	journal	December 1996
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
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
Anti-inflammatory activity of hydroxycinnamic acid derivatives isolated from corn bran in lipopolysaccharide-stimulated Raw 264.7 macrophages Kim, Eun Ok; Min, Kyoung Jin; Kwon, Taeg Kyu Food and Chemical Toxicology, Vol. 50, Issue 5 https://doi.org/10.1016/j.fct.2012.02.011	journal	May 2012
Phenolic compounds from hydrolyzed and extracted fiber-rich by-products Bauer, Jonas Lewin; Harbaum-Piayda, Britta; Schwarz, Karin LWT, Vol. 47, Issue 2 https://doi.org/10.1016/j.lwt.2012.01.012	journal	July 2012
Antioxidant activities of corn fiber and wheat bran and derived extracts Bauer, Jonas Lewin; Harbaum-Piayda, Britta; Stöckmann, Heiko LWT - Food Science and Technology, Vol. 50, Issue 1 https://doi.org/10.1016/j.lwt.2012.06.012	journal	January 2013
Coupling of aromatic amines onto syringylglycerol β-guaiacylether using Bacillus SF spore laccase: A model for functionalization of lignin-based materials Kudanga, Tukayi; Nugroho Prasetyo, Endry; Sipilä, Jussi Journal of Molecular Catalysis B: Enzymatic, Vol. 61, Issue 3-4 https://doi.org/10.1016/j.molcatb.2009.06.003	journal	December 2009
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
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
Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study Elder, Thomas; del Río, José C.; Ralph, John ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 30 https://doi.org/10.1021/acssuschemeng.0c02880	journal	July 2020
Coupling of Flavonoid Initiation Sites with Monolignols Studied by Density Functional Theory Berstis, Laura; Elder, Thomas; Dixon, Richard ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 4 https://doi.org/10.1021/acssuschemeng.0c04240	journal	January 2021
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
Monolignol Benzoates Incorporate into the Lignin of Transgenic Populus trichocarpa Depleted in C3H and C4H Kim, Hoon; Li, Quanzi; Karlen, Steven D. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 9 https://doi.org/10.1021/acssuschemeng.9b06389	journal	February 2020
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
Inhibitory Activity of Corn-Derived Bisamide Compounds against α-Glucosidase Niwa, Toshio; Doi, Umeyuki; Osawa, Toshihiko Journal of Agricultural and Food Chemistry, Vol. 51, Issue 1 https://doi.org/10.1021/jf020758x	journal	November 2002
Inhibition of Aflatoxin Biosynthesis in Aspergillus flavus by Diferuloylputrescine and p -Coumaroylferuloylputrescine Mellon, Jay E.; Moreau, Robert A. Journal of Agricultural and Food Chemistry, Vol. 52, Issue 21 https://doi.org/10.1021/jf040226b	journal	September 2004
Occurrence of Naturally Acetylated Lignin Units Del Río, José C.; Marques, Gisela; Rencoret, Jorge Journal of Agricultural and Food Chemistry, Vol. 55, Issue 14 https://doi.org/10.1021/jf0705264	journal	July 2007
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
Highly Acylated (Acetylated and/or p-Coumaroylated) Native Lignins from Diverse Herbaceous Plants del Río, José C.; Rencoret, Jorge; Marques, Gisela Journal of Agricultural and Food Chemistry, Vol. 56, Issue 20, p. 9525-9534 https://doi.org/10.1021/jf800806h	journal	October 2008
Highly Accurate Coupled Cluster Potential Energy Curves for the Benzene Dimer: Sandwich, T-Shaped, and Parallel-Displaced Configurations Sinnokrot, Mutasem Omar; Sherrill, C. David The Journal of Physical Chemistry A, Vol. 108, Issue 46 https://doi.org/10.1021/jp0469517	journal	November 2004
Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study Sangha, Amandeep K.; Parks, Jerry M.; Standaert, Robert F. The Journal of Physical Chemistry B, Vol. 116, Issue 16 https://doi.org/10.1021/jp2122449	journal	April 2012
Chemical Factors that Control Lignin Polymerization Sangha, Amandeep K.; Davison, Brian H.; Standaert, Robert F. The Journal of Physical Chemistry B, Vol. 118, Issue 1 https://doi.org/10.1021/jp411998t	journal	December 2013
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
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
NMR characterization of altered lignins extracted from tobacco plants down-regulated for lignification enzymes cinnamylalcohol dehydrogenase and cinnamoyl-CoA reductase Ralph, J.; Hatfield, R. D.; Piquemal, J. Proceedings of the National Academy of Sciences, Vol. 95, Issue 22 https://doi.org/10.1073/pnas.95.22.12803	journal	October 1998
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
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
Highly Decorated Lignins in Leaf Tissues of the Canary Island Date Palm Phoenix canariensis Karlen, Steven D.; Smith, Rebecca A.; Kim, Hoon Plant Physiology, Vol. 175, Issue 3 https://doi.org/10.1104/pp.17.01172	journal	September 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
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
Monolignol ferulate conjugates are naturally incorporated into plant lignins Karlen, Steven D.; Zhang, Chengcheng; Peck, Matthew L. Science Advances, Vol. 2, Issue 10 https://doi.org/10.1126/sciadv.1600393	journal	October 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
Identification of Characteristic Phenolic Constituents in Mousouchiku Extract Used as Food Additives Yoshimura, Morio; Ochi, Keisuke; Sekiya, Hiroshi CHEMICAL & PHARMACEUTICAL BULLETIN, Vol. 65, Issue 9 https://doi.org/10.1248/cpb.c17-00401	journal	January 2017
Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study Elder, Thomas; Rencoret, Jorge; del Río, José C. Frontiers in Plant Science, Vol. 12 https://doi.org/10.3389/fpls.2021.642848	journal	March 2021
Lignans, Amides, and Saponins from Haplophyllum tuberculatum and Their Antiprotozoal Activity Mahmoud, Abdelhalim Babiker; Danton, Ombeline; Kaiser, Marcel Molecules, Vol. 25, Issue 12 https://doi.org/10.3390/molecules25122825	journal	June 2020

Similar Records

Unconventional lignin monomers—Extension of the lignin paradigm

Journal Article · 2022 · Advances in Botanical Research · OSTI ID:1863567

del Río, José C.; Rencoret, Jorge; Gutiérrez, Ana; +2 more

Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study

Journal Article · 2021 · Frontiers in Plant Science · OSTI ID:1776819

Elder, Thomas; Rencoret, Jorge; del Río, José C.; +2 more

Lignin Monomers from beyond the Canonical Monolignol Biosynthetic Pathway: Another Brick in the Wall

Journal Article · 2020 · ACS Sustainable Chemistry & Engineering · OSTI ID:1637462

del Río, José C.; Rencoret, Jorge; Gutiérrez, Ana; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Coniferyl alcohol
Cross-couple
Density functional theory
Diferuloylputrescine
Feruloyl amide
Homo-couple
Lignification
Lignin
Radical coupling

Title: Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer

Citation Formats

References (44)

Similar Records

Related Subjects