skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The molecular structure of plant sporopollenin

Journal Article · · Nature Plants (Online)

Sporopollenin is a ubiquitous and extremely chemically inert biopolymer that constitutes the outer wall of all land-plant spores and pollen grains1. Sporopollenin protects the vulnerable plant gametes against a wide range of environmental assaults, and is considered a prerequisite for the migration of early plants onto land2. Despite its importance, the chemical structure of plant sporopollenin has remained elusive1. Using a newly developed thioacidolysis degradative method together with state-of-the-art solid-state NMR techniques, we determined the detailed molecular structure of pine sporopollenin. We show that pine sporopollenin is primarily composed of aliphatic-polyketide-derived polyvinyl alcohol units and 7-O-p-coumaroylated C16 aliphatic units, crosslinked through a distinctive dioxane moiety featuring an acetal. Naringenin was also identified as a minor component of pine sporopollenin. This discovery answers the long-standing question about the chemical make-up of plant sporopollenin, laying the foundation for future investigations of sporopollenin biosynthesis and for the design of new biomimetic polymers with desirable inert properties.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF); Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
SC0001090
OSTI ID:
1566613
Journal Information:
Nature Plants (Online), Vol. 5, Issue 1; ISSN 2055-0278
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

References (42)

Sporopollenin monomer biosynthesis in arabidopsis journal February 2013
The Rise of Chemodiversity in Plants journal June 2012
Whole plant cell wall characterization using solution-state 2D NMR journal August 2012
1H NMR analysis of sporopollenin from Typha Angustifolia journal March 1999
Thioacidolysis book January 1992
The Assignment of Absolute Configuration by NMR journal January 2004
Highly Potent Chiral Labeling Reagents for the Discrimination of Chiral Alcohols* journal January 2003
Development of Highly Potent Chiral Discrimination Methods That Solve the Problems of Diastereomer Method journal January 2008
Chiral discrimination of secondary alcohols by both 1 H-NMR and HPLC after labeling with a chiral derivatization reagent, 2-(2,3-anthracenedicarboximide)cyclohexane carboxylic acid journal January 2005
Environmentally benign metal triflate-catalyzed reductive cleavage of the C–O bond of acetals to ethers journal January 2011
TMDS as a Dual-Purpose Reductant in the Regioselective Ring Cleavage of Hexopyranosyl Acetals to Ethers journal February 2012
Structure and Interactions of Plant Cell-Wall Polysaccharides by Two- and Three-Dimensional Magic-Angle-Spinning Solid-State NMR journal February 2011
Multidimensional solid-state NMR spectroscopy of plant cell walls journal September 2016
Direct Determination of Hydroxymethyl Conformations of Plant Cell Wall Cellulose Using 1 H Polarization Transfer Solid-State NMR journal December 2017
Gradients in Wall Mechanics and Polysaccharides along Growing Inflorescence Stems journal October 2017
High Resolution Solid State 13 C NMR Spectroscopy of Sporopollenins from Different Plant Taxa journal January 1988
Characterization of a nitrogen-rich fulvic acid and its precursor algae from solid state NMR journal August 2007
Abundant and Stable Char Residues in Soils: Implications for Soil Fertility and Carbon Sequestration journal August 2012
Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization journal February 2014
LAP6/POLYKETIDE SYNTHASE A and LAP5/POLYKETIDE SYNTHASE B Encode Hydroxyalkyl α-Pyrone Synthases Required for Pollen Development and Sporopollenin Biosynthesis in Arabidopsis thaliana journal December 2010
Analysis of TETRAKETIDE α-PYRONE REDUCTASE Function in Arabidopsis thaliana Reveals a Previously Unknown, but Conserved, Biochemical Pathway in Sporopollenin Monomer Biosynthesis journal December 2010
Accurate Quantification of Aromaticity and Nonprotonated Aromatic Carbon Fraction in Natural Organic Matter by 13 C Solid-State Nuclear Magnetic Resonance journal May 2004
Methylene spectral editing in solid-state 13C NMR by three-spin coherence selection journal September 2005
Degradation of poly(vinyl butyral) and its stabilization by bases journal April 2008
The origin and evolution of lignin biosynthesis: Tansley review journal June 2010
CYP704B1 Is a Long-Chain Fatty Acid ω -Hydroxylase Essential for Sporopollenin Synthesis in Pollen of Arabidopsis journal August 2009
CYP703 Is an Ancient Cytochrome P450 in Land Plants Catalyzing in-Chain Hydroxylation of Lauric Acid to Provide Building Blocks for Sporopollenin Synthesis in Pollen journal May 2007
The chalcone synthase superfamily of type III polyketide synthases journal December 2002
A Novel Fatty Acyl-CoA Synthetase Is Required for Pollen Development and Sporopollenin Biosynthesis in Arabidopsis journal February 2009
Novel p-coumaric acid esters from Pinus densiflora pollen journal January 1978
The Chalcone Synthase Superfamily of Type III Polyketide Synthases journal April 2003
ChemInform Abstract: TMDS as a Dual-Purpose Reductant in the Regioselective Ring Cleavage of Hexopyranosyl Acetals to Ethers. journal August 2012
Incorporation of Oleic Acid into Sporopollenin and Its Inhibition by the Chloroacetamide Herbicide Metazachlor journal July 1996
p-coumaric acid ? a monomer in the sporopollenin skeleton journal April 1990
Phenols as Integrated Compounds of Sporopollenin from Pinus Pollen journal November 1987
Studies on Sporopollenin Biosynthesis in Cucurbita maxima (DUCH.) — II. The Involvement of Aliphatic Metabolism journal April 1999
Lignin Functionalization through Chemical Demethylation: Preparation and Tannin-Like Properties of Demethylated Guaiacyl-Type Synthetic Lignins journal May 2017
Isolation and Identification of Oligomers from Partial Degradation of Lime Fruit Cutin journal October 2008
Preparation, Isolation, and Characterization of Cutin Monomers and Oligomers from Tomato Peels journal February 1999
Tracer Experiments on Sporopollenin Biosynthesis: An overview journal January 1993
Acetylation and Silylation of Piperidine Solubilized Sporopollenin from Pollen of Typha angustifolia L. journal December 2003
p-Coumaric acid ? a monomer in the sporopollenin skeleton journal October 1989

Cited By (5)

Rice pollen aperture formation is regulated by the interplay between OsINP1 and OsDAF1 journal April 2020
Exploiting pollen and sporopollenin for the sustainable production of microstructures journal January 2020
Lignin biosynthesis: old roads revisited and new roads explored journal December 2019
Artificial pollen walls simulated by the tandem processes of phase separation and self‐assembly in vitro journal October 2019
Chemical variations in Quercus pollen as a tool for taxonomic identification: Implications for long‐term ecological and biogeographical research journal February 2020