Abstract
Terrestrial plants rely on protection conferred by their outer coverings to defend against desiccation, bruising, and microbial invasion. For food staples such as potato tubers, the periderm contains the phellem (tuber skin) which creates a hydrophobic barrier by depositing macromolecular composites comprised of waxes, soluble phenolics, and a complex aliphatic suberin polyester (or suberin aliphatic domain) and lignin-like biopolymer (or suberin polyphenolic domain) within the previously formed polysaccharide cell wall. The antibacterial activity of both the soluble chemical constituents and their solid polymeric assemblies provides essential plant defense; their antioxidant and waterproofing properties also offer practical potential for sustainable food preservation and packaging applications. To characterize these phytochemical composites comprehensively and in molecular detail, we developed an approach that coordinates ‘bottom-up’ analysis of extracted metabolites that include suberin precursors, solid-state NMR spectroscopy of the polymers in intact skins or solid suspensions, and ‘top-down’ analysis of chemical breakdown products of suberin. The usefulness of analytical methods that include LC–MS, GC–MS, multivariate analysis, solid-state NMR, SEM, and TEM is illustrated for studies of molecular and supramolecular structures that underlie protective function in three potato periderm systems: (1) native tuber periderms versus suberized wound-healing tissues including closing layer and wound periderm; (2) metabolites unleashed in rapid response to wounding prior to formation of suberized tissues; (3) wild type versus genetically modified potato varieties with altered suberin deposition. We also demonstrate how enrichment with stable 13C and 15N isotopes can improve our understanding of how the suberin biopolymer molecular structure develops, increasing the reach of MS, 2D solid-state NMR, and dynamic nuclear polarization spectroscopic methods and revealing phenolic amide constituents that could represent an underappreciated part of the plant’s defensive arsenal.
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Copyright 2015 Elsevier
Copyright 2014 American Chemical Society
Copyright 2019 Elsevier
Copyright 2019 Elsevier
Copyright 2015 American Chemical Society
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Copyright 2014 American Chemical Society
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Abbreviations
- CPMAS:
-
Cross polarization magic-angle spinning
- DARR:
-
Dipolar-assisted rotational resonance
- DCP:
-
Double cross polarization
- DNP:
-
Dynamic nuclear polarization
- FHT:
-
Fatty ω-hydroxyacid/fatty alcohol hydroxycinnamoyl transferase
- GC:
-
Gas chromatography
- IR:
-
Infrared spectroscopy
- LC:
-
Liquid chromatography
- MS:
-
Mass spectrometry
- OPLS-DA:
-
Orthogonal partial least-squares discriminate analysis
- PCA:
-
Principal component analysis
- Phe:
-
Phenylalanine
- SEM:
-
Scanning electron microscopy
- ssNMR:
-
Solid-state NMR
- SPIDER:
-
Saturation-Pulse Induced Dipolar Exchange with Recoupling
- TOF:
-
Time-of-flight mass spectrometry
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Acknowledgements
The authors thank Drs. Hsin Wang and Lijia Yang for valuable technical assistance with the NMR and GC-MS instrumentation, respectively, at The City College of New York (CCNY). We express our appreciation to Dr. Boris Itin for technical assistance with the ssNMR and DNP instrumentation at the New York Structural Biology Center (NYSBC). Contributors to our previously published work described in this review included Drs. Wenlin Huang and Barney Yoo, Ph.D. students Liqing Jin and Qing Cai, undergraduate Mathiu Perez Rodriguez, and high school student Janni Lin. This work was supported by grants from the U.S. National Science Foundation (NSF award MCB-1411984 to R.E.S.), the U.S. Department of Agriculture (2022-67014-36387 to R.E.S.), and the Spanish Ministerio de Ciencia, Innovación y Universidades (PID2019-110330GB-C21/MICIU/AEI/10.13039/501100011033) to M.F. and O.S.). The Q-TOF MS instrument was acquired through NSF award CHE-1228921 and is operated by the CUNY Hunter College Department of Chemistry. The GC-MS instrument was acquired through NSF award CHE-0840498. Infrastructural support for the solid-state NMR spectrometer was provided by The City College of New York, the CUNY Institute for Macromolecular Assemblies, and a grant from the U.S. National Institutes of Health (5G12MD007603-30, National Institute on Minority Health and Health Disparities). The NMR instruments at the NYSBC were obtained through a grant from the New York State Office of Science, Technology and Academic Research, an NIH Office of Research Infrastructure Program Facility Improvement Grant (CO6RR015495), and an NIH Equipment Grant (S10RR029249).
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Dastmalchi, K., Phan, V.C., Chatterjee, S. et al. A comprehensive approach to phytochemical analysis of macromolecular composites that protect tubers: case studies in suberized potato periderm tissues. Phytochem Rev (2024). https://doi.org/10.1007/s11101-024-09974-4
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DOI: https://doi.org/10.1007/s11101-024-09974-4