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Title: Pterocarpan synthase (PTS) structures suggest a common quinone methide–stabilizing function in dirigent proteins and proteins with dirigent-like domains

Journal Article · · Journal of Biological Chemistry

The biochemical activities of dirigent proteins (DPs) give rise to distinct complex classes of plant phenolics. DPs apparently began to emerge during the aquatic-to-land transition, with phylogenetic analyses revealing the presence of numerous DP subfamilies in the plant kingdom. The vast majority (>95%) of DPs in these large multigene families still await discovery of their biochemical functions. Here, we elucidated the 3D structures of two pterocarpan-forming proteins with dirigent-like domains. Both proteins stereospecifically convert distinct diastereomeric chiral isoflavonoid precursors to the chiral pterocarpans, (–)- and (+)-medicarpin, respectively. Their 3D structures enabled comparisons with stereoselective lignan– and aromatic terpenoid–forming DP orthologs. Furthermore, each protein provides entry into diverse plant natural products classes, and our experiments suggest a common biochemical mechanism in binding and stabilizing distinct plant phenol–derived mono- and bis-quinone methide intermediates during different C–C and C–O bond–forming processes. These observations provide key insights into both their appearance and functional diversification of DPs during land plant evolution/adaptation. The proposed biochemical mechanisms based on our findings provide important clues to how additional physiological roles for DPs and proteins harboring dirigent-like domains can now be rationally and systematically identified.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH); USDOE
Grant/Contract Number:
AC05-76RL01830; AC02-76SF00515; P41GM103393
OSTI ID:
1769485
Alternate ID(s):
OSTI ID: 1668325
Report Number(s):
PNNL-SA-150677
Journal Information:
Journal of Biological Chemistry, Vol. 295, Issue 33; ISSN 0021-9258
Publisher:
American Society for Biochemistry and Molecular BiologyCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (11)