Absolute Configuration of Native Oligomeric Proanthocyanidins with Dentin Biomodification Potency

Joo-Won Nam; Rasika S Phansalkar; David C Lankin; James B McAlpine; Ariene A Leme-Kraus; Cristina M P Vidal; Li-She Gan; Ana Bedran-Russo; Shao-Nong Chen; Guido F Pauli

doi:10.1021/acs.joc.6b02161

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Absolute Configuration of Native Oligomeric Proanthocyanidins with Dentin Biomodification Potency

Journal article

Peer reviewed

Absolute Configuration of Native Oligomeric Proanthocyanidins with Dentin Biomodification Potency

Joo-Won Nam, Rasika S Phansalkar, David C Lankin, James B McAlpine, Ariene A Leme-Kraus, Cristina M P Vidal, Li-She Gan, Ana Bedran-Russo, Shao-Nong Chen and Guido F Pauli

Journal of organic chemistry, Vol.82(3), pp.1316-1329

02/03/2017

DOI: 10.1021/acs.joc.6b02161

PMCID: PMC5451120

PMID: 28098463

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Abstract

The structurally complex oligomeric proanthocyanidins (OPACs) are promising biomimetic agents, capable of strengthening the macromolecular backbone of teeth via intermolecular and intermicrofibrillar cross-linking. This study establishes analytical methods capable of determining the absolute configuration of the catechin-type monomeric units of underivatized OPACs. This preserves the capacity of their biological evaluation, aimed at understanding the inevitably stereospecific interactions between the OPACs and dentin collagen. Guided by dental bioassays (modulus of elasticity, long-term stability), two new trimeric and tetrameric A-type OPACs were discovered as dentin biomodifiers from pine (Pinus massoniana) bark: epicatechin-(2β→O→7,4β→8)-epicatechin-(2β→O→7,4β→8)-catechin (5) and epicatechin-(2β→O→7,4β→8)-epicatechin-(2β→O→7,4β→6)-epicatechin-(2β→O→7,4β→8)-catechin (6), respectively. Combining 1D/2D NMR, HRESIMS, ECD,\nH iterative full spin analysis (HiFSA), and gauge-invariant atomic orbital (GIAO) δ calculations, we demonstrate how\nC NMR chemical shifts (diastereomeric building blocks (A-type dimers)) empower the determination of the absolute configuration of monomeric units in the higher oligomers 5 and 6. Collectively, NMR with ECD reference data elevates the level of structural information achievable for these structurally demanding molecules when degradation analysis is to be avoided. Considering their numerous and deceptively subtle, but 3D impactful, structural variations, this advances the probing of OPAC chemical spaces for species that bind selectively to collagenous and potentially other biologically important biomacromolecules.

Details

Title: Subtitle: Absolute Configuration of Native Oligomeric Proanthocyanidins with Dentin Biomodification Potency
Creators: Joo-Won Nam - College of Pharmacy, Yeungnam University , Gyeongsan, Gyeongbuk 712-749, Korea
Rasika S Phansalkar
David C Lankin
James B McAlpine
Ariene A Leme-Kraus - Department of Restorative Dentistry, College of Dentistry, University of Illinois at Chicago , Chicago, Illinois 60612, United States
Cristina M P Vidal - Department of Restorative Dentistry, College of Dentistry, University of Illinois at Chicago , Chicago, Illinois 60612, United States
Li-She Gan - College of Pharmaceutical Sciences, Zhejiang University , Hangzhou 310058, People's Republic of China
Ana Bedran-Russo - Department of Restorative Dentistry, College of Dentistry, University of Illinois at Chicago , Chicago, Illinois 60612, United States
Shao-Nong Chen
Guido F Pauli
Resource Type: Journal article
Publication Details: Journal of organic chemistry, Vol.82(3), pp.1316-1329
DOI: 10.1021/acs.joc.6b02161
PMID: 28098463
PMCID: PMC5451120
NLM abbreviation: J Org Chem
ISSN: 0022-3263
eISSN: 1520-6904
Publisher: American Chemical Society (ACS); United States
Grant note: R01 DE021040 / NIDCR NIH HHS\nP41 GM068944 / NIGMS NIH HHS
Language: English
Date published: 02/03/2017
Academic Unit: Operative Dentistry
Record Identifier: 9984065999802771

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