The absolute configuration of the constituent monomers were determined by a combination of (iii) NMR evidence involving NOESY correlations, the "-gauche effect" in the C domain, differential C chemical shift (C) values relative to the four stereochemically fully characterized dimers (terminal unit II), (iv) ECD data, and (v) phloroglucinolysis combined with LC-MS and chiral phase HPLC analysis (Figures ). Factoring in previously reported NMR assignment, these spectroscopic and chemical methods allowed the unambiguous assignment of the structures of all isolated PACs. The presented detailed analytical profiles of 13 PACs (Tables , sorted by H/ C domains and increasing degree of oligomerization) enlarge significantly the space of available NMR data of oligomeric PACs with solid structural information. This also expands the library of PACs that can be used to explore their dentin biomodification mechanisms of action systematically and supports the ongoing establishment of structure-activity relationships.