The complexation of peptides by aminocyclodextrins

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<jats:title>Abstract</jats:title><jats:p>Four β‐cyclodextrins (CDs) were prepared bearing either an (<jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>‐dimethylamino)propylamino group (<jats:bold>1</jats:bold>), an (<jats:italic>N</jats:italic>‐methyl)‐piperazino group (<jats:bold>2</jats:bold>) or a benzylamino group (<jats:bold>3</jats:bold>), or seven methylamino susbtituents (<jats:bold>4</jats:bold>). Association constants <jats:italic>K</jats:italic> in water with di‐ and tripeptides reach up to 200 <jats:sc>M</jats:sc> <jats:sup>−1</jats:sup>, and after protection at the <jats:italic>N</jats:italic>‐terminus up to 680 <jats:sc>M</jats:sc> <jats:sup>−1</jats:sup>. Appreciable binding occurs only in the presence of lipophilic amino acid side‐chains, with preference for this at the <jats:italic>C</jats:italic>‐terminus. A moderate sequence and side‐chain selectivity is observed with <jats:bold>1</jats:bold>, <jats:bold>2</jats:bold> and <jats:bold>3</jats:bold>, but less so with the highly charged <jats:bold>4</jats:bold> where ion pairing dominates. Detailed NMR analyses with advanced techniques including T‐ROESY and GHSQC allow full assigment of most <jats:sup>1</jats:sup>H and <jats:sup>13</jats:sup>C signals, with extraction of many substituent and complexation induced shifts changes (SIS and CIS values, respectively). The CIS values and NOE cross peaks from ROESY experiments provide for insight into the binding modes of selected complexes, indicating, e.g., the simultaneous presence of complexes with a peptide phenyl unit approaching from both the narrow and the wide side of the CD cavity. With <jats:bold>3</jats:bold> one observes self‐inclusion of the pendant phenyl ring within the cavity, and its replacement by analytes such as peptides, or by adamantanecarboxylic acid. The inclusion modes are illustrated with force field simulated structures and many NMR spectra, which are made available in electronic supplements. Copyright © 2001 John Wiley & Sons, Ltd. <jats:italic>Additional material for this paper is available from the epoc website at http://www.wiley.com/epoc: (NMR shift tables; 3D coordinates for molecular structures; 1D‐ and 2D‐NMR spectra)</jats:italic></jats:p>

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