Design of Stable β‐Sheet‐Based Cyclic Peptide Assemblies Assisted by Metal Coordination: Selective Homo‐ and Heterodimer Formation

Abstract

Metal-directed supramolecular construction represents one of the most powerful tools to prepare a large variety of structures and functions. The ability of metals to organize different numbers and types of ligands with a variety of geometries (linear, trigonal, octahedral, etc.) expands the supramolecular synthetic architecture. We describe here the precise construction of homo- and heterodimeric cyclic peptide entities through coordination of a metal (Pd, Au) and to β-sheet-type hydrogen-bonding interactions. The selective coordination properties of the appropriate metal allow control over the cross-strand interaction between the two-peptide strands.

Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

“…Hence for understanding the chemical properties of many small organic and bio-macro molecules, the study of hydrogen bonds [19][20][21][22][23][24][25][26][27][28][29] is extremely important. There are number of chemical reactions in which the transfer of one or more protons (viz., hydride ions or hydrogen atoms) takes place in the rate determining step.…”

Reversible Covalent and Supramolecular Functionalization of Water‐Soluble Gold(I) Complexes

“…The Metzler‐Nolte group has reported a series of amino acid and peptide–gold(I) conjugates based on Au I –NHC, Au I ‐N,S‐heterocyclic carbene (NSHC), and triazolyl gold(I) phosphane complexes . Laguna and Gimeno have reported the synthesis of peptidic thiolate gold(I) phosphane complexes, whereas Amorín and Granja described cyclic peptides linked by hydrophobic alkynyl gold(I) phosphanes . Water‐soluble molecular gold(I) complexes in general and those bearing alkynyl ligands in particular have received increasingly large interest in applications for luminescence, catalysis, and medicinal chemistry…”

Molecular Pom Poms from Self‐Assembling α,γ‐Cyclic Peptides

“…Nicotinic acid was therefore selected for attachment through an ester linkage to a cyclic peptide that bears a serine residue. CP2 , which was obtained from previously published CP1 ,10c was treated with nicotinic acid in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide (EDC), 1‐hydroxybenzotriazole (HOBt), and N , N ‐dimethyl‐4‐aminopyridine (DMAP) to provide the corresponding CP3 in good yields (Scheme ). The CP, because of the lack of C3 symmetry, forms three non‐equivalent dimers, D(Acw)n , D(Accw)n , and D(S)n , two anti isomers (the clockwise, Acw, and the counterclockwise, Accw) and one syn isomer (S) 11.…”