56 research outputs found
Selective complexation of divalent cations by a cyclic α,β-peptoid hexamer: a spectroscopic and computational study
We describe the qualitative and quantitative analysis of the complexation properties towards cations of a cyclic peptoid hexamer composed of alternating α- and β-peptoid monomers, which bear exclusively chiral (S)-phenylethyl side chains (spe) that have no noticeable chelating properties. The binding of a series of monovalent and divalent cations was assessed by 1H NMR, circular dichroism, fluorescence and molecular modelling. In contrast to previous studies on cations binding by 18-membered α-cyclopeptoid hexamers, the 21-membered cyclopeptoid cP1 did not complex monovalent cations (Na+, K+, Ag+) but showed selectivity for divalent cations (Ca2+, Ba2+, Sr2+ and Mg2+). Hexacoordinated C-3 symmetrical complexes were demonstrated for divalent cations with ionic radii around 1 Å (Ca2+ and Ba2+), while 5-coordination is preferred for divalent cations with larger (Ba2+) or smaller ionic radii (Mg2+)
Monopeptide versus Monopeptoid: Insights on Structure and Hydration of Aqueous Alanine and Sarcosine via X-ray Absorption Spectroscopy
Synthesis and Characterization of Nitroaromatic Peptoids: Fine Tuning Peptoid Secondary Structure through Monomer Position and Functionality
Design and Synthesis of Macrocyclic Peptomers as Mimics of a Quorum Sensing Signal from Staphylococcus aureus
Effects of Thionation and Fluorination on Cis–Trans Isomerization in Tertiary Amides: An Investigation of <i>N</i>‑Alkylglycine (Peptoid) Rotamers
Peptoids
constitute a class of peptidomimetics with potential as
protease resistant, biologically active ligands. To harness the full
potential of such compounds, however, detailed predictive insight
into their propensity to adopt well-defined secondary structures is
highly desirable. In this work we present an investigation of the
effects of thioamides and/or fluorides in peptoid monomer model systems
using chemical synthesis, NMR spectroscopy, and X-ray crystallography.
We find that the steric environment surrounding the tertiary amide
bonds is the key promoter of conformational preference, and X-ray
crystallographic interrogation of our model systems did not suggest
the presence of stabilizing <i>n</i> → π* interactions
unless the carbonyls were altered electronically by α-halogenation
or thioamide formation. In addition to the function as an investigative
tool, these two types of modification may thus be utilized as stabilizers
of secondary structure in future oligomer designs, such as the <i>cis-</i>amide-based polypeptoid helices that resemble the polyproline
type-I helix
- …