Noncovalent Chirality Sensing Ensembles for the Detection and Reaction Monitoring of Amino Acids, Peptides, Proteins, and Aromatic Drugs

Abstract

Ternary complexes between the macrocyclic host cucurbit[8]uril, dicationic dyes, and chiral aromatic analytes afford strong induced circular dichroism (ICD) signals in the near-UV and visible regions. This allows for chirality sensing and peptide-sequence recognition in water at low micromolar analyte concentrations. The reversible and noncovalent mode of binding ensures an immediate response to concentration changes, which allows the real-time monitoring of chemical reactions. The introduced supramolecular method is likely to find applications in bioanalytical chemistry, especially enzyme assays, for drug-related analytical applications, and for continuous monitoring of enantioselective reactions, particularly asymmetric catalysis.

Supramolecular Chemistry of Cucurbiturils: Tuning Cooperativity with Multiple Noncovalent Interactions from Positive to Negative

“…On account of their high affinities, CB[n]-mediated host-guest interactions are of great interest in the field of supramolecular chemistry and chemical biology. [25][26][27][28][29][30][31][32] While the ability to exhibit multiple non-covalent interactions, CB [8]-mediated heteroternary and homoternary complexes have been exploited in the construction of supramolecular polymers, 33-36 supramolecular hydrogels, [37][38] supra-amphiphiles [39][40] and other supramolecular functional self-assembled systems [41][42][43][44][45][46] .…”

Second‐Generation Tris(2‐pyridylmethyl)amine–Zinc Complexes as Probes for Enantiomeric Excess Determination of Amino Acids

“…Owing to the strong interest in the chiral sensing of amino acids, [40][41][42][43][44][45][46][47] we decided to investigate whether structural modification of the probe could further improve the dichroic signal and complex stability. This has been achieved by the synthesis of a new ligand in which the aldehyde moiety was moved from the meta to the para position with respect to the pyridine ring.…”

Chiral Discrimination through 1H NMR and Luminescence Spectroscopy: Dynamic Processes and Solid Strip for Chiral Recognition

“…Earlier reports revealed that various spectroscopic (i.e., UV/Vis, fluorescence, NMR, circular dichroism) and electrochemical, polarimetric, and chromatographic techniques have been utilized for studying enantiomeric‐recognition phenomena ,. More recently, Biedermann and Nau utilized self‐assembled ternary complex formation between macrocyclic host molecules, such as cucurbit[8]uril, dicationic dyes, and chiral aromatic analytes, for the recognition of certain chiral amino acids/peptides by probing changes in induced circular dichroism (CD) signals . Among various possibilities, fluorescence‐based enantioselective sensors allow the rapid analysis of the enantiomeric composition of chiral compounds.…”