The synthesis of deep cavitands with functionalized acetals as a fourth-wall is described. Recognition properties and stabilities of the complexes of two representative cavitands with aliphatic, aromatic, carbocyclic and adamantane guests were evaluated by NMR methods.
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http://dx.doi.org/10.1039/c2cc36517k | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, University of California─Riverside, Riverside, California 92521, United States.
A synergistic combination of cationic styrylpyridinium dyes and water-soluble deep cavitand hosts can recognize phosphorylated peptides with both site- and state-selectivity. Two mechanisms of interaction are dominant: either the cationic dye interacts with Trp residues in the peptide or the host:dye pair forms a heteroternary complex with the peptide, driven by both strong dye-peptide and cavitand-peptide binding ( values up to 4 μM). The presence of multiple recognition mechanisms results in varying fluorescence responses dependent on the phosphorylation state and position, eliminating the need for covalent modification of the peptide target.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, OH-43210, USA.
We describe the preparation, assembly, recognition characteristics, and bioactivity of dendritic basket 6. This novel cavitand has a deep aromatic pocket with three (S)-glutamic acid dendrons at the rim to amplify water solubility and prevent self-association. H NMR spectroscopy, calorimetry (ITC), and mass spectrometry (ESI-MS) measurements validate the formation of an inclusion complex between 6 and anticancer drug methotrexate (MTX) in water (K=9.
View Article and Find Full Text PDFPhys Chem Chem Phys
March 2024
Department of Natural Sciences, Pitzer and Scripps Colleges, Claremont, California, 91711, USA.
Sequestration of small molecule guests in the cavity of a water-soluble deep cavitand host has a variety of effects on their NMR properties. The effects of encapsulation on the longitudinal () and transverse () relaxation times of the protons in variably sized guest molecules are analyzed here, using inversion recovery and spin-echo experiments. Sequestration of neutral organic species from the bulk solvent reduces the overall proton relaxation times, but the magnitude of this effect on different protons in the same molecule has a variety of contributors, from the motion of the guest when bound, to the position of the protons in the cavity and the magnetic anisotropy induced by the aromatic walls of the host.
View Article and Find Full Text PDFChemistry
March 2024
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91, Stockholm, Sweden.
Methylation of amines inside an introverted resorcinarene-based deep methyl ester cavitand is investigated by means of molecular dynamics simulations and quantum chemical calculations. Experimentally, the cavitand has been shown to bind a number of amines and accelerate the methylation reaction by more than four orders of magnitude for some of them. Eight different amines are considered in the present study, and the geometries and energies of their binding to the cavitand are first characterized and analyzed.
View Article and Find Full Text PDFChemistry
December 2023
Department of Chemistry & Biochemistry, The Ohio State University, 1100 W. 18th Avenue, Columbus, OH, 43210, USA.
We describe the preparation, dynamic, assembly characteristics of vase-shaped basket 1 along with its ability to form an inclusion complex with anticancer drug mitoxantrone in abiotic and biotic systems. This novel cavitand has a deep nonpolar pocket consisting of three naphthalimide sides fused to a bicyclic platform at the bottom while carrying polar glycines at the top. The results of H Nuclear Magnetic Resonance (NMR), H NMR Chemical Exchange Saturation Transfer (CEST), Calorimetry, Hybrid Replica Exchange Molecular Dynamics (REMD), and Microcrystal Electron Diffraction (MicroED) measurements are in line with 1 forming dimer [1 ] , to be in equilibrium with monomers 1 (relaxed) and 1 (squeezed).
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