Supramolecular capsules are nanoscale containers useful for the study of molecular behavior in confined spaces. They offer practical applications in catalysis, molecular transport, drug delivery, and materials science. Self-assembly has proven to be an effective approach in constructing supramolecular capsules and a variety of well-known noncovalent interactions including hydrogen bonding, metal coordination and ionic interactions have been deployed. Bowl-shaped cavitand structures built up from resorcinarenes have particular advantages for the construction of supramolecular capsules, and this highlight discusses the unconventional self-assembly of molecular capsules held together by halogen and chalcogen bonds.
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http://dx.doi.org/10.1039/d0cc07784d | DOI Listing |
Chemistry
December 2024
Dipartimento di Scienze Molecolari e Nanosistemi, Universitá Ca' Foscari di Venezia, Via Torino 155, Mestre Venezia, Italy.
The supramolecular resorcinarene hexameric capsule efficiently promotes the unprecedented reaction between isocyanides and electron-deficient aromatic aldehydes leading to the formation of imines and carbon monoxide. The mechanism of the reaction was investigated via isotope labelling, kinetic analysis of the reaction, computational studies and the independent synthesis of a proposed intermediate. Control experiments indicate that the formation of the key aziridinone intermediate is limited to the cavity of the capsule.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2024
Department of Chemistry 'Ugo Schiff', University of Florence, via della Lastruccia 3-13, 50019 Sesto Fiorentino (FI), Italy. Electronic address:
The polyallylamine hydrochloride (PAH) polymer is here functionalized with branched and biocompatible polysaccharide dextran (DEX) molecules. Covalent conjugation of DEX to PAH has been achieved through a straightforward reductive amination approach, allowing for a controlled number of DEX chains per PAH polymer (PAH:DEX, n = 0.1, 0.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Metal-organic cages and capsules exhibit space-specific functions based on their discrete hollow structures. To acquire enzyme-like asymmetric or intricate structures, they have been modified by desymmetrization with two or more different ligands. There is a need to establish new strategies that can desymmetrize structures in a simple way using only one type of ligand, which is different from the mixed-ligand approach.
View Article and Find Full Text PDFMacromol Rapid Commun
November 2024
PCFM, LIFM Lab and GD HPPC Lab, School of Chemistry, Sun Yat-sen University, Guangzhou, 510275, P. R. China.
Nanostructures with curved surfaces and chiral-directing residues are highly desirable in the synthesis of asymmetric chemicals, but they remain challenging to synthesize without using unique templates due to the disfavored torsion energy of twisted architectures toward chiral centers. Here, a strategy for the facile fabrication of highly cured capsule-shaped catalysts with chiral interiors by the amplification of molecular chirality via the irreversible cross-linking of 2D asymmetric laminates is presented. The key to the success of these irregular 2D layers is the use of hierarchical assembly of chiral macrocycles, which can exactly regulate the cured nanostructures as well as asymmetric catalysis.
View Article and Find Full Text PDFNat Commun
November 2024
School of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College Green, Dublin, D02 PN40, Ireland.
Contrary to common chemical intuition, cation-π interactions can persist in polar, aqueous reaction solutions, rather than in dry non-coordinative solvent systems. This account highlights how alkali ion-π interactions impart distinctive structure-influencing supramolecular forces that can be exploited in the preparation of nanoscopic metal-organic capsules. The incorporation of alkali ions from polar solutions into molecular pockets promotes the assembly of otherwise inaccessible capsular entities whose structures are distinctive to those of common polyoxovanadate clusters in which {V=O} moieties usually point radially to the outside, shielding the molecular entities.
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