Dimeric Self-Assembly of Pyridyl Guanidinium Carboxylates in Polar Solvents

Muhammad Irfan Ashiq, Biniam F. Tesfatsion, Francesca Gaggini, Sally Dixon, Jeremy Dunbar Kilburn

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    4 Citations (Scopus)

    Abstract

    A series of pyridyl guanidinium-carboxylates has been prepared and the dimeric self-assembly of these studied in H(2)O/DMSO mixtures, principally using dilution isothermal calorimetry. Compounds 5 and 6, incorporating an aromatic ring in the "tethering" region between the guanidinium and carboxylate groups, demonstrate the strongest dimerisation in neat DMSO. X-ray crystal structures of 5 and 6 reveal two different dimerisation architectures in the solid-state, but both involve carboxylate-guanidinium salt bridges as anticipated, and pi-pi interactions. Compounds 10-16 incorporating peptidic fragments between the guanidinium and carboxylate groups, showed reduced dimerisation strength with increased amino acid content, but also sustained dimerisation under increasingly aqueous conditions, up to 50% H(2)O/DMSO in the case of 14 and 15. The extent of our study in H(2)O/DMSO mixtures was determined by substrate solubility of 10-16, and not the limit of self-assembly.

    Original languageEnglish
    Pages (from-to)12387-12397
    Number of pages11
    JournalChemistry : a European Journal
    Volume16
    Issue number41
    DOIs
    Publication statusPublished - 2010

    Keywords

    • calorimetry
    • dimerization
    • molecular recognition
    • self-assembly
    • supramolecular chemistry
    • BETA-HAIRPIN PEPTIDE
    • ENTHALPY-ENTROPY COMPENSATION
    • SIDE-CHAIN INTERACTIONS
    • AMINO-ACID BINDING
    • THERMODYNAMIC ANALYSIS
    • MOLECULAR RECOGNITION
    • OXOANION BINDING
    • MODEL SYSTEMS
    • BIOMOLECULAR INTERACTIONS
    • RECEPTOR LIBRARIES

    Cite this

    Ashiq, M. I., Tesfatsion, B. F., Gaggini, F., Dixon, S., & Kilburn, J. D. (2010). Dimeric Self-Assembly of Pyridyl Guanidinium Carboxylates in Polar Solvents. Chemistry : a European Journal, 16(41), 12387-12397. https://doi.org/10.1002/chem.201001861