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Related Experiment Videos

Chemical triple-mutant boxes for quantifying cooperativity in intermolecular interactions.

Christopher A Hunter1, Philip S Jones, Pascale Tiger

  • 1Centre for Chemical Biology, Krebs Institute for Biomolecular Science, Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK. c.hunter@sheffield.ac.uk

Chemistry (Weinheim an Der Bergstrasse, Germany)
|February 4, 2003
PubMed
Summary

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This study quantifies molecular interactions in H-bonded zipper complexes. Edge-to-face aromatic interactions remain stable despite significant changes in overall complex stability.

Area of Science:

  • Supramolecular Chemistry
  • Chemical Thermodynamics

Background:

  • Chemical double-mutant cycles are a method for quantifying intermolecular interactions.
  • Hydrogen-bonded zipper complexes provide a model system for studying molecular interactions.
  • Cooperativity between interactions can influence the stability of molecular complexes.

Purpose of the Study:

  • To quantify intermolecular functional-group interactions in H-bonded zipper complexes.
  • To assess the impact of overall complex stability on specific interactions.
  • To investigate cooperativity effects using a triple-mutant box construct.

Main Methods:

  • Utilized chemical double-mutant cycles in chloroform.
  • Employed a triple-mutant box approach to measure cooperativity.

Related Experiment Videos

  • Varied overall complex stability to observe effects on specific interactions.

    • Main Results:

    • Quantified the sum of two edge-to-face aromatic interactions as -2.9 +/- 0.5 kJ mol-1.
    • Demonstrated that these interactions are insensitive to stability changes up to 13.7 +/- 0.2 kJ mol-1.
    • Found that enthalpic cooperative effects due to entropy-enthalpy compensation are within measurement error for this system.

    Conclusions:

    • Edge-to-face aromatic interactions in H-bonded zippers are robust and independent of overall complex stability.
    • The triple-mutant box approach effectively quantifies cooperativity without significant perturbation from entropy-enthalpy compensation.
    • This work validates the use of double-mutant cycles for accurate interaction measurements in systems with varying stability.