Probing substrate binding inside a paramagnetic cavity: a NMR spectroscopy toolbox for combined experimental and...

Area of Science:

• Supramolecular Chemistry
• Analytical Chemistry
• Biophysical Chemistry

Background:

• Paramagnetic metal centers in protein active sites are crucial for biological catalysis.
• Selective substrate detection is vital for environmental monitoring and biological research.

Purpose of the Study:

• To develop a covalently linked Fe(iii)porphyrin dimer-based paramagnetic sensory cavity.
• To achieve accurate detection and simultaneous identification of phenol binding within the cavity.

Main Methods:

• Spectroscopic studies including UV-vis, 1H NMR, and 19F NMR.
• X-ray crystallography to determine binding modes.
• Theoretical 19F NMR analysis for validating binding modes.

Main Results:

• The sensory cavity provided unique spectroscopic signatures for phenol binding.
• Distinguished between exo and endo binding modes of phenol.
• Theoretical 19F NMR analysis accurately replicated experimental data, revealing phenolato species chemical shifts.

Conclusions:

• The developed sensory cavity enables selective detection and identification of phenol.
• The study provides insights into substrate binding modes and the cavity's chemical environment.
• This work can lead to advanced diagnostic tools for monitoring conformational changes and interactions.