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Ultrafast dynamics of hemin aggregates.

Arpita Nath1, J A Dharmadhikari, A K Dharmadhikari

  • 1Tata Institute of Fundamental Research, 1, Homi Bhabha Road, Mumbai 400005, India. shyamal@tifr.res.in.

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Summary

Solvent effects on hemin conformation were studied using time-resolved optical Kerr effect (OKE). A novel libration process in heme oligomers was discovered, offering insights into self-assembly and biological implications.

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Area of Science:

  • Physical Chemistry
  • Biophysical Chemistry
  • Spectroscopy

Background:

  • Hemin conformation and dynamics are influenced by solvent environments.
  • Understanding heme self-assembly is crucial for biological systems.
  • Nonlinear optical properties of hemin are not fully characterized.

Purpose of the Study:

  • To investigate the impact of solvents on hemin conformation and dynamics.
  • To measure the nonlinear electronic susceptibility (χ(3)) of hemin solutions.
  • To identify novel dynamic processes in hemin solutions.

Main Methods:

  • Time-resolved optical Kerr effect (OKE) spectroscopy.
  • Ultrafast laser pulses (35 fs, 800 nm).
  • Analysis of nonlinear electronic susceptibility (χ(3)).

Main Results:

  • Hemin solutions exhibit a significantly smaller χ(3) compared to thin films.
  • Negative real and imaginary components of χ(3) indicate one- and two-photon absorption.
  • A novel femtosecond libration process, possibly due to π-π hemin oligomers, was detected.

Conclusions:

  • Solvent interactions significantly affect hemin's conformational dynamics.
  • The study reveals a previously undetected libration process in hemin oligomers.
  • Findings provide insights into heme self-assembly and potential roles in pathogenic conditions.