Infrared probes based on nitrile-derivatized prolines: Thermal insulation effect and enhanced dynamic range

Kwang Hee Park, Jonggu Jeon, Yumi Park, Soyoung Lee, Hyeok Jun Kwon, Cheonik Joo, Sungnam Park, Hogyu Han, Minhaeng Cho

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Vibrational chromophores that are sensitive to local electrostatic environment are useful probes of structural variations of proteins on subnanosecond time scales, but their short vibrational lifetimes often limit their applicability. Here we explore a possibility to increase the lifetime of nitrile probes by introducing heavy atoms between the probe and protein side chains. Stereoisomers of thiocyanato- and selenocyanato-derivatized prolines, Pro-SCN and Pro-SeCN, are synthesized, and their CN stretch lifetimes in D 2O and chloroform are measured with polarization-controlled IR pump-probe spectroscopy. The measured lifetimes of 170-330 ps for Pro-SeCN are three to four times longer than those for Pro-SCN, indicating that selenium atom is more effective than sulfur atom in blocking the intramolecular vibrational relaxation pathways of the CN stretch mode. This is further confirmed by carrying out nonequilibrium molecular dynamics simulations of the vibrational relaxation processes. Given the crucial role of the proline residue in determining protein structures, we anticipate that the Pro-SeCN probe can be an excellent site-specific probe of changes in protein local environment.

Original languageEnglish
Pages (from-to)2105-2110
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume4
Issue number13
DOIs
Publication statusPublished - 2013 Jul 3

Fingerprint

Nitriles
Thermal insulation
Proline
Hot Temperature
Infrared radiation
Proteins
Atoms
Stereoisomerism
Molecular Dynamics Simulation
Selenium
Chloroform
Static Electricity
Sulfur
Spectrum Analysis
Relaxation processes
Chromophores
Chlorine compounds
Molecular dynamics
Electrostatics
Pumps

Keywords

  • IR probe
  • IR pump-probe spectroscopy
  • nonequilibrium molecular dynamics simulation
  • vibrational relaxation

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Infrared probes based on nitrile-derivatized prolines : Thermal insulation effect and enhanced dynamic range. / Park, Kwang Hee; Jeon, Jonggu; Park, Yumi; Lee, Soyoung; Kwon, Hyeok Jun; Joo, Cheonik; Park, Sungnam; Han, Hogyu; Cho, Minhaeng.

In: Journal of Physical Chemistry Letters, Vol. 4, No. 13, 03.07.2013, p. 2105-2110.

Research output: Contribution to journalArticle

Park, Kwang Hee ; Jeon, Jonggu ; Park, Yumi ; Lee, Soyoung ; Kwon, Hyeok Jun ; Joo, Cheonik ; Park, Sungnam ; Han, Hogyu ; Cho, Minhaeng. / Infrared probes based on nitrile-derivatized prolines : Thermal insulation effect and enhanced dynamic range. In: Journal of Physical Chemistry Letters. 2013 ; Vol. 4, No. 13. pp. 2105-2110.
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