Abstract
The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl 3. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.
| Original language | English |
|---|---|
| Pages (from-to) | 23-29 |
| Number of pages | 7 |
| Journal | Chemical Physics |
| Volume | 396 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2012 Mar 2 |
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Keywords
- Azido stretch mode
- Proline dynamics
- Two-dimensional infrared spectroscopy
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Physics and Astronomy(all)
Cite this
Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline : Chemical exchange 2DIR spectroscopic investigations. / Lee, Kyung Koo; Park, Kwang Hee; Joo, Cheonik; Kwon, Hyeok Jun; Han, Hogyu; Ha, Jeong Hyon; Park, Sungnam; Cho, Minhaeng.
In: Chemical Physics, Vol. 396, No. 1, 02.03.2012, p. 23-29.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline
T2 - Chemical exchange 2DIR spectroscopic investigations
AU - Lee, Kyung Koo
AU - Park, Kwang Hee
AU - Joo, Cheonik
AU - Kwon, Hyeok Jun
AU - Han, Hogyu
AU - Ha, Jeong Hyon
AU - Park, Sungnam
AU - Cho, Minhaeng
PY - 2012/3/2
Y1 - 2012/3/2
N2 - The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl 3. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.
AB - The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl 3. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.
KW - Azido stretch mode
KW - Proline dynamics
KW - Two-dimensional infrared spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=84859542624&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84859542624&partnerID=8YFLogxK
U2 - 10.1016/j.chemphys.2011.04.024
DO - 10.1016/j.chemphys.2011.04.024
M3 - Article
AN - SCOPUS:84859542624
VL - 396
SP - 23
EP - 29
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 1
ER -