Abstract
Developing infrared (IR) probes is of great interest in biomolecular imaging and spectroscopy. We report our attempt to improve the IR properties of alkyne-derivatized compounds. The vibrational properties of the alkyne (CC) stretch mode of aromatic silylacetylene 1 and aliphatic silylacetylene 2 were studied using Fourier transform infrared and femtosecond IR pump-probe spectroscopies. We find that the insertion of silicon at the position adjacent to the alkyne group, separating it from the compound's main body, causes an approximately 10-fold increase in the dipole strength of the CC stretch mode and a lengthening of its vibrational lifetime from 5.6 ps for the acetylenic compound without a silicon atom acting like a thermal insulator to 50.6 and 50.4 ps for 1 and 2, respectively. The enhanced dipole strength and the increased lifetime of 1 allowed us to measure the 2D IR spectra for long waiting times up to 450 ps, which suggests that the dynamic observation range of 2D IR spectroscopy with these IR probes can be extended into the subnanosecond range where protein skeletal movements occur.
| Original language | English |
|---|---|
| Pages (from-to) | 6274-6281 |
| Number of pages | 8 |
| Journal | Journal of Physical Chemistry B |
| Volume | 123 |
| Issue number | 29 |
| DOIs | |
| Publication status | Published - 2019 May 25 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry
Cite this
Rational Design of an Acetylenic Infrared Probe with Enhanced Dipole Strength and Increased Vibrational Lifetime. / Kossowska, Dorota; Park, Kwanghee; Park, Jun Young; Lim, Chaiho; Kwak, Kyungwon; Cho, Minhaeng.
In: Journal of Physical Chemistry B, Vol. 123, No. 29, 25.05.2019, p. 6274-6281.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Rational Design of an Acetylenic Infrared Probe with Enhanced Dipole Strength and Increased Vibrational Lifetime
AU - Kossowska, Dorota
AU - Park, Kwanghee
AU - Park, Jun Young
AU - Lim, Chaiho
AU - Kwak, Kyungwon
AU - Cho, Minhaeng
PY - 2019/5/25
Y1 - 2019/5/25
N2 - Developing infrared (IR) probes is of great interest in biomolecular imaging and spectroscopy. We report our attempt to improve the IR properties of alkyne-derivatized compounds. The vibrational properties of the alkyne (CC) stretch mode of aromatic silylacetylene 1 and aliphatic silylacetylene 2 were studied using Fourier transform infrared and femtosecond IR pump-probe spectroscopies. We find that the insertion of silicon at the position adjacent to the alkyne group, separating it from the compound's main body, causes an approximately 10-fold increase in the dipole strength of the CC stretch mode and a lengthening of its vibrational lifetime from 5.6 ps for the acetylenic compound without a silicon atom acting like a thermal insulator to 50.6 and 50.4 ps for 1 and 2, respectively. The enhanced dipole strength and the increased lifetime of 1 allowed us to measure the 2D IR spectra for long waiting times up to 450 ps, which suggests that the dynamic observation range of 2D IR spectroscopy with these IR probes can be extended into the subnanosecond range where protein skeletal movements occur.
AB - Developing infrared (IR) probes is of great interest in biomolecular imaging and spectroscopy. We report our attempt to improve the IR properties of alkyne-derivatized compounds. The vibrational properties of the alkyne (CC) stretch mode of aromatic silylacetylene 1 and aliphatic silylacetylene 2 were studied using Fourier transform infrared and femtosecond IR pump-probe spectroscopies. We find that the insertion of silicon at the position adjacent to the alkyne group, separating it from the compound's main body, causes an approximately 10-fold increase in the dipole strength of the CC stretch mode and a lengthening of its vibrational lifetime from 5.6 ps for the acetylenic compound without a silicon atom acting like a thermal insulator to 50.6 and 50.4 ps for 1 and 2, respectively. The enhanced dipole strength and the increased lifetime of 1 allowed us to measure the 2D IR spectra for long waiting times up to 450 ps, which suggests that the dynamic observation range of 2D IR spectroscopy with these IR probes can be extended into the subnanosecond range where protein skeletal movements occur.
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UR - http://www.scopus.com/inward/citedby.url?scp=85070875346&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.9b04925
DO - 10.1021/acs.jpcb.9b04925
M3 - Article
VL - 123
SP - 6274
EP - 6281
JO - Journal of Physical Chemistry B Materials
JF - Journal of Physical Chemistry B Materials
SN - 1520-6106
IS - 29
ER -