Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations

Lee, Kyungkoo; Park, Kwang Hee; Joo, Cheonik; Kwon, Hyeok Jun; Han, Hogyu; Ha, Jeong Hyon; Park, Sungnam; Cho, Minhaeng

doi:10.1016/j.chemphys.2011.04.024

Cited by 21 publications

(12 citation statements)

References 39 publications

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“…In addition to the reorientation of the whole molecules, internal rotation of the azide group around the CN bond axis in N 3 -Ala and N 3 -Pro ± 2 ps, which is related to interconversion between the bound and free azide group. 16 Based on the similar anisotropy decays of N 3 -Ala and N 3 -Pro to that of N 3 − , we concluded that the internal rotation of the azide group plays a significant role in the anisotropy decays of N 3 -Ala and N 3 -Pro. As mentioned in Ref.…”

Section: B Vibrational Energy Relaxationmentioning

confidence: 56%

“…34 Lee et al showed that the IR spectrum of 4-azideproline derivative, Ac-(4S)-Azp-NHMe (SA), in CHCl 3 has two peaks which correspond to two different conformers in the N 3 antisymmetric stretching region. 16,17 An asymmetric band was also observed in the IR spectrum of azidealanine dipeptide in THF, as a result of two distinct conformers of the peptide. 35 Therefore, we consider that various kinds of conformers of N 3 -Ala and N 3 -Pro are present in water, and these conformers yield different environments around the azide group, which cause an inhomogeneous distribution of the vibrational transition frequencies.…”

Section: Resultsmentioning

confidence: 88%

“…15 Cho and co-workers reported vibrational energy relaxation and internal rotational mode of the proline derivatives which have azide or thiocyanate probes in D 2 O and CHCl 3 . [16][17][18] The Bredenbeck group monitored vibrational energy transfer process between two non-native amino acids, β-(1-azulenyl)--alanine and -azidohomoalanine, in a model peptide. 19 There are various kinds of unnatural amino acids bearing vibrational probes which can be incorporated into peptides and proteins by a peptide synthesis or genetic procedure.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Vibrational dynamics of azide-derivatized amino acids studied by nonlinear infrared spectroscopy

Okuda

Ohta

Tominaga

2015

The Journal of Chemical Physics

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Recently, biomolecules which are labeled by azide or thiocyanate groups in solutions and proteins have been studied to examine microscopic environment around a solute by nonlinear infrared (IR) spectroscopy. In this study, we have performed two-dimensional infrared (2D-IR) spectroscopy to investigate the vibrational frequency fluctuations of two different azide-derivatized amino acids, Ala (N3-Ala) and Pro (N3-Pro), and N3(-) in water. From the 2D-IR experiments, it was found that the frequency-frequency time correlation function (FFTCF) of solute can be modeled by a delta function plus an exponential function and constant. FFTCF for each probe molecule has a decay component of about 1 ps, and this result suggests that the stretching mode of the covalently bonded azide group is sensitive to the fluctuations of hydrogen bond network system, as found in previous studies of N3(-) in water. In contrast to FFTCF of N3(-), FFTCF of the azide-derivatized amino acids contains static component. This static component may reflect dynamics of water affected by the solutes or the structural fluctuations of the solute itself. We also performed the IR pump-probe measurements for the probe molecules in water in order to investigate vibrational energy relaxation (VER) and reorientational relaxation. It was revealed that the charge fluctuations in the azide group are significant for the VER of this mode in water, reflecting that the VER rate of N3(-) is faster than those of the azide-derivatized amino acids. While the behaviors of the anisotropy decay of N3-Ala and N3(-) are similar to each other, the anisotropy decay of N3-Pro contains much slower decaying component. By considering the structural difference around the vibrational probe between N3-Ala and N3-Pro, it is suggested that the structural freedom of the probe molecules can affect the reorientational processes.

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Section: B Vibrational Energy Relaxationmentioning

confidence: 56%

Section: Resultsmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational dynamics of azide-derivatized amino acids studied by nonlinear infrared spectroscopy

Okuda

Ohta

Tominaga

2015

The Journal of Chemical Physics

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“…1,9,16 In the field of vibrational spectroscopy experimental advances in ultrafast multidimensional methods have demonstrated how the study of relaxation dynamics can elucidate some important aspects of the interaction between a molecule and its environment. 17–23 Recent examples include the solvation dynamics in bulk and at the interfaces, 19,21,23–25 chemical exchange, 26–28 conformational dynamics, 29,30 and binding processes in proteins and drugs. 31–33 …”

mentioning

confidence: 99%

Quantum Beats and Coherence Decay in Degenerate States Split by Solvation

Chuntonov

Kuroda

Ghosh

et al. 2013

J. Phys. Chem. Lett.

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Coherent dynamics of degenerate quantum states symmetry-broken on the femtosecond timescale is found to exhibit the phenomenon of quantum beats. Frequency-resolved and polarization-selective heterodyned transient grating spectroscopy enabled us to retrieve the oscillation pattern characteristic of the beating in systems undergoing ultrafast dynamical processes. This methodology applies to the general phenomena of coherence dynamics which is important in any ultrafast multidimensional spectroscopy. A particular application to the vibrational spectroscopy of coherence in the degenerate normal modes of the tricyanomethanide anion solvated in water is explored in this study. The relaxation of the cross-polarization transient grating anisotropy is shown to reflect the loss of the vibrational coherence, which is caused by ultrafast dynamics of the water solvation shell.

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“…Because the transition dipole moments of the vibrational states are localized more in a molecule than those of the electronic states, the information provided by vibrational spectroscopy about the conformational dynamics is complementary to that provided by electronic spectroscopy. Using polarization-controlled IR pump−probe and/or two-dimensional IR measurements, several groups have examined the internal rotational motions of vibrational probes in CHCl 3 18,19 and CCl 4 20 solutions. For molecules with many single covalent bonds, multiple rotational motions around the bond axes are expected if these motions are energetically and conformationally allowed.…”

Section: Introductionmentioning

confidence: 99%

Rotational Dynamics of Solutes with Multiple Single Bond Axes Studied by Infrared Pump–Probe Spectroscopy

2018

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To investigate the relationship between the structural degrees of freedom around a vibrational probe and the rotational relaxation process of a solute in solution, we studied the anisotropy decays of three different N3-derivatized amino acids in primary alcohol solutions. By performing polarization-controlled IR pump–probe measurements, we reveal that the anisotropy decays of the vibrational probe molecules in 1-alcohol solutions possess two decay components, at subpicosecond and picosecond time scales. On the basis of results showing that the fast relaxation component is insensitive to the vibrational probe molecule, we suggest that the anisotropy decay of the N3 group on a subpicosecond time scale results from a local, small-amplitude fluctuation of the flexible vibrational probe, which does not depend on the details of its molecular structure. However, the slow relaxation component depends on the solute: with longer alkyl chains attached to the N3 group, the anisotropy decay of the slow component is faster. Consequently, we conclude that the slow relaxation component corresponds to the reorientational motion of the N3 group correlated with other intramolecular rotational motions (e.g., rotational motions of the neighboring alkyl chain). Our experimental results provide important insight into understanding the rotational dynamics of solutes with multiple single bond axes in solution.

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Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations

Cited by 21 publications

References 39 publications

Vibrational dynamics of azide-derivatized amino acids studied by nonlinear infrared spectroscopy

Vibrational dynamics of azide-derivatized amino acids studied by nonlinear infrared spectroscopy

Quantum Beats and Coherence Decay in Degenerate States Split by Solvation

Rotational Dynamics of Solutes with Multiple Single Bond Axes Studied by Infrared Pump–Probe Spectroscopy

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