10.1002/anie.201803849
Angewandte Chemie International Edition
COMMUNICATION
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Figure 4. Simulated 2D IR spectra of Trp5CN–Gly–Phe4CN in water, zero
coupling (top) and 1.4 cm-1 coupling (bottom).
and proteins via tryptophan. The synthesized 5-cyano-L-
tryptophan was incorporated into a short peptide system as
second cyano- label, Trp5CN–Gly–Phe4CN, to validate the efficacy
of measuring spatial distance using this probe pair via 2D IR
spectroscopy. The vibrational coupling, 1.4 cm-1 between the
cyano- probes was quantified via simulation of the 2D IR spectrum
and analysis of the slope along the max contours of the positive
transitions. The spatial distance, ~13 Å, between the two labels
was found experimentally using transition dipole coupling theory
and confirmed theoretically. Other cyano-tryptophan regioisomers
are currently being synthesized, and the spectroscopic studies of
such compounds will be presented in due course.
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Experimental Section
5-Cyano-L-tryptophan (Trp5CN) was synthesized as described above and
characterized via Fourier transform infrared (FTIR) spectroscopy.
Additionally, a short peptide system, Trp5CN–Gly–Phe4CN, was synthesized
via standard fluorenylmethyloxycarbonyl chloride (FMOC) solid-state
peptide synthesis to include the Trp5CN. FTIR spectra (Nicolet 6700,
Thermo Scientific) of Trp5CN, indole3CN, indole4CN, indole5CN, indole6CN, and
the short peptide Trp5CN–Gly–Phe4CN were collected with 1 cm-1 resolution
and a nitrogen-cooled MCT detector. 2D IR spectra were measured using
the box-CARS configuration as described in prior literature.[20e] The optical
densities for both methods were between 0.01-0.03. See SI for more
details.
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Acknowledgements
[7]
The research was supported by NIH (R15GM1224597) to MJT.
PHG and MWF acknowledge the University of Scranton for
support for this research.
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Conflict of interest
The authors declare no conflict of interest.
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Keywords: Cyano-Tryptophan • 2D IR • Vibrational Coupling •
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Spectroscopic Reporters • Probe Pairs
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