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A B3LYP investigation of the conformational and environmental sensitivity of carbon–deuterium frequencies of aryl-perdeuterated phenylalanine and tryptophan

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Abstract

Carbon–deuterium labeled amino acids can serve as sensitive probes for biophysical characterization. Although multiple research groups have used infrared spectroscopy in conjunction with alkyl backbone or side-chain deuterated amino acids for the biophysical characterization of conformational and/or environmental changes, it was not entirely clear to the authors that perdeuterated aryl rings would demonstrate a similar sensitivity toward conformational or environmental changes. In an effort to evaluate the sensitivity of aryl carbon–deuterium (C–D) IR frequencies, a B3LYP investigation of the sensitivity of aryl C–D frequencies toward conformational and environmental changes was conducted for phenylalanine (Phe) and tryptophan (Trp). To compensate for the low molar absorptivity of C–D frequencies, perdeuterated aryl rings were investigated, which are commercially available and can be readily compared to experimental data. B3LYP results suggest that aryl-deuterated Phe and Trp will exhibit moderate sensitivities toward conformational and environmental changes with frequency shifts upward of 13 and 26 cm−1 for Phe and Trp, respectively. B3LYP predicts that conformational sensitivity arises from dipole changes and not orbital alignment changes. In an effort to mimic what might be observed experimentally, simulated IR spectra were created and show absorption band changes with conformational and environmental changes, which indicate that IR characterization of perdeuterated aryl rings in amino acids could serve as a biophysical tool.

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Acknowledgments

We thank Matt Bergman, Dr. Steven Corcelli, Dr. Ruel Desamero, Brett Hendricks, Jason Schnagl, and the Gonzaga University Department of Chemistry and Biochemistry. Computer time was provided by the Intel Corp. Computer Science Laboratory at Gonzaga University. This research was supported in part by a grant to Gonzaga University from the Howard Hughes Medical Institute through the Undergraduate Science Education Program, the Gonzaga Science Research Program, Gonzaga University Start-up Funds, and Donor Funds administered by Gonzaga’s Office of the Dean for the School of Arts and Sciences.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Gonzaga University, 502 East Boone Avenue, Spokane, WA, 99258, USA

    Alyssa S. Hickert, Andrew C. Durgan, Duncan A. Patton, Samantha A. Blake & Matthew E. Cremeens

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  1. Alyssa S. Hickert
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  2. Andrew C. Durgan
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  3. Duncan A. Patton
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  4. Samantha A. Blake
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  5. Matthew E. Cremeens
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Correspondence to Matthew E. Cremeens.

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Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Hickert, A.S., Durgan, A.C., Patton, D.A. et al. A B3LYP investigation of the conformational and environmental sensitivity of carbon–deuterium frequencies of aryl-perdeuterated phenylalanine and tryptophan. Theor Chem Acc 130, 883–889 (2011). https://doi.org/10.1007/s00214-011-1050-5

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  • DOI: https://doi.org/10.1007/s00214-011-1050-5

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