Laser desorption supersonic jet spectroscopy of hydrated tyrosine June 18th, 2013 Hikari OBA Tokyo Tech, Japan.

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Laser desorption supersonic jet spectroscopy of hydrated tyrosine June 18th, 2013 Hikari OBA Tokyo Tech, Japan

Cooperative effect of hydrogen bond *R. Nathaniel Pribble, et al. J. Chem. Phys., 106, 2145 (1997). Bz-(MeOH) 1 Bz-(MeOH) 2

Why tyrosine-water cluster ? Phenylalanine X Tyrosine XR Dopa different !almost same [1] L. C. Snoek, et al., CPL, [2] Y. Shimozono, et al., PCCP, 2013, 15, [3] S. Ishiuchi, et al., PCCP, 2011, 13, 7812

Why tyrosine-water cluster ? Stronger H-bond To Investigate cooperative effect of separate hydrogen bond more enhanced ? Dopa weaker H-bond Tyr XR-(H 2 O) 1

Laser desorption supersonic jet

REMPI and IR dip spectroscopy REMPIIR dip

REMPI spectra bands 1 bands 2 [1] Y. Shimozono, et al., PCCP, 2013, 15, 5163 [1]

REMPI A) B) Different structures! IR dip spectra of Tyr-(H 2 O) 1 cluster

Assignment of water binding site free OHH-bonded OH * T. Ebata, et al., International Journal of Mass Spectrometry and Ion Processes, 1996, 159, 111. * A) B) Tyr-(H 2 O) 1 Phenol Phenol-(H 2 O) 1 *

Assignment of water binding site bands 1bands 2 (phenolic OH bound)

Assignment of conformation of tyrosine-(H 2 O) 1 Tyr XR-(H 2 O) 1 Tyr XR Tyr XR-(H 2 O) 1 [1] [1] Y. Shimozono, et al., PCCP, 2013, 15, 5163 phenolic OH bound

Phe X Tyr XR Dopa Tyr XR-(H 2 O) 1 Comparison of the effect on hydrogen bond in amino acid stronger H-bond weaker H-bond This work ! ?

Importance of direction of dipole moments Dopa Tyr XR-(H 2 O) 1 Different direction !

Summary REMPI and IR dip spectra of tyrosine-(H 2 O) 1 were measured. Direction of dipole moments is important to enhance the hydrogen bond strength in cooperative effect.

Acknowledgment Merci beaucoup ! ( 1, ISMO 2 ) Hikari Oba 1, Ms. Yoko Shimozono Dr. Shun-ichi Ishiuchi Prof. Masaaki Fujii Chemical Resources Lab., Tokyo Tech. Dr. Pierre Çarçabal Institut des Sciences Moléculaires d’Orsay, U. Paris-Sud.

IR-UV Hole Burning spectra

Dipole moment of amino acid site and OH site

REMPI spectra of Tyr, Tyr-(H 2 O) 1, Dopa

Assignment of conformation A) B)

Amino acid bound Phenolic OH bound

IR spectra of 12 conformers of tyrosine [1] Assignment of amino acid chain [1] Y. Shimozono, et al., PCCP, 2013.