Decay and cooling of biomolecules in an electrostatic storage ring S. Tomita Department of Physics and Astronomy University of Aarhus DK-8000 Aarhus C,

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Decay and cooling of biomolecules in an electrostatic storage ring S. Tomita Department of Physics and Astronomy University of Aarhus DK-8000 Aarhus C, Denmark June 27 -July 2, rth annual LEIF meeting - Belfast, N. Ireland4rth annual LEIF meeting

Ubiquitin 76 amino acid protein 8.6 k amu 40 Å Helical structure:  helix Sheet structure:  sheets

Common amino acids

Photo absorption in solution Photo absorption Tryptophan Tyrosine Phenylalanine Absorption Wavelength Tryptophan280 nm Tyrosine274 nm Phenylalanine257 nm

Molecules investigated Lys-Trp-LysTrp

Electrospray J.B. Fenn (1988) Nobel Prize in Chemistry (2002) ~3kV ~1cm ~10  M/L ~1  L/min

Electrospray Source 1 mbar mbar10 -5 mbar10 -6 mbar Rotary pump Turbo pump Turbo pump Heated capillary ESI needle 4kV Fused silica capillary 22 pole Ion trap Tube lens Skimmer Octapole Lenses Acceleration tube

ELISA 1 m Detector for neutrals Laser Accelerator with electrospray ion source Magnet Laser power meter Injection Channeltron t Counts Pulsed Alexandrite Laser nm (3 rd harmonic) Pulsed NdYAG Laser 266nm (4 th harmonic)

Photo absorption in solution Heating by photo absorption h TrTr

1/t decay law Distribution at time t Yield of decay Maximum at E m (t) 1/k = t at E m (t)

[Lys-Trp-Lys+H] + 266nm Injection Laser

[Lys-Trp-Lys+H] + 243nm  E = 5.10 eV  = 0.48ms 260nm  E = 4.77 eV  = 0.86ms Lower photon energy Longer life time Higher photon energy Shorter life time

Arrhenius plot We can determine pre-exponential factor and dissociation energy. 243nm 260nm

Dependence on temperature of ion trap HOT COLD Temperature of ion trap

[Trp+H] nm InjectionLaser 1/t

Fluorescence

Quantum yield Solvent Amino AcidPolypeptide EmissionQuantumEmissionQuantum PhenylalanineDMSO TyrosineDMSO TyrosineH20H TryptophanDMSO TryptophanH20H Quantum yield is very sensitive to the environment. (Amino Acid) > (Polypeptide) DMSO > H 2 0

Summary Lys-Trp-Lys Narrow internal energy distribution Exponential decay after photo absorption Statistical decay through ergonic process Determination of dissociation energy Trp 1/t Decay Due to high fluorescence quantum yield?

Collaborators Stockholm H. Cederquist H.T. Schmidt J. Jensen H. Zettergren CAEN B.A. Huber B. Manil L. Maunoury Canada J.S. Forstar Group at Univ. of Aarhus P. Hvelplund J.U. Andersen S.B. Nielsen J. Rangama B. Liu