Electronic Spectroscopy of Cold, Protonated Tryptophan and Tyrosine

We report here a new method to obtain electronic spectra of biomolecular ions that are produced in the gas phase by electrospray and cooled to ∼10 K in a 22-pole ion trap, and we demonstrate this technique by applying it to protonated tryptophan and tyrosine. Cooling in the trap greatly simplifies the spectrum of protonated tyrosine, which exhibits a well-defined band origin and clearly resolved low frequency vibrational bands. In contrast, the spectrum of protonated tryptophan exhibits only broad features, even at low temperatures, suggesting that a fast nonradiative process broadens the individual vibronic features, even upon excitation at the electronic band origin. The method demonstrated here should be applicable to a wide variety of biological molecules.