title: Thermal vaporization of biological nanoparticles: fragment-free vacuum ultraviolet photoionization mass spectra of tryptophan, phenylalanine-glycine-glycine, and beta-carotene.
abstract: A simple, new way to introduce fragile biomolecules into the gas phase via thermal vaporization of nanoparticles is described. The general utility of this technique for the study of biomolecules is demonstrated by coupling this source to tunable synchrotron vacuum ultraviolet radiation. Fragment-free photoionization mass spectra of tryptophan, phenylalanine-glycine-glycine, and beta-carotene are detected with signal-to-noise ratios exceeding 100. The 8.0 eV photoionization mass spectrum of tryptophan nanoparticles vaporized at 373 K is dominated by a single parent ion peak that exhibits a 20-fold enhancement over the methylene indole fragment ion. The degree of dissociative photoionization of tryptophan can be precisely controlled either by the thermal energy imparted into the neutral tryptophan molecule or by the energy of the ionizing photon. The results reveal how approximately 0.5 eV changes in internal energy affect both the photoionization mass spectrum of tryptophan and the appearance energy of the daughter ion fragments. This method allows the ionization energies of glycine (9.3 +/- 0.1 eV), tryptophan (7.3 +/- 0.2 eV), phenylalanine (8.6 +/- 0.1 eV), phenylalanine-glycine-glycine (9.1 +/- 0.1 eV), and beta-carotene (<7.0 eV) molecules to be determined directly from the photoionization efficiency spectra.
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720, USA.
authors.forename: Kevin R
authors.initials: KR
authors.lastname: Wilson
authors.forename: Michael
authors.initials: M
authors.lastname: Jimenez-Cruz
authors.forename: Christophe
authors.initials: C
authors.lastname: Nicolas
authors.forename: Leonid
authors.initials: L
authors.lastname: Belau
authors.forename: Stephen R
authors.initials: SR
authors.lastname: Leone
authors.forename: Musahid
authors.initials: M
authors.lastname: Ahmed
mesh_terms: D004735:Energy Transfer; D013058:Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D049329:Nanostructures / Q000032:analysis* / Q000737:chemistry; D036103:Nanotechnology; D009842:Oligopeptides / Q000032:analysis*; D010316:Particle Size; D017785:Photons; D012680:Sensitivity and Specificity; D014364:Tryptophan / Q000032:analysis*; D014835:Volatilization; D019207:beta Carotene / Q000032:analysis*
chemical_list: D009842:Oligopeptides; D019207:beta Carotene; C043963:phenylalanyl-glycyl-glycine; D014364:Tryptophan