A sensitive photoabsorption technique for studies of gas-phase biomolecules has been used at the ELISA electrostatic heavy-ion storage ring. We show that the anion form of the chromophore of the green fluorescent protein in vacuo has an absorption maximum at 479 nm, which coincides with one of the two absorption peaks of the protein. Its absorption characteristics are therefore ascribed to intrinsic chemical properties of the chromophore. Evidently, the special beta-can structure of the protein provides shielding of the chromophore from the surroundings without significantly changing the electronic structure of the chromophore through interactions with amino acid side chains.

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Articles you may be interested inFirst storage of ion beams in the Double Electrostatic Ion-Ring Experiment: DESIREE Rev. Sci. Instrum. 84, 055115 (2013); 10.1063/1.4807702 Upgrade of the MIT Linear Electrostatic Ion Accelerator (LEIA) for nuclear diagnostics development for Omega, Z and the NIF Rev. Sci. Instrum. 83, 043502 (2012); 10.1063/1.3703315 The double electrostatic ion ring experiment: A unique cryogenic electrostatic storage ring for merged ion-beams studies Rev. Sci. Instrum. 82, 065112 (2011);An electrospray ion source has been coupled to an accelerator that injects ions into an electrostatic heavy-ion storage ring. Since the dc ion current produced by electrospray ionization is low (ϳ10 6 ions/s), ions are accumulated in a cylindrical ion trap filled with a helium buffer gas. The ions are collisionally damped in the buffer gas and confined to the central trap region by a rf field. Extraction from the trap occurs within a few microseconds and after acceleration through 22 kV, the ions of interest are selected by a magnet according to their mass to charge ratio. The ion bunch is subsequently injected into the ring. Both positive and negative ions have been stored, with masses ranging over 3 orders of magnitude (ϳ10 2 -10 4 Da). From a pickup signal in the ring, the number of ions in a bunch is estimated to be of the order of 10 3 -10 4 when the accumulation time is 0.1 s. Our first measurements show that we can store a sufficient number of ions to study the decay of metastable ions and to determine relative destruction cross sections. The technique could be useful to probe conformers differing only in size. Furthermore, our setup can be used for spectroscopic measurements of the ion-photon interaction such as the excitation of ͓Cytochrome cϩ17H] 17ϩ protein ions with 532 nm photons.

We have stored positively charged fullerene ions C(+)(n) (n even, from 48 to 70 and 76), C(2+)(60) and C(2+)(70) in an electrostatic storage ring and have measured the rate of emission of neutral fragments as a function of time. In the time range of the measurements, 50 micros to a few milliseconds, the rate decreases strongly due to radiative cooling of the molecules. Using the cooling rate predicted from a dielectric model, we have extracted the dissociation energies for C(2) loss from the measurements. As expected, the energies are largest for the "magic" fullerenes, C(50), C(60), and C(70), and the value of 9.8+/-0.1 eV for C(2) loss from C(+)(60) is in reasonable agreement with theory and with other recent experiments.

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The authors find even-odd variations as functions of r (...+[C60]2(r+)([C60C70](r+)) electron-transfer collisions. This even-odd behavior is in sharp contrast to the smooth one for fullerene monomers and may be related to even-odd effects in dimer ionization energies in agreement with results from an electrostatic model. The kinetic energy releases for dimer dissociations [predominantly yielding intact fullerenes [C60]2(r+)-->C60(r1+)+C60(r2+) in the same (r1=r2) or nearby (r1=r2+/-1) charge states] are found to be low in comparison with the corresponding model results indicating that internal excitations of the separating (intact) fullerenes are important. Experimental appearance sizes for the heavier clusters of fullerenes [C60]n(r+) (n>3 and r=2-5) compare well with predictions from a new nearest-neighbor model assuming that r unit charges in [C60]n(r+) are localized to r C60 molecules such that the Coulomb energy of the system is minimized. The system is then taken to be stable if (i) two (singly) charged C60 are not nearest neighbors and (ii) the r C60(+) molecules have binding energies to their neutral nearest neighbors which are larger than the repulsive energies for the (r-1) C60(+)-C60(+) pairs. Essential ingredients in the nearest-neighbor model are cluster geometries and the present results on dimer stabilities.

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Clusters of fullerenes (C60,C70)(n) are produced in a gas aggregation source and are multiply ionized in collisions with highly charged Xe(20+,30+) ions. Their stabilities and decay processes are analyzed with high-resolution time-of-flight mass spectrometry. Fullerene clusters in charge states up to q=5 have been observed and appearance sizes are found to be as small as n(app)=5, 10, 21, and 33 for q=2, 3, 4, and 5, respectively. The analysis of the multicoincident fragmentation spectra indicates a high charge mobility. This is in contrast to charge localization effects which have been reported for Ar(q+)(n) rare gas clusters. Clusters of fullerenes are found to be conducting when multiply charged.