Development of High Throughput Microscope Mode Secondary Ion Mass Spectrometry Imaging.

This paper describes the development and initial results from a secondary ion mass spectrometer coupled with microscope mode detection. Stigmatic ion microscope imaging enables us to decouple the primary ion (PI) beam focus from spatial resolution and is a promising route to attaining higher throughput for mass spectrometry imaging (MSI). Using a commercial C60+ PI beam source, we can defocus the PI beam to give uniform intensity across a 2.5 mm2 area. By coupling the beam with a position-sensitive spatial detector, we can achieve mass spectral imaging of positive and negative secondary ions (SIs), which we demonstrate using samples comprising metals and dyes. Our approach involves simultaneous desorption of ions across a large field of view, enabling mass spectral images to be recorded over an area of 2.5 mm2 in a matter of seconds. Our instrument can distinguish spatial features with a resolution of better than 20 µm, and has a mass resolution of >500 at 500 u. There is considerable scope to improve this, and through simulations we estimate the future performance of the instrument.

Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study.

A carboxylated adenosine analog (C-Ado-) has been synthesized and probed via time-resolved photoelectron spectroscopy in order to induce intra-molecular charge transfer from the carboxylic acid moiety to the nucleobase. Intra-molecular charge transfer can be exploited as starting point to probe low-energy electron (LEE) damage in DNA and its derivatives. Time-dependent density functional theory (TD-DFT) calculations at the B3LYP-6311G level of theory have been performed to verify that the highest occupied molecular orbital (HOMO) was located on carboxylic acid and that the lowest occupied molecular orbital (LUMO) was on the nucleobase. Hence, the carboxylic acid could work as electron source, whilst the nucleobase could serve the purpose of electron acceptor. The dynamics following excitation at 4.66 eV (266 nm) were probed using time-resolved photoelectron spectroscopy using probes at 1.55 eV (800 nm) and 3.10 eV (400 nm). The data show rapid decay of the excited state population and, based on the similarity of the overall dynamics to deoxy-adenosine monophosphate (dAMP-), it appears that the dominant decay mechanism is internal conversion following 1ππ* excitation of the nucleobase, rather than charge-transfer from the carboxylic acid to the nucleobase.

Ultrafast Dynamics of the Isolated Adenosine-5'-triphosphate Dianion Probed by Time-Resolved Photoelectron Imaging.

The excited state dynamics of the doubly deprotonated dianion of adenosine-5'-triphosphate, [ATP-H2]2-, has been spectroscopically explored by time-resolved photoelectron spectroscopy following excitation at 4.66 eV. Time-resolved photoelectron spectra show that two competing processes occur for the initially populated 1ππ* state. The first is rapid electron emission by tunneling through a repulsive Coulomb barrier as the 1ππ* state is a resonance. The second is nuclear motion on the 1ππ* state surface leading to an intermediate that no longer tunnels and subsequently decays by internal conversion to the ground electronic state. The spectral signatures of the features are similar to those observed for other adenine-derivatives, suggesting that this nucleobase is quite insensitive to the nearby negative charges localized on the phosphates, except of course for the appearance of the additional electron tunneling channel, which is open in the dianion.

Site-Specific Photo-oxidation of the Isolated Adenosine-5'-triphosphate Dianion Determined by Photoelectron Imaging.

Photoelectron imaging of the isolated adenosine-5'-triphosphate dianion excited to the 1ππ* states reveals that electron emission is predominantly parallel to the polarization axis of the light and arises from subpicosecond electron tunneling through the repulsive Coulomb barrier (RCB). The computed RCB shows that the most probable electron emission site is on the amino group of adenine. This is consistent with the photoelectron imaging: excitation to the 1ππ* states leads to an aligned ensemble distributed predominantly parallel to the long axis of adenine; the subsequent electron tunneling site is along this axis; and the negatively charged phosphate groups guide the outgoing electron mostly along this axis at long range. Imaging of electron tunneling from polyanions combined with computational chemistry may offer a general route for probing the intrinsic photo-oxidation site and dynamics as well as the overall structure of complex isolated species.

On the stability of a dipole-bound state in the presence of a molecule.

Dipole-bound states (DBSs) are diffuse non-valence molecular orbitals of anions where the electron is bound by the permanent dipole moment of the neutral core. Here, an experimental study of the stability of such orbitals under the influence of a perturbing molecular alkyl chain is presented. Photodetachment action and photoelectron imaging spectroscopy of five para-substituted phenolate anions with progressively longer alkyl chains show that the DBS survives in all cases, suggesting that the perturbation of the orbital is not critical to the existence of the DBS.