Probing the electronic relaxation pathways and photostability of the synthetic nucleobase Z via laser interfaced mass spectrometry.

The photostability of synthetic (unnatural) nucleobases is important in establishing the integrity of new genetic alphabets, and critical for developing healthy semisynthetic organisms. Here, we report the first study to explore the photostability and electronic decay pathways of the synthetic nucleobase, Z (6-amino-5-nitro-2(1H)-pyridone), combining UV laser photodissociation and collisional dissociation measurements to characterise the decay pathways across the region from 3.1-4.9 eV. Photoexcitation across this region produced the m/z 138 ion as the dominant photofragment, mirroring the dominant fragment produced upon higher-energy collisional excitation. Analysis of the ion-yield production curve profile for the m/z 138 ion indicates that it is produced following ultrafast excited state decay with boil off of the OH functional group of Z from the hot electronic ground state. Electronic structure calculations provide physical insight into why this is the dominant fragmentation pathway, since a node in the electron density along the C-OH bond is found for all tautomers of Z. While the dominant decay pathway for Z is consistent with ultrafast excited state decay, we also identify several minor dissociative photochemistry decay pathways, associated with intrinsic photoinstability. The results presented here can be used to guide the development of more photostable synthetic nucleobases.

A "one pot" mass spectrometry technique for characterizing solution- and gas-phase photochemical reactions by electrospray mass spectrometry.

The characterization of new photochemical pathways is important to progress the understanding of emerging areas of light-triggered inorganic and organic chemistry. In this context, the development of platforms to perform routine characterization of photochemical reactions remains an important goal for photochemists. Here, we demonstrate a new instrument that can be used to characterise both solution-phase and gas-phase photochemical reactions through electrospray ionisation mass spectrometry (ESI-MS). The gas-phase photochemistry is studied by novel laser-interfaced mass spectrometry (LIMS), where the molecular species of interest is introduced to the gas-phase by ESI, mass-selected and then subjected to laser photodissociation in the ion-trap. On-line solution-phase photochemistry is initiated by LEDs prior to ESI-MS in the same instrument with ESI-MS again being used to monitor photoproducts. Two ruthenium metal carbonyls, [Ru(η5-C5H5)(PPh3)2CO][PF6] and [Ru(η5-C5H5)(dppe)CO][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane) are studied using this methodology. We show that the gas-phase photofragmentation pathways observed for the ruthenium complexes via LIMS (i.e. loss of CO + PPh3 ligands from [Ru(η5-C5H5)(PPh3)2CO]+ and loss of just CO from [Ru(η5-C5H5)(dppe)CO]+) mirror the solution-phase photochemistry at 3.4 eV. The advantages of performing the gas-phase and solution-phase photochemical characterisations in a single instrument are discussed.

Photoproducts of the Photodynamic Therapy Agent Verteporfin Identified via Laser Interfaced Mass Spectrometry.

Verteporfin, a free base benzoporphyrin derivative monoacid ring A, is a photosensitizing drug for photodynamic therapy (PDT) used in the treatment of the wet form of macular degeneration and activated by red light of 689 nm. Here, we present the first direct study of its photofragmentation channels in the gas phase, conducted using a laser interfaced mass spectrometer across a broad photoexcitation range from 250 to 790 nm. The photofragmentation channels are compared with the collision-induced dissociation (CID) products revealing similar dissociation pathways characterized by the loss of the carboxyl and ester groups. Complementary solution-phase photolysis experiments indicate that photobleaching occurs in verteporfin in acetonitrile; a notable conclusion, as photoinduced activity in Verteporfin was not thought to occur in homogenous solvent conditions. These results provide unique new information on the thermal break-down products and photoproducts of this light-triggered drug.

Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone.

A key decay pathway by which organic sunscreen molecules dissipate harmful UV energy involves excited-state hydrogen atom transfer between proximal enol and keto functional groups. Structural modifications of this molecular architecture have the potential to block ultrafast decay processes, and hence promote direct excited-state molecular dissociation, profoundly affecting the efficiency of an organic sunscreen. Herein, we investigate the binding of alkali metal cations to a prototype organic sunscreen molecule, oxybenzone, using IR characterization. Mass-selective IR action spectroscopy was conducted at the free electron laser for infrared experiments, FELIX (600-1800 cm-1), on complexes of Na+, K+ and Rb+ bound to oxybenzone. The IR spectra reveal that K+ and Rb+ adopt binding positions away from the key OH intermolecular hydrogen bond, while the smaller Na+ cation binds directly between the keto and enol oxygens, thus breaking the intramolecular hydrogen bond. UV laser photodissociation spectroscopy was also performed on the series of complexes, with the Na+ complex displaying a distinctive electronic spectrum compared to those of K+ and Rb+, in line with the IR spectroscopy results. TD-DFT calculations reveal that the origin of the changes in the electronic spectra can be linked to rupture of the intramolecular bond in the sodium cationized complex. The implications of our results for the performance of sunscreens in mixtures and environments with high concentrations of metal cations are discussed.

Unravelling the Keto-Enol Tautomer Dependent Photochemistry and Degradation Pathways of the Protonated UVA Filter Avobenzone.

Avobenzone (AB) is a widely used UVA filter known to undergo irreversible photodegradation. Here, we investigate the detailed pathways by which AB photodegrades by applying UV laser-interfaced mass spectrometry to protonated AB ions. Gas-phase infrared multiple-photon dissociation (IRMPD) spectra obtained with the free electron laser for infrared experiments, FELIX, (600-1800 cm-1) are also presented to confirm the geometric structures. The UV gas-phase absorption spectrum (2.5-5 eV) of protonated AB contains bands that correspond to selective excitation of either the enol or diketo forms, allowing us to probe the resulting, tautomer-dependent photochemistry. Numerous photofragments (i.e., photodegradants) are directly identified for the first time, with m/z 135 and 161 dominating, and m/z 146 and 177 also appearing prominently. Analysis of the production spectra of these photofragments reveals that that strong enol to keto photoisomerism is occurring, and that protonation significantly disrupts the stability of the enol (UVA active) tautomer. Close comparison of fragment ion yields with the TD-DFT-calculated absorption spectra give detailed information on the location and identity of the dissociative excited state surfaces, and thus provide new insight into the photodegradation pathways of avobenzone, and photoisomerization of the wider class of ß-diketone containing molecules.

Mapping the intrinsic absorption properties and photodegradation pathways of the protonated and deprotonated forms of the sunscreen oxybenzone.

Sunscreens provide vital protection against the photodamaging effects of UV radiation, however, many fundamental questions remain about the detailed mechanisms by which they dissipate UV energy. One such issue is the extent to which the pH environment of an organic sunscreen molecule alters its effectiveness, both in terms of ability to absorb UV radiation, and also its potential to photodegrade. Here, we use gas-phase laser photodissociation spectroscopy for the first time to measure the intrinsic UVA-UVC absorption spectra and associated photodegradation products of protonated and deprotonated oxybenzone, away from the complications of bulk mixtures. Our results reveal that protonation state has a dramatic effect on the absorption and photodissociation properties of this sunscreen. While the UV absorption profile of oxybenzone is only modestly affected by protonation across the range from 400-216 nm, deprotonated oxybenzone displays a significantly modified absorption spectrum, with very low photoabsorption between 370-330 nm. Protonated oxybenzone primarily photofragments by rupture of the bonds on either side of the central carbonyl group, producing cationic fragments with m/z 151 and 105. Additional lower mass photofragments (e.g. m/z 95 and 77) are also observed. The production spectra for the photofragments from protonated oxybenzone fall into two distinct categories, which we discuss in the context of different excited state decay pathways. For deprotonated oxybenzone, the major photofragments observed are m/z 211 and 212, which are associated with the ejection of methane and the methyl free radical from the parent ion, respectively. Implications for the suitability of oxybenzone in its protonated and deprotonated forms as an optimum sunscreen molecule are discussed.

Excited-State Dynamics of Isocytosine: A Hybrid Case of Canonical Nucleobase Photodynamics.

We present resonant two-photon ionization (R2PI) spectra of isocytosine (isoC) and pump-probe results on two of its tautomers. IsoC is one of a handful of alternative bases that have been proposed in scenarios of prebiotic chemistry. It is structurally similar to both cytosine (C) and guanine (G). We compare the excited-state dynamics with the Watson-Crick (WC) C and G tautomeric forms. These results suggest that the excited-state dynamics of WC form of G may primarily depend on the heterocyclic substructure of the pyrimidine moiety, which is chemically identical to isoC. For WC isoC we find a single excited-state decay with a rate of ∼1010 s-1, while the enol form has multiple decay rates, the fastest of which is 7 times slower than for WC isoC. The excited-state dynamics of isoC exhibits striking similarities with that of G, more so than with the photodynamics of C.

Excited State Dynamics of 6-Thioguanine.

Here we present the excited state dynamics of jet-cooled 6-thioguanine (6-TG), using resonance-enhanced multiphoton ionization (REMPI), IR-UV double resonance spectroscopy, and pump-probe spectroscopy in the nanosecond and picosecond time domains. We report data on two thiol tautomers, which appear to have different excited state dynamics. These decay to a dark state, possibly a triplet state, with rates depending on tautomer form and on excitation wavelength, with the fastest rate on the order of 1010 s-1. We also compare 6-TG with 9-enolguanine, for which we observed decay to a dark state with a 2 orders of magnitude smaller rate. At increased excitation energy (∼+500 cm-1) an additional pathway appears for the predominant thiol tautomer. Moreover, the excited state dynamics for 6-TG thiols is different from that recently predicted for thiones.

Direct Analysis of Xanthine Stimulants in Archaeological Vessels by Laser Desorption Resonance Enhanced Multiphoton Ionization.

Resonance enhanced multiphoton ionization spectroscopy (REMPI) generates simultaneous vibronic spectroscopy and fragment free mass spectrometry to identify molecules within a complex matrix. We combined laser desorption with REMPI spectroscopy to study organic residues within pottery sherds from Maya vessels (600-900 CE) and Mississippian vessels (1100-1200 CE), successfully detecting three molecular markers, caffeine, theobromine, and theophylline, associated with the use of cacao. This analytical approach provides a high molecular specificity, based on both wavelength and mass identification. At the same time, the high detection limit allows for direct laser desorption from sherd scrapings, avoiding the need for extracting organic constituents from the sherd matrix.

Remote sensing of emissions from in-use small engine marine vessels.

This paper reports the first use of a remote sensing device to measure emissions from in-use marine vessels. Emissions from 307 small marine vessels were measured as they passed through the Hiram M. Chittenden locks near Seattle, WA. Of these vessels, 89 were matched to state registration information to allow for further analysis of emissions vs model year, fuel type, and engine type. Emission factors are reported for CO, HC, and NOx in grams of pollutant per kilogram of fuel. The measured emission factors generally agreed with those derived from laboratory studies. HC emissions are disproportionately skewed across the fleet where 40% of the emissions come from just 10% of the fleet. These are most likely due to the remaining two-stroke engines in the fleet. CO and HC emissions show no improvement with newer vessels.