UV photodissociation action spectra of protonated formylpyridines.

The first ππ* transition for protonated 2-, 3-, and 4-formylpyridine (FPH+) (m/z 108) is investigated by mass spectrometry coupled with photodissociation action spectroscopy at room temperature and 10 K. The photoproduct ions are detected over 35 000-43 000 cm-1, and the major product channel for 3-FPH+ and 4-FPH+ is the loss of CO forming protonated pyridine at m/z 80. For 2-FPH+, the CO loss product is present but a more abundant photoproduct arises from the loss of CH2O to form m/z 78. Plausible potential energy pathways that lead to dissociation are mapped out and comparisons are made to products arising from collision-induced dissociation. Although, in all cases, the elimination of CO is the overwhelming thermodynamically preferred pathway, the protonated 2-FPH+ results suggest that the CH2O product is kinetically driven and competitive with CO loss. In addition, for each isomer, radical photoproduct ions are detected at lower abundances. SCS-CC2/aug-cc-pVTZ Franck-Condon simulations assist with the assignment of vibrionic structure and adiabatic energies (0-0) for 2-FPH+ at 36 560 cm-1, 37 430 cm-1 for 3-FPH+, and 36 140 cm-1 for 4-FPH+, yielding an accurate prediction, on average, within 620 cm-1.

Actinic Wavelength Action Spectroscopy of the IO- Reaction Intermediate.

Iodinate anions are important in the chemistry of the atmosphere where they are implicated in ozone depletion and particle formation. The atmospheric chemistry of iodine is a complex overlay of neutral-neutral, ion-neutral, and photochemical processes, where many of the reactions and intermediates remain poorly characterized. This study targets the visible spectroscopy and photostability of the gas-phase hypoiodite anion (IO-), the initial product of the I- + O3 reaction, by mass spectrometry equipped with resonance-enhanced photodissociation and total ion-loss action spectroscopies. It is shown that IO- undergoes photodissociation to I- + O (3P) over 637-459 nm (15700-21800 cm-1) because of excitation to the bound first singlet excited state. Electron photodetachment competes with photodissociation above the electron detachment threshold of IO- at 521 nm (19200 cm-1) with peaks corresponding to resonant autodetachment involving the singlet excited state and the ground state of neutral IO possibly mediated by a dipole-bound state.

Picosecond excited-state lifetimes of protonated indazole and benzimidazole: The role of the N-N bond.

Certain chemical groups give rise to characteristic excited-state deactivation mechanisms. Here, we target the role of a protonated N-N chemical group in the excited-state deactivation of protonated indazole by comparison to its isomer that lacks this group, protonated benzimidazole. Gas-phase protonated indazole and protonated benzimidazole ions are investigated at room temperature using picosecond laser pump-probe photodissociation experiments in a linear ion-trap. Excited state lifetimes are measured across a range of pump energies (4.0-5.4 eV). The 1ππ* lifetimes of protonated indazole range from 390 ± 70 ps using 4.0 eV pump energy to ≤18 ps using 4.6 eV pump energy. The 1ππ* lifetimes of protonated benzimidazole are systematically longer, ranging from 3700 ± 1100 ps at 4.6 eV pump energy to 400 ± 200 ps at 5.4 eV. Based on these experimental results and accompanying quantum chemical calculations and potential energy surfaces, the shorter lifetimes of protonated indazole are attributed to πσ* state mediated elongation of the protonated N-N bond.

Laser Photodissociation Action Spectroscopy for the Wavelength-Dependent Evaluation of Photoligation Reactions.

The nitrile imine-mediated tetrazole-ene cycloaddition is a widely used class of photoligation. Optimizing the reaction outcome requires detailed knowledge of the tetrazole photoactivation profile, which can only partially be ascertained from absorption spectroscopy, or otherwise involves laborious reaction monitoring in solution. Photodissociation action spectroscopy (PDAS) combines the advantages of optical spectroscopy and mass spectrometry in that only absorption events resulting in a mass change are recorded, thus revealing the desired wavelength dependence of product formation. Moreover, the sensitivity and selectivity afforded by the mass spectrometer enable reliable assessment of the photodissociation profile even on small amounts of crude material, thus accelerating the design and synthesis of next-generation substrates. Using this workflow, we demonstrate that the photodissociation onset for nitrile imine formation is red-shifted by ca. 50 nm with a novel N-ethylcarbazole derivative relative to a phenyl-substituted archetype. Benchmarked against solution-phase tunable laser experiments and supported by quantum chemical calculations, these discoveries demonstrate that PDAS is a powerful tool for rapidly screening the efficacy of new substrates in the quest toward efficient visible light-triggered ligation for biological applications.

Electrostatically Tuning the Photodissociation of the Irgacure 2959 Photoinitiator in the Gas Phase by Cation Binding.

The low-lying electronic states of Irgacure 2959, a Norrish-type I photoinitiator, complexed with a single metal cation are investigated in the gas phase by photodissociation action spectroscopy. Analysis of the band shifts using quantum chemical calculations (TD-DFT and SCS-CC2) reveals the underlying influence of the charge on the key electronic energy levels. Since the cations (H+, Li+, Na+, K+, Zn2+, Ca2+, and Mg2+) bind at varying distances, the magnitude of the electric field at the center of the chromophore due to the cation is altered, and this shifts the electronic states by different amounts. Photodissociation action spectra of cation-Irg complexes show that absorption transitions to the first 1ππ* state are red-shifted with a magnitude proportional to the electric field strength (with red shifts >1 eV), and in most cases, the cation is essentially acting as a point charge. Calculations show that a neighboring 3nπ* state, a key state for the α-cleavage pathway, is destabilized (blue-shifted) by the orientated electric field. As such, if the 1ππ*-3nπ* energy gap is reduced, increased intersystem crossing rates are expected, resulting in higher yields of the desired radical photoproducts, and this is controlled by the orientated electric field arising from the cation.

Next-generation derivatization reagents optimized for enhanced product ion formation in photodissociation-mass spectrometry of fatty acids.

Ultraviolet-photodissociation (UVPD) mass spectrometry is an emerging analytical tool for structural elucidation of biomolecules including lipids. Gas phase UVPD of ionised fatty acids (FAs) can promote fragmentation that is diagnostic for molecular structure including the regiochemistry of carbon-carbon double bonds and methyl branching position(s). Typically, however, lipids exhibit poor conversion to photoproducts under UVPD and thus require longer integration times to achieve the signal-to-noise required for structural assignments. Consequently, the integration of UVPD into liquid-chromatography mass spectrometry (LC-MS) workflows for FAs has been limited. To enhance photofragmentation efficiency, an alternative strategy has been devised using wet-chemical derivatization of FAs to explicitly incorporate photolabile groups. FA derivatives that include an aryl-iodide motif have photodissociation conversions of up to 28% when activated by a single 266 nm photon. The radical-directed dissociation product ions resulting from UVPD of these derivatives provide key details of molecular structure and discriminate between lipid isomers. Herein, we describe the structure-activity guided development of new FA derivatives capable of photoproduct yields of up to 97%. UVPD-action spectroscopy demonstrates that photodissociation for FAs derivatized with N-(2-aminoethyl)-4-iodobenzamide (NIBA) is maximised near 266 nm and highlights the key role of the 4-iodobenzamide motif in the efficient formation of [M - I]˙+ radical cations (and diagnostic secondary product ions). The high photodissociation yield of NIBA-derivatized lipids is maintained across 37 commonly observed FAs with the resulting UVPD mass spectra shown to be effective in the discrimination of isomeric FAs that differ in the position(s) of carbon-carbon double bonds. Integration of this strategy with reversed-phase LC-MS workflows is confirmed with high-quality UVPD mass spectra acquired across each chromatographic peak.

Gas phase reactions of iodide and bromide anions with ozone: evidence for stepwise and reversible reactions.

Despite the impacts - both positive and negative - of atmospheric ozone for life on Earth, there remain significant gaps in our knowledge of the products, mechanisms and rates of some of its most fundamental gas phase reactions. This incomplete understanding is largely due to the experimental challenges involved in the study of gas-phase reactions of ozone and, in particular, the identification of short-lived reaction intermediates. Here we report direct observation of the stepwise reaction of the halide anions iodide (I-) and bromide (Br-) with ozone to produce XO3- (where X = I and Br, respectively). These results substantially revise the rate constant for the I- + O3 reaction to 1.1 (± 0.5) × 10-12 cm3 molecule-1 s-1 (0.13% efficiency) and the Br- + O3 reaction to 6.2 (± 0.4) × 10-15 cm3 molecule-1 s-1 (0.001% efficiency). Exploiting five-orders of temporal dynamic range on a linear ion trap mass spectrometer enabled explicit measurement of the rate constants for the highly efficient intermediate, XO- + O3 and XO2- + O3, reactions thus confirming a stepwise addition of three oxygen atoms (i.e., X- + 3O3 → XO3- + 3O2) with the first addition representing the rate determining step. Evidence is also presented for (i) slow reverse reactions of XO- and XO2-, but not XO3-, with molecular oxygen and (ii) the photodissociation of IO-, IO2- and IO3- to release I-. Collectively, these results suggest relatively short lifetimes for Br- and I- in the tropospere with direct gas-phase oxidation by ozone playing a role in both the formation of atmospheric halogen oxides and, conversely, in the ozone depletion associated with springtime polar bromine explosion events.

Discrimination between Protonation Isomers of Quinazoline by Ion Mobility and UV-Photodissociation Action Spectroscopy.

The influence of oriented electric fields on chemical reactivity and photochemistry is an area of increasing interest. Within a molecule, different protonation sites offer the opportunity to control the location of charge and thus orientation of electric fields. New techniques are thus needed to discriminate between protonation isomers in order to understand this effect. This investigation reports the UV-photodissociation action spectroscopy of two protonation isomers (protomers) of 1,3-diazanaphthalene (quinazoline) arising from protonation of a nitrogen at either the 1- or 3-position. It is shown that these protomers are separable by field-asymmetric ion mobility spectrometry (FAIMS) with confirmation provided by UV-photodissociation (PD) action spectroscopy. Vibronic features in the UVPD action spectra and computational input allow assignment of the origin transitions to the S1 and S5 states of both protomers. These experiments also provide vital benchmarks for protomer-specific calculations and examination of isomer-resolved reaction kinetics and thermodynamics.

Selecting and identifying gas-phase protonation isomers of nicotineH+ using combined laser, ion mobility and mass spectrometry techniques.

The detection and assignment of protonation isomers, termed protomers, of gas-phase ions remains a challenge in mass spectrometry. With the emergence of ion-mobility techniques combined with tuneable-laser photodissociation spectroscopy, new experimental combinations are possible to now meet this challenge. In this paper, the differences in fragmentation and electronic spectroscopy of singly protonated (S)-nicotine (nicH+) ions are analysed using action spectroscopy in the ultraviolet region and field asymmetric ion mobility spectrometry (FAIMS). Experiments are supported by quantum chemical calculations (DFT, TD-DFT and CC2) of both spectroscopic and thermochemical properties. Electrospray ionisation (ESI) of (S)-nicotine from different solvents leads to different populations of two nicH+ protomers corresponding to protonation on the pyridine nitrogen and pyrrolidine nitrogen, respectively. FAIMS gives partial resolution of these protomers and enables characteristic product ions to be identified for each isomer as verified directly by analysis of product-ion specific action spectroscopy. It is shown that while characteristic, these product ions are not exclusive to each protomer. Calculations of vertical electronic transitions assist in rationalising the photodissociation action spectra. The integration of photodissociation action spectroscopy with FAIMS-mass spectrometry is anticipated to be a useful approach for separating and assigning protonation isomers of many other small molecular ions.