Polycyclic Aromatic Hydrocarbon Ions Research Articles

An X-ray spectroscopy study of structural stability of superhydrogenated pyrene derivatives

ABSTRACT The stability of polycyclic aromatic hydrocarbons (PAHs) upon soft X-ray absorption is of crucial relevance for PAH survival in X-ray dominated regions. PAH stability depends on molecular size but also on the degree of hydrogenation that is related to H2 formation in the interstellar medium. In this project, we intend to reveal the changes of electronic structure caused by hydrogenation and the impact of hydrogenation on the stability of the carbon backbone for cationic pyrene and its hydrogenated derivatives by analysis of near C K-edge soft X-ray photoions. In our experiments, the PAH cations were trapped in a cryogenic radiofrequency linear ion trap and exposed to monochromatic X-rays with energies from 279 to 300 eV. The photoproducts were mass-analysed by means of time-of-flight spectroscopy. Partial ion yields were then studied as a function of photon energy. X-ray absorption spectra computed by time-dependent density functional theory (TD-DFT) aided the interpretation of the experimental results. A very good agreement between experimental data and TD-DFT with short-range corrected functionals for all PAH ions was reached. The near-edge X-ray absorption mass spectra exhibit clear peaks due to C 1s transitions to singly occupied molecular orbitals and to low-lying unoccupied molecular orbitals. In contrast to coronene cations, where hydrogen attachment drastically increases photostability of coronene, the influence of hydrogenation on photostability is substantially weaker for pyrene cations. Here, hydrogen attachment even destabilizes the molecular structure. An astrophysical model describes the half-life of PAH ions in interstellar environments.

Cooling dynamics of energized naphthalene and azulene radical cations.

Naphthalene and azulene are isomeric polycyclic aromatic hydrocarbons (PAHs) and are topical in the context of astrochemistry due to the recent discovery of substituted naphthalenes in the Taurus Molecular Cloud-1 (TMC-1). Here, the thermal- and photo-induced isomerization, dissociation, and radiative cooling dynamics of energized (vibrationally hot) naphthalene (Np+) and azulene (Az+) radical cations, occurring over the microsecond to seconds timescale, are investigated using a cryogenic electrostatic ion storage ring, affording "molecular cloud in a box" conditions. Measurement of the cooling dynamics and kinetic energy release distributions for neutrals formed through dissociation, until several seconds after hot ion formation, are consistent with the establishment of a rapid (sub-microsecond) Np+ ⇌ Az+ quasi-equilibrium. Consequently, dissociation by C2H2-elimination proceeds predominantly through common Az+ decomposition pathways. Simulation of the isomerization, dissociation, recurrent fluorescence, and infrared cooling dynamics using a coupled master equation combined with high-level potential energy surface calculations [CCSD(T)/cc-pVTZ], reproduce the trends in the measurements. The data show that radiative cooling via recurrent fluorescence, predominately through the Np+ D0 ← D2 transition, efficiently quenches dissociation for vibrational energies up to ≈1eV above dissociation thresholds. Our measurements support the suggestion that small cations, such as naphthalene, may be more abundant in space than previously thought. The strategy presented in this work could be extended to fingerprint the cooling dynamics of other PAH ions for which isomerization is predicted to precede dissociation.

PHANGS–JWST First Results: Measuring Polycyclic Aromatic Hydrocarbon Properties across the Multiphase Interstellar Medium

Ratios of polycyclic aromatic hydrocarbon (PAH) vibrational bands are a promising tool for measuring the properties of the PAH population and their effect on star formation. The photometric bands of the MIRI and NIRCam instruments on JWST provide the opportunity to measure PAH emission features across entire galaxy disks at unprecedented resolution and sensitivity. Here we present the first results of this analysis in a sample of three nearby galaxies: NGC 628, NGC 1365, and NGC 7496. Based on the variations observed in the 3.3, 7.7, and 11.3 μm features, we infer changes to the average PAH size and ionization state across the different galaxy environments. High values of F335MPAH/F1130W and low values of F1130W/F770W are measured in H ii regions in all three galaxies. This suggests that these regions are populated by hotter PAHs, and/or that the PAH ionization fraction is larger. We see additional evidence of heating and/or changes in PAH size in regions with higher molecular gas content as well as increased ionization in regions with higher Hα intensity.

Nanoliter atmospheric pressure photoionization-mass spectrometry for direct bioanalysis of polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are a class of low-polarity environmental contaminants that have severe carcinogenic effects and have drawn worldwide attention. However, there remain challenges for current mass spectrometric ionization techniques in the analysis of low-polarity compounds in small-volume biosamples, such as single cells. In this work, we developed a nanoliter atmospheric pressure photoionization (nano-APPI) source and optimized its parameters for the detection of PAHs in small-volume samples. We evaluated the ionization performance of the source in direct and auxiliary gas-assisted photoionization modes and analyzed different PAH compounds as well as spiked biosamples. By combining the advantages of nano-electrospray ionization (nano-ESI) and atmospheric pressure photoionization (APPI), our newly developed nano-APPI source achieved high sensitivity for the analysis of PAHs down to the fmol level. Compared to conventional atmospheric pressure chemical ionization (APCI), the detection limit of PAHs was increased by 1-2 orders of magnitude. By optimizing various parameters, we achieved highly efficient ionization of PAHs, effective analysis of PAHs in mixed components, and sensitive detection of low-abundance PAHs in single-cell samples. Our optimized nano-APPI source was successfully applied for the sensitive analysis of PAHs in complex biological samples. Based on our study, we believe that nano-APPI holds great promise for toxicological studies on complex biological samples. The present work has implications for improving the detection sensitivity of low-polarity environmental contaminants and advancing the field of MS-based analysis of small-volume biosamples.

The Ionization and Destruction of Polycyclic Aromatic Hydrocarbons in Powerful Quasars

Abstract We reanalyze the mid-infrared (5–40 μm) Spitzer spectra of 86 low-redshift (z < 0.5) Palomar–Green quasars to investigate the nature of polycyclic aromatic hydrocarbon (PAH) emission and its utility as a star formation rate (SFR) indicator for the host galaxies of luminous active galactic nuclei (AGNs). We decompose the spectra with our recently developed template-fitting technique to measure PAH fluxes and upper limits, which we interpret using mock spectra that simulate the effects of AGN dilution. While luminous quasars can severely dilute and affect the detectability of emission lines, PAHs are intrinsically weak in some sources that are otherwise gas-rich and vigorously forming stars, conclusively demonstrating that powerful AGNs destroy PAH molecules. Comparing PAH-based SFRs with independent SFRs derived from the mid-infrared fine-structure neon lines and the total infrared luminosity reveals that PAHs can trace star formation activity in quasars with bolometric luminosities ≲1046 erg s−1, but increasingly underestimate the SFR for more powerful quasars, typically by ∼0.5 dex. Relative to star-forming galaxies and low-luminosity AGNs, quasars have a comparable PAH 11.3 μm/7.7 μm ratio but characteristically lower ratios of 6.2 μm/7.7 μm, 8.6 μm/7.7 μm, and 11.3 μm/17.0 μm. We suggest that these trends indicate that powerful AGNs preferentially destroy small grains and enhance the PAH ionization fraction.

Characterizing spatial variations of PAH emission in the reflection nebula NGC 1333

ABSTRACT Infrared emission features at 3.3, 6.2, 7.7, 8.6, and 11.2 µm, attributed to polycyclic aromatic hydrocarbons (PAHs), show variations in relative intensity, shape, and peak position. These variations depend on the physical conditions of the photodissociation region (PDR) in which strong PAH emission arises but their relationship has yet to be fully quantified. We aim to better calibrate the response of PAH species to their environment using observations with matching apertures and spatial resolution. We present observations from the Field-Imaging Far-Infrared Line Spectrometer onboard the Stratospheric Observatory for Infrared Astronomy of the gas cooling lines [O i] 63, 146 µm and [C ii] 158 µm in the reflection nebula NGC 1333 and use archival dust continuum observations from the Photodetector Array Camera and Spectrometer (PACS) onboard Herschel. We employ PDR modelling to derive the physical conditions and compare these with the characteristics of the PAH emission as observed with the Infrared Spectrometer onboard Spitzer. We find distinct spatial characteristics for the various PAH spectral components. We conclude that the ionic bands (6.2, 7.7, 8.6, and 11.0) and the 7–9 µm emission are due to multiple PAH subpopulations and that the plateaus are distinct from the features perched on top. The 6–9 µm PAH emission exhibits a significant change in behaviour between the irradiated PDR and diffuse outskirts, confirming these bands arise from multiple PAH subpopulations with different underlying molecular properties. We find multiple promising relationships between PAH ratios and the far-ultraviolet radiation field strength but no clear correlations with the PAH ionization parameter.

Characterizing the PAH emission in the Orion Bar

ABSTRACT We present 5–14 $\mu$m spectra at two different positions across the Orion Bar photodissociation region (PDR) obtained with the Infrared Spectrograph onboard the Spitzer Space Telescope and 3.3 $\mu$m PAH observations obtained with the Stratospheric Observatory for Infrared Astronomy (SOFIA). We aim to characterize emission from Polycyclic Aromatic Hydrocarbon (PAH), dust, atomic and molecular hydrogen, argon, sulfur, and neon as a function of distance from the primary illuminating source. We find that all the major PAH bands peak between the ionization front and the PDR front, as traced by H2, while variations between these bands become more pronounced moving away from this peak into the face-on PDRs behind the PDR front and at the backside of the H ii region. While the relative PAH intensities are consistent with established PAH characteristics, we report unusual behaviours and attribute these to the PDR viewing angle and the strength of the FUV radiation field impinging on the PDRs. We determine the average PAH size which varies across the Orion Bar. We discuss subtle differences seen between the cationic PAH bands and highlight the photochemical evolution of carbonaceous species in this PDR environment. We find that PAHs are a good tracer of environmental properties such as the strength of the FUV radiation field and the PAH ionization parameter.

Unimolecular fragmentation and radiative cooling of isolated PAH ions: A quantitative study.

Time-resolved spontaneous and laser-induced unimolecular fragmentation of perylene cations (C20H12 +) has been measured on timescales up to 2 s in a cryogenic electrostatic ion beam storage ring. We elaborate a quantitative model, which includes fragmentation in competition with radiative cooling via both vibrational and electronic (recurrent fluorescence) de-excitation. Excellent agreement with experimental results is found when sequential fragmentation of daughter ions co-stored with the parent perylene ions is included in the model. Based on the comparison of the model to experiment, we constrain the oscillator strength of the D1 → D0 emissive electronic transition in perylene (fRF = 0.055 ± 0.011), as well as the absolute absorption cross section of the D5 ← D0 excitation transition (σabs > 670 Mb). The former transition is responsible for the laser-induced and recurrent fluorescence of perylene, and the latter is the most prominent in the absorption spectrum. The vibrational cooling rate is found to be consistent with the simple harmonic cascade approximation. Quantitative experimental benchmarks of unimolecular processes in polycyclic aromatic hydrocarbon ions like perylene are important for refining astrochemical models.

The influence of different types of reactant ions on the ionization behavior of polycyclic aromatic hydrocarbons in corona discharge ion mobility spectrometry

Some polycyclic aromatic hydrocarbons (PAHs) are considered to be cancer-causing chemicals, and ion mobility spectrometry (IMS) is used for on-site detection of such hazardous chemicals. In IMS, the ionization behavior of analytes is affected by the types of reactant ions (RIs). In the present work, the influence of different types of RIs on the ionization behaviors of PAHs in an ion mobility spectrometer equipped with a corona discharge ionization source was investigated using various RIs. Selected PAHs were dissolved in anisole, fluorobenzene, chlorobenzene, or bromobenzene. The IMS analysis procedure was performed as follows: (a) the PAH solution was dropped onto the smear matrix; (b) the smear matrix was immediately inserted into the sample inlet to minimize evaporation of the solvent; and (c) the IMS analysis was performed. The lowest amount studied was 10 ng. Variations in the IMS spectra with time were investigated. PAHs were not ionized by RIs of protonated molecules ([M + H]+ ) such as air/moisture and acetone, but they were ionized by charge transfer reactions with RIs of molecular ions (M•+ ) of solvents such as anisole, fluorobenzene, chlorobenzene, and bromobenzene. The PAH ions were detected following a time delay of ~1-5 s after the sample introduction, and the times at which the maximum intensities for the PAHs were observed were different. The detection limits of PAHs in chlorobenzene were on the whole better than those in other solvents, whereas those in fluorobenzene were worse. The detection limits of pyrene and benzo[a]anthracene were better than those of the other PAHs irrespective of the solvent used. PAH molecules were ionized by charge transfer reactions with RIs of the solvents, and their ions were detected ~1-5 s after sample introduction. The order of the ionization efficiency was chlorobenzene > anisole > bromobenzene > fluorobenzene.

Nonionic and anionic surfactant-washing of polycyclic aromatic hydrocarbons in estuarine sediments around an industrial harbor in southern Taiwan

Various surfactants, such as nonionic Triton X-100 and Simple Green™ (SG), and anionic sodium dodecylsulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS) were utilized to remove polycyclic aromatic hydrocarbons (PAHs) from heavily contaminated harbor sediments dredged from Kaohsiung Harbor in Taiwan. Desorption/re-sorption equilibrium, kinetics, and washability of PAHs using the selected surfactant were evaluated under different critical micelle concentrations (CMC). Experimental results revealed that the desorption rate of high molecular weight PAHs was greater than those of low molecular weight PAHs, and the anionic SDS was relatively effective in the removal of total PAHs (>50%) compared to the other surfactants. The correlation between the effectiveness of the surfactant washing processes and the physicochemical properties of individual PAH was statistically analyzed. The resulting data suggested that hydrophobic factors (Kow, Koc and Sw) affected PAH treatability more than the reactivity of PAH (electron affinity and ionization potential). Since the adsorption of anionic surfactant altered the hydrophobicity of organic matter in the sediment, PAHs preferred transferring from the sediment to the hydrophobic core of micelles in aqueous solution. Nevertheless, the nonionic surfactant enhanced the PAH partition in the aqueous phase, thus increasing the micellar solubilization of PAH.

How does successive hydrogen addition to PAH ions impact their unimolecular chemistry?

Hydrogenated polycyclic aromatic hydrocarbons (PAHs) have been proposed to contribute to the formation of interstellar H2 by acting as a surface catalyst for the adsorption of hydrogen atoms and desorption of H2 molecules. In the present study, imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and tandem mass spectrometry were employed to examine the unimolecular chemistry of four hydrogenated polycyclic aromatic hydrocarbon ions: 9,10-dihydroanthracene (DHA+•) and 1,2,3,4,5,6,7,8-octahydroanthracene (OHA+•), having opposite patterns of hydrogenation, and 1,2,3,4-tetrahydrophenanthrene (THP+•) and 1,2,3,4,9,10-hexahydrophenanthrene (HHP+•). DHA+• exhibits the same reactions previously observed for 1,2-dihydronaphthalene and 9,10-dihydrophenanthrene, namely competing loss of H• and CH3•. However, the energy required for H•-loss, as predicted by RRKM modeling of the iPEPICO results, was lower than the latter ions, presumably due to charge delocalization across the central ring upon dehydrogenation. OHA+• behaves similarly to ionized tetralin, displaying losses of H•, CH3•, C2H4 and C3H5• in its collision induced dissociation (CID) mass spectra, but under iPEPICO conditions CH3•-loss is not observed. THP+• and HHP+• have aspects of both DHA+• and OHA+• chemistries, displaying losses of H•, CH3•, C2H4 and C3H5•. RRKM modeling produced minimum energies for all observed reaction channels, which were also computationally explored at the B3LYP/6–31+G(d,p) level of theory. The results indicate that small PAH ions may not be effective surfaces for the catalytic formation of H2 in the ISM, but rather sources of small hydrocarbons.

Hydroxy-Substituted Polycyclic Aromatic Hydrocarbon Ions as Sources of CO and HCO in the Interstellar Medium.

Tandem mass spectrometry was used to explore the trends in the unimolecular fragmentation of the ionized hydroxy-substituted polycyclic aromatic hydrocarbons 1-naphthol, 9-hydroxyphenanthrene, and 1-hydroxypyrene. The main dissociation reactions across all ring systems were CO- and HCO-losses, with ionized 1-naphthol also losing H atoms. Both ionized 1-naphthol and 9-hydroxyphenanthrene displayed the sequential loss of C2H2 and C4H2 from the [M-HCO]+ ions, reminiscent of unsubstituted PAH ions. CO-loss is slightly favored for 1-naphthol and 9-hydroxyphenanthrene, at low collision energy, but less so for 1-hydroxypyrene. Reaction mechanisms for HCO- and CO-losses from 1-hydroxypyrene were derived from CCSD/6-31G(d)//B3-LYP/6-31G(d) calculations. The CO-loss mechanism is dominated by two transition states: TS-A governing a 1,3-H shift in the molecular ion and TS-C which governs a ring-closing step to form a five-member ring in the product ion. HCO-loss occurs over a much flatter potential energy surface with the intermediate being the product ion bound to the carbon atom of HCO. Imaging photoelectron photoion coincidence spectroscopy of 1-hydroxypyrene yielded threshold photon-energy resolved breakdown curves and time-of-flight distributions that were modeled with RRKM theory to give 0 K reaction energies for HCO- and CO-losses of 3.92 ± 0.05 and 2.91 ± 0.05 eV, respectively. The entropies of activation for the two channels were very different, 14 and 95 JK-1 mol-1, respectively, a result consistent with the calculated mechanisms. The threshold photoelectron spectrum yielded an IE value of 7.14 ± 0.01 eV for 1-hydroxypyrene.

Destruction and multiple ionization of PAHs by X-rays in circumnuclear regions of AGNs

ABSTRACT The infrared signatures of polycyclic aromatic hydrocarbons (PAHs) are observed in a variety of astrophysical objects, including the circumnuclear medium of active galactic nuclei (AGNs). These are sources of highly energetic photons (0.2–10 keV), exposing the PAHs to a harsh environment. In this work, we examined experimentally the photoionization and photostability of naphthalene (C10H8), anthracene (C14H10), 2-methyl-anthracene (C14H9CH3), and pyrene (C16H10) upon interaction with photons of 275, 310, and 2500 eV. The measurements were performed at the Brazilian Synchrotron Light Laboratory using time-of-flight mass-spectrometry. We determined the absolute photoionization and photodissociation cross-sections as a function of the incident photon energy; the production rates of singly, doubly, and triply charged ions; and the molecular half-lives in regions surrounding AGNs. Even considering moderate X-ray optical depth values (τ = 4.45) due to attenuation by the dusty torus, the half-lives are not long enough to account for PAH detection. Our results suggest that a more sophisticated interplay between PAHs and dust grains should be present in order to circumvent molecular destruction. We could not see any significant difference in the half-life values by increasing the size of the PAH carbon backbone, NC, from 10 to 16. However, we show that the multiple photoionization rates are significantly greater than the single ones, irrespective of the AGN source. We suggest that an enrichment of multiply charged ions caused by X-rays can occur in AGNs.

Release of large polycyclic aromatic hydrocarbons and fullerenes by cosmic rays from interstellar dust

Context. Top-down chemistry is believed to be responsible for the formation of the large molecular compounds such as the polycyclic aromatic hydrocarbon-like molecules and the fullerenes observed in the interstellar medium. The release of these large molecules from the parent grains remains an important issue to be investigated. Aims. Cosmic rays irradiate the dust grains during their journey in the interstellar medium. In this study we probe to what extent electronic sputtering and/or desorption processes induced by high-energy ion projectiles contribute to the creation of the large molecular component in space. Methods. Carbonaceous dust analogues were produced in an ethylene flame. The resulting soot nanoparticles generated under well-defined conditions were irradiated by swift heavy ions, and mass spectra of the ionic and neutral molecular fragments emitted shortly after the impact were monitored. Results. Large molecular fragments were detected, including neutral and ionic polycyclic aromatic hydrocarbons containing up to several tens of carbon atoms, as well as ionic fullerenes. Although the absolute efficiencies were not obtained, these experiments provide a proof of principle of a top-down scenario involving interaction processes of interstellar dust with high-energy projectiles yielding large molecular compounds observed in space.

Influence of smear matrix types on detection behaviors and efficiencies of polycyclic aromatic hydrocarbons using ion mobility spectrometry

Influence of smear matrix types on detection behaviors and efficiencies of polycyclic aromatic hydrocarbons (PAHs) with different molecular weights in ion mobility spectrometry (IMS) were investigated. Various smear matrices of stainless steel mesh (SM), cellulose paper (CP), and cotton fabric (CF) were employed. Anisole was used as the solvent and IMS analysis was performed without evaporation step of the solvent to apply charge transfer reactions between PAH molecules and the molecular ions of solvent. Shapes of reactant ion peaks (RIPs) were varied according to the smear matrix types. At the beginning of the sample inlet, intensity of RIPs of air and moisture notably decreased due to the lots of solvent vapor. The SM with good gas permeability showed relatively strong RIPs of air and moisture, whereas the CP with no gas permeability showed weak ones. Detection times and efficiencies of PAH ions were varied according to the smear matrix types as well as the kinds of PAHs. PAHs were on the whole detected well in 1–3 s after the sample inlet. Detection limits of PAHs measured using the SM were slightly better than those measured using the CP, while those measured using the CP were much better than those measured using the CF. The experimental results could be explained by structures of the smear matrices and evaporation behaviors of the PAH solutions.

What do we expect from the dissociation of ionized nitro-substituted polycyclic aromatic hydrocarbons in the interstellar medium?

The unimolecular dissociations of four nitro-substituted polycyclic aromatic hydrocarbon (PAH) ions were explored using tandem mass spectrometry, imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and computational chemistry. Ionized 1-nitronaphthalene and 9-nitroanthracene both exhibit the loss of C2O2 (likely sequential loss of two CO molecules), NO and CO2 as primary fragmentation channels, while for the larger 3-nitrofluoranthene and 1-nitropyrene ions CO2 loss is replaced by NO2 loss. The reaction pathways for 1-nitropyrene ions were calculated at the CCSD/6-31G(d)//B3-LYP/6-31G(d) level of theory. NO loss is preceded by a nitro-to-nitrite isomerization requiring 2.09 eV, while NO2 loss was found to form the triplet state [pyrene – H]+ ion (requiring 2.36 eV), consistent with the behavior of this class of PAH ions. iPEPICO-derived energies for these two reactions are in excellent agreement with theory, 2.05 ± 0.09 eV and 2.38 ± 0.12 eV, respectively. The iPEPICO-derived reaction energy for C2O2 loss is 2.76 ± 0.08 eV, but we were unable to calculate this reaction pathway. The most energetically-favorable products of sequential CO loss lie 3.2 eV and 2.05 eV, respectively, lower in energy than the precursor ion, indicating that what was measured was an effective barrier height for this reaction.

The Charge State of Polycyclic Aromatic Hydrocarbons across a Reflection Nebula, an H ii Region, and a Planetary Nebula

Abstract Low-resolution Spitzer-IRS spectral map data of a reflection nebula (NGC 7023), H ii region (M17), and planetary nebula (NGC 40), totaling 1417 spectra, are analyzed using the data and tools available through the NASA Ames PAH IR Spectroscopic Database. The polycyclic aromatic hydrocarbon (PAH) emission is broken down into PAH charge and size subclass contributions using a database-fitting approach. The resulting charge breakdown results are combined with those derived using the traditional PAH band strength ratio approach, which interprets particular PAH band strength ratios as proxies for PAH charge. Here the 6.2/11.2 μm PAH band strength ratio is successfully calibrated against its database equivalent: the ratio. In turn, this ratio is converted into the PAH ionization parameter, which relates it to the strength of the radiation field, gas temperature, and electron density. Population diagrams are used to derive the density and temperature. The bifurcated plot of the 8.6 versus 11.2 μm PAH band strength for the northwest photo dissociation region in NGC 7023 is shown to be a robust diagnostic template for the ratio in all three objects. Template spectra for the PAH charge and size subclasses are determined for each object and shown to favorably compare. Using the determined template spectra from NGC 7023 to fit the emission in all three objects yields, upon inspection of the Structure SIMilarity maps, satisfactory results. The choice of extinction curve proves to be critical. Concluding, the distinctly different astronomical environments of a reflection nebula, H ii region, and planetary nebula are reflected in their PAH emission spectra.

Ionization of Gas-Phase Polycyclic Aromatic Hydrocarbons in Electrospray Ionization Coupled with Gas Chromatography.

Herein, gas-phase polycyclic aromatic hydrocarbons (PAHs) as nonpolar compounds were ionized to protonated molecular ions [M + H]+ without radical cations and simultaneously analyzed using gas chromatography (GC)/electrospray ionization (ESI)-tandem mass spectrometry (MS/MS). The ionization profile, dissociation, and sensitivity were first investigated to understand the significant behavior of gas-phase PAHs under ESI. The formation of protonated molecular ions of PAHs was distinguished according to the analyte phase and ESI spray solvents. The protonated PAHs exhibited characteristic dissociations, such as H-loss, H2-loss, and acetylene-loss, via competition of internal energy. In addition, GC/ESI-MS/MS resulted in relatively lower concentration levels (better sensitivity) for the limits-of-detection (LODs) of PAHs than liquid chromatography (LC)/ESI-MS/MS, and it seems to result from the characteristic ionization mechanism of the gas-phase analyte under ESI. Furthermore, the LODs of gas-phase PAHs depended on molecular weight and proton affinity (PA). Consequently, we demonstrated the relationship among the analyte phases, sensitivities, and structural characteristics (molecular weight and PA) under ESI. The gas-phase PAHs provided enhanced protonation efficiency and sensitivity using GC/ESI-MS/MS, as their molecular weight and PA increased. Based on these results, we offered important information regarding the behavior of gas-phase analytes under ESI. Therefore, the present GC/ESI-MS/MS method has potential as an alternative method for simultaneous analysis of PAHs.

Optimal Laser Wavelength for Femtosecond Ionization of Polycyclic Aromatic Hydrocarbons and Their Nitrated Compounds in Mass Spectrometry.

The ionization and fragmentation processes were examined for a standard sample mixture containing 16 polycyclic aromatic hydrocarbons (PAHs) and 3 nitro-PAHs (NPAHs) by gas chromatography combined with mass spectrometry (GC/MS) using a femtosecond laser emitting at 400, 800, or 1200 nm as the ionization source. The signal intensities of NPAHs were lower and the fragmentation more extensive compared to those values for PAHs, especially at shorter wavelengths (400 nm). These results can be explained by efficient intersystem crossing to triplet levels and the shorter excited-state lifetimes of neutral NPAHs molecules, compared to the pulse width of the laser. Fragmentation was significantly suppressed by nonresonant multiphoton ionization when a laser emitting at longer wavelengths (1200 nm) was used. This result can be explained by the absorption spectrum of the molecular ion and the excess energy remaining in the ionized state. In fact, there was no absorption band at 1200 nm for the molecular ion, and the excess energy would be minimal when a near-infrared laser is used, which suppresses the fragmentation even for NPAHs. A doubly charged molecular ion was observed for PAHs but not for NPAHs, probably owing to the higher stability of the PAH molecule, the electrons of which are more strongly bound and are more resistive to field ionization. To demonstrate the utility of this technique, the sample extracted from particulate matter 2.5 (PM2.5) emitted from a diesel engine was measured. NPAHs as well as PAHs were clearly determined at 1200 nm, at which the background signal arising from the interference was drastically suppressed.

Unimolecular reaction energies for polycyclic aromatic hydrocarbon ions.

Imaging photoelectron photoion coincidence spectroscopy was employed to explore the unimolecular dissociation of the ionized polycyclic aromatic hydrocarbons (PAHs) acenaphthylene, fluorene, cyclopenta[d,e,f]phenanthrene, pyrene, perylene, fluoranthene, dibenzo[a,e]pyrene, dibenzo[a,l]pyrene, coronene and corannulene. The primary reaction is always hydrogen atom loss, with the smaller species also exhibiting loss of C2H2 to varying extents. Combined with previous work on smaller PAH ions, trends in the reaction energies (E0) for loss of H from sp2-C and sp3-C centres, along with hydrocarbon molecule loss were found as a function of the number of carbon atoms in the ionized PAHs ranging in size from naphthalene to coronene. In the case of molecules which possessed at least one sp3-C centre, the activation energy for the loss of an H atom from this site was 2.34 eV, with the exception of cyclopenta[d,e,f]phenanthrene (CPP) ions, for which the E0 was 3.44 ± 0.86 eV due to steric constraints. The hydrogen loss from PAH cations and from their H-loss fragments exhibits two trends, depending on the number of unpaired electrons. For the loss of the first hydrogen atom, the energy is consistently ca. 4.40 eV, while the threshold to lose the second hydrogen atom is much lower at ca. 3.16 eV. The only exception was for the dibenzo[a,l]pyrene cation, which has a unique structure due to steric constraints, resulting in a low H loss reaction energy of 2.85 eV. If C2H2 is lost directly from the precursor cation, the energy required for this dissociation is 4.16 eV. No other fragmentation channels were observed over a large enough sample set for trends to be extrapolated, though data on CH3 and C4H2 loss obtained in previous studies is included for completeness. The dissociation reactions were also studied by collision induced dissociation after ionization by atmospheric pressure chemical ionization. When modeled with a simple temperature-based theory for the post-collision internal energy distribution, there was reasonable agreement between the two sets of data.