Positive Ion Spectra Research Articles

A study on the surface responses and degradation mechanisms of epoxy-amine coating subjected to UV accelerated weathering and hygrothermal ageing using ToF-SIMS and FTIR analysis

Epoxy amine coatings were subjected to hygrothermal ageing and accelerated weathering conditions that is comprised of neutral salt spray test and UV accelerated degradation condition. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Fourier Transform Infrared Spectroscopy (FTIR) were employed to study the surface responses and spectral variation of epoxy amine coatings subjected to different ageing conditions. As a result, principal component analysis (PCA) of ToF-SIMS positive ion spectra illustrated that principal component 1 (PC1) has collected information on a variation of surface responses caused by accelerated weathering and hygrothermal ageing conditions as compared to fresh epoxy amine coatings. On the other hand, principal component 2 (PC2) has distinguished the different surface responses generated on epoxy amine coatings that were subjected to UV accelerated degradation conditions and those that were not. FTIR analysis has demonstrated the hydrolysis and photooxidation of epoxy amine coatings from the growth of two absorption bands at 1709 cm−1 and 1650 cm−1, indicating the formation of carbonyl-containing groups such as ketones, aldehydes, phenyl formates, imine or tertiary amides. This comprehensive analysis provides significant insights into the degradation mechanisms of epoxy amine coatings subjected to corrosion under insulation (CUI) and/or artificial weathering (AW) environment. Understanding these mechanisms is pivotal for industries reliant on epoxy coatings, such as oil and gas, ensuring enhanced performance and extended lifespan of their products under varying environmental conditions. The findings also contribute to the broader field of materials science by offering methodologies and analytical approaches that can be applied to other polymeric coatings and materials.

Taxonomic Identification of Commercial Boswellia spp. Resins by Ambient Ionization Mass Spectrometry

Historically, Boswellia resin, commonly known as frankincense, has been used for a variety of applications, including medicinal purposes and in religious ceremonies. These practices continued into the modern era, in which the trade of resin has increased dramatically. The genus Boswellia contains many species that are not currently protected by the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES), but research has found that some of these populations are predicted to decrease by 50 % in the next two decades due to overexploitation (Bongers et al., 2019). This highlights the need for a method that can identify Boswellia resins. In this research, resin from nine different species of Boswellia were collected and analyzed in positive ion mode by Direct Analysis in Real Time Time-of-Flight mass spectrometry (DART TOFMS) by dissolving the resin in methanol to obtain a chemotype devoid of background noise. Chemometric analysis of the data indicated that positive ion spectra from the resins separated the species effectively, indicating that DART TOFMS can be used to identify resins in trade.

Hydrated Formic Acid Clusters and their Interaction with Electrons.

We investigate ion formation in hydrated formic acid (FA) clusters upon collision with electrons of variable energy, focusing on electron ionization at 70 eV (EI) and low-energy (1.5-15 eV) electron attachment (EA). To uncover details about the composition of neutral clusters, we aim to elucidate the ion formation processes in FAM ⋅ WN clusters initiated by interaction with electrons and determine the extent of cluster fragmentation. EI predominantly produces protonated [FAm+H]+ ions, and in FA-rich clusters, the stable ring structures surrounding H3O+ ions are formed. In contrast, EA leads to a competition between the formation of intact [FAm ⋅ Wn]- and dissociated [FAm ⋅ Wn-H]- fragment ions, influenced by the cluster size, level of hydration, and electron energy. Our findings reveal a predisposition of low-energy EA towards forming [FAm ⋅ Wn]-, while higher electron energies tend to favor the formation of [FAm ⋅ Wn-H]- due to intracluster ion-molecule reactions. The comparison of positive and negative ion spectra suggests that the mass spectra of FA-rich clusters may indicate their actual size and composition. On the other hand, the more weakly bound water evaporation from the clusters depends strongly on the ionization. Thus, for the hydrated clusters, the neutral cluster size can hardly be estimated from the mass spectra.

Secondary ion mass spectrometry, a powerful tool for revealing ink formulations and animal skins in medieval manuscripts.

Book production by medieval scriptoria have gained growing interest in recent studies. In this context, identifying ink compositions and parchment animal species from illuminated manuscripts is of great importance. Here, we introduce time-of-flight secondary ion mass spectrometry (ToF-SIMS) as a non-invasive tool to identify both inks and animal skins in manuscripts, at the same time. For this purpose, both positive and negative ion spectra in inked and non-inked areas were recorded. Chemical compositions of pigments (decoration) or black inks (text) were determined by searching for characteristic ion mass peaks. Animal skins were identified by data processing of raw ToF-SIMS spectra using principal component analysis (PCA). In illuminated manuscripts from the fifteenth to sixteenth century, malachite (green), azurite (blue), cinnabar (red) inorganic pigments, as well as iron-gall black ink, were identified. Carbon black and indigo (blue) organic pigments were also identified. Animal skins were identified in modern parchments of known animal species by a two-step PCA procedure. We believe the proposed method will find extensive application in material studies of medieval manuscripts, as it is non-invasive, highly sensitive and able to identify both inks and animal skins at the same time, even from traces of pigments and tiny scanned areas.

An Investigation on the Relationships between Mass Spectrometric Collisional Data and Biological Activity/Stability of Some N-Acylethanolamine Acid Amidase (NAAA) β-Lactone Inhibitors

The rationale of the present study is that relationships between in vitro biological activity and mass spectrometric (MS) collisional data of molecular species have been already reported in the literature. Herein, the same approach has been employed to investigate possible correlations between MS stability and biological activity/stability data of a series of β-lactone amides and carbamates N-acylethanolamine acid amidase (NAAA) inhibitors. Electrospray ionization MS experiments were performed using an LCQ Deca ion trap and samples were introduced by direct infusion. Mass spectra of positive and negative ions have been obtained, and collisional experiments were performed on selected ionic species. Collisional-induced fragmentation pathways of molecular species related to β-lactone amide inhibitors are different in comparison to those of carbamates, being the former species more stable than the latter, due to β-lactone reactivity. Correlations were found between the characteristic collision energy (CE50) obtained by the breakdown curves and in vitro NAAA inhibitory potency of the β-lactone amides and carbamates analyzed. In the case of carbamates, a relationship between CE50 values and bovine serum albumin (BSA) stability data was also found, while any correlation was not found for amides due to their instability to BSA. β-Lactone NAAA inhibitors’ activity can be qualitatively associated with their lability, as measured by CE50 values. The results obtained could suggest that MS may be used as a preliminary experimental tool to identify carbamate NAAA inhibitors endowed with good biological stability.

Phytochemical Compound Profile and the Estimation of the Ferruginol Compound in Different Parts (Roots, Leaves, and Seeds) of Juniperus procera

Secondary plant metabolites and their derivatives play a significant role in human health. Ferruginol is a diterpene phenol that has recently received attention for its pharmacological properties, including antibacterial, antitumor, antimalarial, and cardioprotective effects. Recently, we detected the ferruginol compound in the leaf and seed extracts of Juniperus procera using different analytical approaches. The present work aims at detecting phytochemical compounds in a root extract of J. procera and estimating the amount of ferruginol compound in different parts of Juniperus procera. To screen the phytochemical compounds present in the root extract of J. procera, Gas chromatography/mass spectrometry (GC/MS) was performed. For ferruginol identification and estimation, high-performance liquid chromatography (HPLC) with the ferruginol reference standard and high-resolution direct analysis in real-time (DART) time-of-flight mass spectrometry (TOFMS) (DART-TOF-MS) analysis were used. GC/MS analysis revealed more than 20 bioactive compounds related to secondary plant metabolites in the root extract of J. procera with biological activity. The DART-TOF-MS result showed the typical positive ion spectra of ferruginol, and the HPLC result confirmed that the root extract of J. procera contains the ferruginol compound. In contrast, the root extract of J. procera contained a significant amount of ferruginol compared to that in the leaf and seed extracts. All parts of the J. procera contained the ferruginol compound and proved that ferruginol might be accumulated in the roots, leaves, and seeds of J. procera.

Positive and negative cluster ions of amino acids formed by electrospray droplet impact/secondary ion mass spectrometry (EDI/SIMS)

Cluster ions of amino acids (AAs) have been measured by several ionization methods such as electrospray, sonic spray, thermal desorption, and gas cluster ion beam (Arn+) bombardment. Prior research has primarily focused on positively charged cluster ions, whereas the formation of negatively charged cluster ions remains largely unexplored. In this study, mass spectra of both positive and negative cluster ions for 20 amino acids were measured by electrospray droplet impact/secondary ion mass spectrometry (EDI/SIMS). Because EDI is capable of generating abundant negative ions as well as positive ions, it is best suited for the comparative study on the dependence of polarity for AA cluster ions. For AAs with apolar side chains such as Ala, Val, Leu, and Ile, while large cluster sizes of positive cluster ions [n(AA) + H]+ (n = 11–21) were observed, negative cluster ions [n(AA) − H]− were observed with only n up to 3. The AAs with polar side chains (Ser, Thr, Asn, Gln, Tyr and Cys) gave similar n up to 7–12 for both [n(AA) + H]+ and [n(AA) − H]−. For basic AAs (Lys and Arg), the maximum n values observed for [n(AA) + H]+ are larger than those for [n(AA) − H]− and vice versa for acidic AA (Asp and Glu). A sharp intensity drop with n→(n+1) was observed for [n(AA) + H]+ with n of 12, 8, 8 and 11 for Pro, Ser, Thr, and Tyr, respectively. The magic number 8 for positive and 6 for negative cluster ions of Ser and Thr are in agreement with previous work. No magic numbers were observed for [n(AA) + H]+ and [n(AA) − H]− for acidic amino acids (Asp and Glu). The ligands (n−1)AAs in the negative clusters [AA − H]−⋅⋅⋅⋅(n−1)AA are bound more loosely than those in the positive clusters [AA + H]+ ⋅⋅⋅⋅(n−1)AA. The stability of amino acid cluster ions is critically affected by the polarities and structures of amino acids.

SIMS Analysis of Thin EUV Photoresist Films.

This study reports on the application of secondary ion mass spectrometry (SIMS) for examining thin (20-50 nm) chemically amplified resist films on silicon. SIMS depth profiling was carried out using a gas cluster ion beam to ensure minimal sputter-induced damage to the organic constituents of interest. Specific attention concerned the distribution of the photo acid generator (PAG) molecule within these films, along with the photo-induced fragmentation occurring on extreme ultra-violet photo exposure. Positive secondary ion spectra were collected using a traditional time of flight (ToF)-SIMS and the latest generation IONTOF Hybrid SIMS instrumentation equipped with an OrbitrapTM mass analyzer. Tandem mass spectrometry (MS/MS) capability within the OrbitrapTM secondary ion column was utilized to verify that the C19H17S+ secondary ion did indeed have the molecular structure consistent with the PAG structure. The superior mass resolving power of the OrbitrapTM mass analyzer (∼20× of the ToF mass analyzer) along with improved mass accuracy (a few ppm) proved pivotal in the mass spectral and depth profile analysis of these films. This was not the case for the ToF-SIMS experiments, as the mass spectra, as well as the associated depth profiles, exhibited severe molecular (isobaric) interferences.

Online composition detection and cluster analysis of Tibetan incense

Two optical technique: laser-induced breakdown spectroscopy (LIBS) and single particle aerosol mass spectrometry (SPAMS) were combined to study Tibetan incense. The ash and smoke of Tibetan incense were online detected with LIBS, and there existed more metal elements in the ash, such as Fe, Mg, Ba, Sr, Mn and so on. SPAMS technique focused on online recording mass spectra of the smoke, and the positive and negative ion spectra were obtained. What’s more, the lead isotopes in Tibetan incense smoke were analyzed and four isotopes (m/z = 204, 206, 207 and 208) were all observed in the mass spectrum. The principal component analysis (PCA) model was also introduced to achieve the clustering and classification of incenses, which could provide a reference for the traceability of particulate matter.

Time-of-flight secondary ion mass spectrometry fragment regularity in gallium-doped zinc oxide thin films

Time-of-flight secondary ion mass spectrometry fragment analysis remains a challenging task. The fragment appearance regularity (FAR) rule is particularly useful for two-element compounds such as ZnO. Ion fragments appearing in the form of ZnxOy obey the rule 2x ge 2y + 1 in the positive secondary ion spectrum and 2x le 2y + 1 in the negative spectrum where the valence of Zn is + 2 and that of O is − 2. Fragment analysis in gallium-doped ZnO (GZO) films can give insights into the bonding of the elements in this important semiconductor. Fragment analysis of 1 and 7 wt% GZO films shows that only the negative ion fragments obey the FAR rule where ZnO‒, 66ZnO‒, 68ZnO‒ and ZnO2‒ ion fragments appear. In the positive polarity, subdued peaks from out-of-the-rule ZnO+, 66ZnO+ and 68ZnO+ ion fragments are observed. The Ga ion peaks are present in both the positive and negative spectra. The secondary ion spectra of undoped ZnO also shows consistency with the FAR rule. This implies that Ga doping even in amounts that exceed the ZnO lattice limit of solubility does not affect the compliance with the FAR rule.

Tandem Electrospray Mass Spectrometry of Cyclic N-Substituted Oligo-β-(1→6)-D-glucosamines.

High-resolution electrospray mass spectra (MS and MS/MS CID) of positive ions of a series of protonated, ammoniated, and metallated molecules of cyclic N-substituted oligo-β-(1→6)-D-glucosamines differing in cycle size and N-acyl substituents were registered and interpreted. It was shown that the main type of fragmentation is a cleavage of glycosidic bonds of a cycle, and in some cases fragmentation of amide side chains is possible. If labile fragments in substituents (e.g., carbohydrate chains) are present, a decay of the cycle and an elimination of labile fragments are of comparable possibility. It was found that in some cases rearrangements with loss of an internal carbohydrate residue (IRL), or an internal part of a side chain, are feasible.

Analysis of kerogens and model compounds by time-of-flight secondary ion mass spectrometry (TOF-SIMS)

Here, kerogens of differing heat treatments are subjected to extremely high dissociation energies by sample bombardment by 25 keV Bi3+ primary ions during analysis by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Positive and negative secondary ions are produced from this decomposition and fragment ion distributions of model compounds and kerogens are compared and starkly different results are obtained for cations versus anions. Cations exhibit a large range of C/H ratios and include highly unsaturated linear chain ions and aromatic ions. Cations of kerogens possess predominantly no heteroatoms. Positive fragment ion distributions depend on the source material being bombarded. Mature, more aromatic kerogens produce higher yields of fragment ions of highly unsaturated carbon chains while immature, more aliphatic kerogens produce more aromatic fragment ions, particularly at the higher carbon numbers. This is consistent with the observation that aromatic model compounds produce a greater fraction of hydrogen-deficient, carbon chain fragment ions, as compared to a purely aliphatic model compound. There is substantial suppression of free radical fragment cations, except for large fragments. In contrast, there is little free radical suppression of the anions. The anions tend to be very hydrogen deficient, spanning a small range of C/H ratios. Highly unsaturated to pure carbon chain fragment anions dominate while aromatic anions are not found. In both positive and negative ion spectra, the yields of fragment ions corresponding to derivatives of the carbon chain molecules, polyynes and allenes, are substantial. Some heteroatom-containing fragment anions are produced, all of which are very hydrogen deficient.

High‐resolution peak analysis in TOF SIMS data

High mass resolution time‐of‐flight secondary ion mass spectrometry (TOF SIMS) can provide a wealth of chemical information about a sample, but the analysis of such data is complicated by detector dead‐time effects that lead to systematic shifts in peak shapes, positions, and intensities. We introduce a new maximum‐likelihood analysis that incorporates the detector behavior in the likelihood function, such that a parametric spectrum model can be fit directly to as‐measured data. In numerical testing, this approach is shown to be the most precise and lowest‐bias option when compared with both weighted and unweighted least‐squares fitting of data corrected for dead‐time effects. Unweighted least‐squares analysis is the next best, while weighted least‐squares suffers from significant bias when the number of pulses used is small. We also provide best‐case estimates of the achievable precision in fitting TOF SIMS peak positions and intensities and investigate the biases introduced by ignoring background intensity and by fitting to just the intense part of a peak. We apply the maximum‐likelihood method to fit two experimental data sets: a positive‐ion spectrum from a multilayer MoS2 sample and a positive‐ion spectrum from a TiZrNi bulk metallic glass sample. The precision of extracted isotope masses and relative abundances obtained is close to the best‐case predictions from the numerical simulations despite the use of inexact peak shape functions and other approximations. Implications for instrument calibration, incorporation of prior information about the sample, and extension of this approach to the analysis of imaging data are also discussed.

NEGATIVE ION MASS SPECTROMETRY FOR THE ANALYSIS OF N-LINKED GLYCANS.

N-glycans from glycoproteins are complex, branched structures whose structural determination presents many analytical problems. Mass spectrometry, usually conducted in positive ion mode, often requires extensive sample manipulation, usually by derivatization such as permethylation, to provide the necessary structure-revealing fragment ions. The newer but, so far, lesser used negative ion techniques, on the contrary, provide a wealth of structural information not present in positive ion spectra that greatly simplify the analysis of these compounds and can usually be conducted without the need for derivatization. This review describes the use of negative ion mass spectrometry for the structural analysis of N-linked glycans and emphasises the many advantages that can be gained by this mode of operation. Biosynthesis and structures of the compounds are described followed by methods for release of the glycans from the protein. Methods for ionization are discussed with emphasis on matrix-assisted laser desorption/ionization (MALDI) and methods for producing negative ions from neutral compounds. Acidic glycans naturally give deprotonated species under most ionization conditions. Fragmentation of negative ions is discussed next with particular reference to those ions that are diagnostic for specific features such as the branching topology of the glycans and substitution positions of moieties such as fucose and sulfate, features that are often difficult to identify easily by conventional techniques such as positive ion fragmentation and exoglycosidase digestions. The advantages of negative over positive ions for this structural work are emphasised with an example of a series of glycans where all other methods failed to produce a structure. Fragmentation of derivatized glycans is discussed next, both with respect to derivatives at the reducing terminus of the molecules, and to methods for neutralization of the acidic groups on sialic acids to both stabilize them for MALDI analysis and to produce the diagnostic fragments seen with the neutral glycans. The use of ion mobility, combined with conventional mass spectrometry is described with emphasis on its use to extract clean glycan spectra both before and after fragmentation, to separate isomers and its use to extract additional information from separated fragment ions. A section on applications follows with examples of the identification of novel structures from lower organisms and tables listing the use of negative ions for structural identification of specific glycoproteins, glycans from viruses and uses in the biopharmaceutical industry and in medicine. The review concludes with a summary of the advantages and disadvantages of the technique. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

Identification and Determination of the Molecular Structure of Phosphate Esters by the Joint Application of Positive Ion and Negative Ion Electron Ionization Mass Spectrometry

The decay paths of negative molecular ions of phosphate esters, formed under the conditions of resonance electron capture, are of the same type and, therefore, predictable. A combination of mass spectra of the studied substances obtained by this method with the mass spectra of positive ions recorded in the convential electron ionization mode significantly expands the possibilities of their identification and determination of the characteristics of their molecular structures. In this case, only one mass spectrometer can be used, quickly switched from one mode to another.

Source Apportionment and Mixing State of Single Particles in the Nanjing Jiangbei New Area

To characterize the ambient particles in the Nanjing Jiangbei New Area, a single particle aerosol mass spectrometer (SPAMS) was deployed from December 1 to 31, 2015. A total of 7.478 million particles were analyzed with both positive and negative ion spectra. The air quality of Nanjing during the measurement period was poor, and the percentage of pollution days was 49.2%. The correlation (R) between the SPAMS particle number and PM2.5 concentration was 0.83, showing that the particle number could reflect the trend in the variation of atmospheric pollution. The dominant pollutant source at the monitoring site was coal combustion, followed by vehicle emissions and industrial emissions, with a contribution ratio of 63.5%. The increase in the PM2.5 mass concentration was accompanied by a high proportion of coal combustion or vehicle emissions. A high mixing state between EC, ECOC, and OC and NO2-, NO3-, and SO4- was observed for the sources of biomass burning, dust, vehicle emissions, coal combustion, and industrial emissions.

MALDI Mass Spectrometry of Fullero[C60]tetrahydropyridines

Mass spectra of positive and negative MALDI ions of the series of fullero[C60] tetrahydropyridines with different substituents in a heterocycle are systematically studied for the first time. All mass spectra contain C60 fullerene peaks as a result of the reduction of fullero[C60]tetrahydropyridines. The intensities of the protonated molecular ions’ [M + H]+ peaks are highest in the mass spectra of positive ions of the studied compounds, while molecular radical ion [M]+ is less intense. The intensities of the peaks of molecular radical ion [M]– are highest in the mass spectra of the negative ions. The [C60C2H5] ions formed during the decay of the molecular ions with the detachment of neutral nitrile molecules is characteristic of all compounds. Using DFT quantum–chemical calculations (PBE/3z), the energies of the highest (HOMO) and lowest unoccupied molecular orbitals (LUMO) are determined for fullero[C60]tetrahydropyridines with substituents in the heterocycle.

Simple structural elucidation of ostreocin-B, a new palytoxin congener isolated from the marine dinoflagellate Ostreopsis siamensis, using complementary positive and negative ion liquid chromatography/quadrupole time-of-flight mass spectrometry.

Ostreocin-B is a new palytoxin congener of comparable complexity. Elucidation of the chemical structure by nuclear magnetic resonance has been hampered due to limited sample availability. More importantly, the dihedral angles of protons at the base of the hydroxyl groups on the ring structures are predicted to produce little couplings and thus disrupt connectivity. The present investigation solved the problem through mass spectrometry. Structural elucidation was performed by high-performance liquid chromatograph coupled to a quadrupole time-of-flight mass spectrometer equipped with an electrospray ionization source operated in positive and negative ion mode. Measurement parameters were optimized to achieve high sensitivity and a high ratio of singly charged ions. Ostreocin-D (C127 H219 N3 O53 ), another palytoxin congener possessing an unambiguously determined structure, was used as a template. The molecular formula of ostreocin-B, C127 H219 N3 O54 , indicates that it has one more oxygen atom than ostreocin-D. Comparison of the product ion spectra in negative ion mode indicates the occurrence of hydroxyl substitution at C44 in ostreocin-B, unlike in ostreocin-D. Positive ion spectra also support the 44-OH substructure by producing conjugated polyenes ascribable to the sequential loss of hydroxyls on the cyclic hemiacetal. The planar structure of ostreocin-B is assigned to 42-hydroxy-3,26-didemethyl-19-deoxypalytoxin (=44-hydroxyostreocin-D). The method used in this study is an excellent tool to obtain structural information on interspecies and intrastrain variation of palytoxin congeners in marine organisms.

Interactions of Dimethyltin(IV) with Uracil As Studied in the Gas Phase.

The gas-phase interactions of uracil (Ura) with dimethyltin(IV) were studied by a combined experimental and theoretical approach. Positive-ion electrospray spectra show that the interaction of dimethyltin(IV) with Ura results in the formation of the [(CH3)2Sn(Ura-H)]+ ion. The tandem mass spectrometry spectrum of this complex is characterized by numerous fragmentation processes, notably associated with elimination of H,N,C,O and C3,H3,N,O moieties, as well as the unusual loss of C2H6 leading to the [Sn(Ura-H)]+ complex. In turn, the [Sn(Ura-H)]+ complex fragments according to pathways already observed for the [Pb(Ura-H)]+ analogue. Sequential losses of ·CH3 radicals are also observed from the [(CH3)2Sn(N,C,O)]+ species (m/z 192). Comparison between density functional theory-computed vibrational spectra and the infrared multiple photon dissociation spectrum recorded between 1000 and 1900 cm-1 shows a good agreement as far as the global minimum is concerned. This comparison points to a bidentate interaction with a deprotonated canonical diketo form of uracil, involving both the N3 and O4 electronegative centers. This binding scheme has been already reported for the Pb/uracil system. The bidentate form characterized by the interaction between dimethyltin with N3 and O2 centers is slightly less stable. Interconversion between the two structures is associated with a small activation barrier (56 kJ/mol). The potential energy surfaces were explored to account for the main fragmentations observed upon collision-induced dissociation.

ToF‐SIMS and computation analysis: Fragmentation mechanisms of polystyrene, polystyrene‐d5, and polypentafluorostyrene

We studied the time‐of‐flight secondary ion mass spectrometry fragmentation mechanisms of polystyrenes—phenyl‐fluorinated polystyrene (5FPS), phenyl‐deuterated polystyrene (5DPS), and hydrogenated polystyrene (PS). From the positive ion spectra of 5FPS, we identified some characteristic molecular ion structures with isomeric geometries such as benzylic, benzocyclobutene, benzocyclopentene, cyclopentane, and tropylium systems. These structures were evaluated by the B3LYP‐D/jun‐cc‐pVDZ computation method. The intensities of the C7H2F5+ (m/z = 181), CyPent‐C9H3F4+ (m/z = 187), CyPent‐C9H4F5+ (m/z = 207), and CyPent‐C9H2F5+ (m/z = 205) ions were enhanced by resonance stabilization. The positive fluorinated ions from 5FPS tended to rearrange and produce fewer fluorine‐containing molecular ions through the loss of F (m/z = 19), CF (m/z = 31), and CF2 (m/z = 50) ion fragments. Consequently, the fluorine‐containing polycyclic aromatic ions had much lower intensities than their hydrocarbon counterparts. We propose the fragmentation mechanisms for the formation of C5H5+, C6H5+, and C7H7+ ion fragments, substantiated with detailed analyses of the negative ion spectra. These ions were created through elimination of a pentafluoro‐phenyl anion (C6F5−) and H+, followed by a 1‐electron‐transfer process and then cyclization of the newly generated polyene with carbon‐carbon bond formation. The pendant groups with elements of different electronegativities exerted strong influences on the intensities and fragmentation processes of their corresponding ions.