Collision-induced dissociation of protonated fentanyl: A DFT study

Lau, Justin Kai-Chi; Romanov, V. I.; Lukow, Stefan; Hopkinson, Alan C.; Verkerk, Udo H.

doi:10.1016/j.comptc.2020.113117

Cited by 6 publications

(15 citation statements)

References 24 publications

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“…Bond distance (BD) between the proton and the O-amide was calculated according to lowest energy (LE) and the Boltzmann weighted (BW) BD. b This fentanyl data was generated through optimizing the protonated structure provided in Lau et al 5 at the same level of theory used for other molecules in Table 1. competitive ionization sites that were part of a separate Rgroup of the fentanyl compound as opposed to the N-amide and O-amide locations of the core fentanyl structure.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…was for n number of conformers. Bond distance (BD) between the proton and the O-amide was calculated according to lowest energy (LE) and the Boltzmann weighted (BW) BD. b This fentanyl data was generated through optimizing the protonated structure provided in Lau et al at the same level of theory used for other molecules in Table . …”

Section: Resultsmentioning

confidence: 99%

“…Techniques such as Raman spectroscopy and Fourier transform infrared spectroscopy can be used for the identification of bulk materials. , Trace detection techniques provide another means of detection by identifying residues and vapors, thus indicating the potential for detection of illicit materials within a container . Mass spectrometry − and ion mobility spectrometry , employing atmospheric pressure chemical ionization (APCI) are sensitive technologies for the detection of illicit drugs. APCI, also known as ambient ionization, is a soft ionization technique with little to no molecular fragmentation in the ionization process.…”

Section: Introductionmentioning

confidence: 99%

“…Protonated fentanyl has recently been studied with DFT (no PA or GB calculations) by Lau et al using the B3LYP functional at the 6-31G(d) − and 6-311++G(d,p) ,− basis set levels. A range of DFT exchange-correlation functionals and basis sets were found in the PA literature but not associated with a fentanyl application.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Proton Affinity Values of Fentanyl and Fentanyl Analogues Pertinent to Ambient Ionization and Detection

Denis

Bade

Renslow

et al. 2022

J. Am. Soc. Mass Spectrom.

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Proton affinity is a major factor in the atmospheric pressure chemical ionization of illicit drugs. The detection of illicit drugs by mass spectrometry and ion mobility spectrometry relies on the analytes having greater proton affinities than background species. Evaluating proton affinities for fentanyl and its analogues is informative for predicting the likelihood of ionization in different environments and for optimizing the compounds’ ionization and detection, such as through the addition of dopant chemicals. Herein, density functional theory was used to computationally determine the proton affinity and gas-phase basicity of 15 fentanyl compounds and several relevant molecules as a reference point. The range of proton affinities for the fentanyl compounds was from 1018 to 1078 kJ/mol. Fentanyl compounds with the higher proton affinity values appeared to form a bridge between the oxygen on the amide and the protonated nitrogen on the piperidine ring based on models and calculated bond distances. Experiments with fragmentation of proton-bound clusters using atmospheric flow tube-mass spectrometry (AFT-MS) provided estimates of relative proton affinities and showed proton affinity values of fentanyl compounds >1000 kJ/mol, which were consistent with the computational results. The high proton affinities of fentanyl compounds facilitate their detection by ambient ionization techniques in complex environments. The detection limits of the fentanyl compounds with AFT-MS are in the low femtogram range, which demonstrates the feasibility of trace vapor drug detection.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Proton Affinity Values of Fentanyl and Fentanyl Analogues Pertinent to Ambient Ionization and Detection

Denis

Bade

Renslow

et al. 2022

J. Am. Soc. Mass Spectrom.

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show abstract

“…As shown in Figure a, an abundant fragment ion was observed at m/z 105 for 1-phenethyl-4-piperidone by the loss of a 4-piperidone moiety. The characteristic fragment ions of depropionylfentanyl were found at m/z 188 and 105, which might originate from successive losses of an aniline moiety and a piperidine moiety , (Figure b). The two characteristic fragment ions could be potentially used as discerning product ions for broad screening of fentanyl compounds without structural substitution on the piperidine ring and the phenethyl group based on fixed precursor ion scans.…”

Section: Resultsmentioning

confidence: 99%

Suspect Screening of Fentanyl Analogs Using Matrix-Assisted Ionization and a Miniature Mass Spectrometer with a Custom Expandable Mass Spectral Library

Guo

Shang

et al. 2021

Anal. Chem.

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The reliable identification of fentanyl and its analogs is of great significance for public security. However, with the growing prevalence of fentanyl compounds, current analytical strategies cannot fully meet the need for fast and high-throughput detection. In this study, a simple, rapid, and on-site analytical protocol was developed based on a miniature mass spectrometer. A dramatically simplified workflow was implemented using matrixassisted ionization, bypassing complex sample pretreatment and chromatographic separation. The tandem mass spectrometry (MS/ MS) capability afforded by the miniature ion trap mass spectrometer facilitated the investigation of fragmentation patterns for 49 fentanyl analogs during collision-induced dissociation, revealing valuable information on marker fragment ions and characteristic neutral loss. Calculations on Laplacian bond order values further verified the mass spectrometric behavior. A computation-assisted expandable mass spectral library was constructed in-house for fentanyl compounds. Smart suspect screening was carried out based on the full-scan MS and MS/MS data. The present study demonstrates an appealing potential for forensic applications, enabling streamlined screening for the presence of illicit fentanyl compounds at the point of seizures of suspect samples.

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Dependency of fentanyl analogue protomer ratios on solvent conditions as measured by ion mobility‐mass spectrometry

Johnson,

Sabatini,

Aderorho

et al. 2024

J Mass Spectrom

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Recently, our group has shown that fentanyl and many of its analogues form prototropic isomers (“protomers”) during electrospray ionization. These different protomers can be resolved using ion mobility spectrometry and annotated using mobility‐aligned tandem mass spectrometry fragmentation. However, their formation and the extent to which experimental variables contribute to their relative ratio remain poorly understood. In the present study, we systematically investigated the effects of mixtures of common chromatographic solvents (water, methanol, and acetonitrile) and pH on the ratio of previously observed protomers for 23 fentanyl analogues. Interestingly, these ratios (N‐piperidine protonation vs. secondary amine/O = protonation) decreased significantly for many analogues (e.g., despropionyl ortho‐, meta‐, and para‐methyl fentanyl), increased significantly for others (e.g., cis‐isofentanyl), and remained relatively constant for the others as solvent conditions changed from 100% organic solvent (methanol or acetonitrile) to 100% water. Interestingly, pH also had significant effects on this ratio, causing the change in ratio to switch in many cases. Lastly, increasing conditions to pH ≥ 4.0 also prompted the appearance of new mobility peaks for ortho‐ and para‐methyl acetyl fentanyl, where all previous studies had only showed one single distribution. Because these ratios have promise to be used qualitatively for identification of these (and emerging) fentanyl analogues, understanding how various conditions (i.e., mobile phase selection and/or chromatographic gradient) affect their ratios is critically important to the development of advanced ion mobility and mass spectrometry methodologies to identify fentanyl analogues.

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Collision-induced dissociation of protonated fentanyl: A DFT study

Cited by 6 publications

References 24 publications

Proton Affinity Values of Fentanyl and Fentanyl Analogues Pertinent to Ambient Ionization and Detection

Proton Affinity Values of Fentanyl and Fentanyl Analogues Pertinent to Ambient Ionization and Detection

Suspect Screening of Fentanyl Analogs Using Matrix-Assisted Ionization and a Miniature Mass Spectrometer with a Custom Expandable Mass Spectral Library

Dependency of fentanyl analogue protomer ratios on solvent conditions as measured by ion mobility‐mass spectrometry

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