Electrospray ionization mass spectrometry of metalloporphyrins

Vandell, Victor E.; Limbach, Patrick A.

doi:10.1002/(sici)1096-9888(199803)33:3<212::aid-jms619>3.0.co;2-e

Cited by 56 publications

(51 citation statements)

References 4 publications

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“…ESI mass spectrometry is becoming a popular technique for the analyses of porphyrins and metalloporphyrins [10][11][12][13][14][15][16]. Free base porphyrins are readily protonated [14,16].…”

Section: Resultsmentioning

confidence: 99%

Electrospray ionization (ESI) tandem mass spectrometric analysis of meso-tetrakis(heptafluoropropyl)porphyrin

Lau

Sadı́lek

Khalil

et al. 2005

J. Am. Soc. Mass Spectrom.

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The results of an electrospray ionization (ESI(ϩ) and ESI(Ϫ)) collision-induced fragmentation investigation of meso-tetrakis(heptafluoropropyl)porphyrin (T F HP) are reported. The fragmentation patterns of T F HP show, in both ionization modes, the formation of fragments with direct covalent meso-alkyl-to-␤-linkages on elimination of HF. In addition, in the ESI(ϩ) mode, the losses of perfluoroalkyl radicals are observed. A detailed analysis of the fragmentation patterns allows conclusions to be drawn on the identification of the fragment species. Comparable cyclized products were previously produced using radical-initiated solution- In particular, the mesoperfluoroalkylporphyrins have proved useful in, for example, the design of synthetic monooxygenase mimicks [6]. In addition, their potential in both photodynamic therapy and in the in vivo imaging by fluorescence and 19 F NMR (nuclear magnetic resonance) spectroscopy was evaluated [7].Recently, the groups of Guo and Chen described, inter alia, the functionalization of meso-arylporphyrins with meso-fluoroiodo-alkanes (1) or fluorochloro-alkanes (2). Radical-induced deiodination or debromination resulted in the formation of terminal radicals that efficiently ring-closed with the neighboring ␤-positions to form products 3 and 4, respectively (Scheme 1) [8,9]. Thus, a range of fused ring products enclosing five-and six-membered rings were prepared. These findings prompted the question whether meso-perfluoroalkylporphyrins such as meso-tetrakis(heptafluoropropyl)-porphyrin (T F HP) also undergo similar cyclizations. This study will answer this question affirmatively.Here, we report the analysis of T F HP by tandem electrospray ionization (ESI) mass spectrometry in the positive and negative mode. Using collision-induced fragmentation techniques, we find that rich fragmentation patterns in positive and negative ionization modes are observed. Next to the expected losses of radical fragments, HF eliminations are observed, which we attribute to the formation of polycyclic systems containing meso-alkyl-to-␤-fusions. A detailed analysis of the spectra allows some conclusions to be drawn as to the nature of these products.

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Section: Resultsmentioning

confidence: 99%

Electrospray ionization (ESI) tandem mass spectrometric analysis of meso-tetrakis(heptafluoropropyl)porphyrin

Lau

Sadı́lek

Khalil

et al. 2005

J. Am. Soc. Mass Spectrom.

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“…The classes of organic compounds include polycyclic aromatic hydrocarbons (PAH) [29] , polyenes [30][31][32] , organometallics (e.g. metallocenes and metalloporphyrins) [33][34][35][36][37] , quinines [38] , and fullerenes [39] . Van Berkel et al [33,34] were the first to systematically investigate the electrospray ionization of model metalloporphyrins, and observed the molecular ions.…”

Section: Meanwhile According To Reports About Characterization Of Pementioning

confidence: 99%

“…On the one hand, it can be attributed to the different oxidation potentials of metal porphyrins. As reported by previous researchers [35] , vanadium-containing porphyrins have higher oxidation potentials than nickel-containing porphyrins.…”

Section: Meanwhile According To Reports About Characterization Of Pementioning

confidence: 99%

Characterization of Vanadyl and Nickel Porphyrins Enriched from Heavy Residues by Positive-Ion Electrospray Ionization FT-ICR Mass Spectrometry

Liu

Wang

et al. 2015

Energy Fuels

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Petroporphyrins were enriched and purified from atmospheric residues of two typical heavy oils, Canadian oil sand bitumen (OSAR, Ni: 80 ppm, V: 190 ppm, S: 3.97 wt%) and Chinese Liaohe heavy oil (LHAR, Ni: 68.7 ppm, V: 1.81 ppm, S: 0.36 wt%) by silica gel chromatography. The separation and purification were confirmed by atomic absorption spectroscopy (AAS) combined with UV-vis spectroscopy, and the petroporphyrins were characterized by positive-ion electrospray ionization (ESI) Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Vanadyl and nickel porphyrins in OSAR are simultaneously identified by mass measurement and isotopic fine structure. Vanadyl porphyrins with structures of N 4 VO, N 4 VO 2 and N 4 VOS are all detected as protonated analyte ([M+H] + ). Both molecular ion (M +• ) and analyte ([M+H] + ) as well as their corresponding isotopes are observed for N 4 Ni porphyrins in OSAR and LHAR with an average mass resolving power of over 400 000 (m/∆m 50% ). This is rarely detected by FT-ICR MS using ESI technique previously. Formation of molecular ion can be attributed to the low oxidation potential of nickel porphyrins, effect of oil matrix on the solution conductivity and the relatively low flow rate of solution into the capillary. Three more highly unsaturated types of N 4 VO porphyrins were identified in addition to the six well-documented structures. Compared to N 4 VO porphyrins, N 4 VOS porphyrins present higher DBE ranging from 21 to 27 while N 4 VO 2 porphyrins show lower DBE ranging from 18 to 20 and narrower carbon number distribution, suggesting possible different origins of sulfur (pyrolysis of kerogen) and oxygen (diagenesis of chlorophyills). Ni/V and ratio of relative abundance of ETIO porphyrins to DPEP porphyrins (∑ETIO/∑DPEP) for nickel porphyrins indicate that Liaohe oil and Canadian oil sand bitumen are continental and marine sediment, respectively, and Liaohe oil has a higher maturity.Enrichment by the simple chromatographic method facilitates the mass spectral identification of nickel porphyrins even for heavy residue with low content of nickel and high content of sulfur.

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“…Electrospray ionization (ESI) mass spectrometry (MS) is becoming a popular technique for the analyses of porphyrins [25][26][27][28][29][30][31][32][33][34][35].…”

mentioning

confidence: 99%

Observation of phenyl-fused porphyrinoids during the ESI mass spectrometric analysis of meso-pentafluorophenyl-substituted porphyrin and corrole

Lau

Sadı́lek

Gouterman

et al. 2006

J. Am. Soc. Mass Spectrom.

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The results of ESI(ϩ) and ESI(Ϫ) mass spectrometry/mass spectrometry investigations of meso-tetrakisphenylporphyrin (TPP) and meso-trisphenylcorrole (TPC) in comparison with their meso-tetrakis(pentafluorophenyl)-substituted analogs T F PP and T F PC are reported. The fragmentation patterns of TPP and TPC show the expected loss of meso-aryl radicals. Analyzing the meso-pentafluorophenyl substituted analogs T F PP and T F PC, we found ESI(Ϫ) to be an excellent ionization mode. Rich and well-defined HF-elimination fragmentation patterns unique to the presence of meso-tetrafluorophenyl groups and evocative for the formation of fragments with direct covalent o-phenyl-to-␤-linkages are observed. A computation of the feasibility and relative energies of the resulting species corroborates the interpretation of the experimental findings. The computations indicate the presence of cooperative interactions between the linkages that direct the linkage formations to occur in a unidirectional fashion. MS/MS/MS experiments also provide indications for the regioselectivity of the fusions. Our observations further detail earlier reports of similar HF-eliminations and allow a generalization of the findings. The results presented may also point to strategies towards the bulk synthesis of novel porphyrinoid structures. (J Am Soc Mass Spectrom 2006, 17, 1306 -1314

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Electrospray ionization mass spectrometry of metalloporphyrins

Cited by 56 publications

References 4 publications

Electrospray ionization (ESI) tandem mass spectrometric analysis of meso-tetrakis(heptafluoropropyl)porphyrin

Electrospray ionization (ESI) tandem mass spectrometric analysis of meso-tetrakis(heptafluoropropyl)porphyrin

Characterization of Vanadyl and Nickel Porphyrins Enriched from Heavy Residues by Positive-Ion Electrospray Ionization FT-ICR Mass Spectrometry

Observation of phenyl-fused porphyrinoids during the ESI mass spectrometric analysis of meso-pentafluorophenyl-substituted porphyrin and corrole

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