University of Warwick crest Dr. Mark P. Barrow: Research in mass spectrometry

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Fullerene related

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Research during my PhD was focused upon studying fullerenes and fullerene derivatives by mass spectrometry, and some of my published findings have been listed below. You can also find more fullerene related information on my fullerene links page.

  1. The use of laser desorption/ionization (LDI) to generate C50, C60, and C70 using Mn(CO)3(Cp(Cp5)) as a precursor. The generation of fullerenes from this organometallic species was successful, although the low resulting yields meant that this would not be a viable technique for the production of bulk quantities of fullerenes. (J. Organomet. Chem., 1998, 572, 135-139)
  2. A study of C60On revealed that under MALDI conditions, the oxide coalesces to form a "dumb-bell-like" species, with two C60 moieties bridged by one or two oxygen atoms. Under LDI conditions, however, the oxides fused to form larger fullerenes (ie not bridged species), with oxygen atoms also present on the exterior of such a structure. These two ionization-technique-dependent reactions had not been previously observed and compared. (Chem. Phys. Lett., 1998, 293, 302-308)
  3. C60 was found to degrade to C120O under ambient conditions. This major discovery has strong implications for any developing applications of C60. Degradation must now become a serious consideration when utilizing C60. (Chem. Commun., 1998, 2497-2498)
  4. In follow up to the study of C60On oxides, the first successful fusion of C70 oxides was performed. Attempts by others to fuse them in the solution phase have proven unsuccessful, but our use of LDI conditions resulted in the observation of a (C70On)2 species in the gas phase for the first time. (Int. J. Mass Spectrom., 1999, 184, L1-L4)
  5. A PSD study of pure fullerenes on an LDI-ToF instrument with a time-based ion gate led to the discovery that artifacts arising from the delayed ionization of fullerenes may cause interference in the resulting spectra. Delayed ionization is a known phenomenon exhibitied by fullerenes and metal clusters. This discovery has implications for all instruments that rely on use of time-based ion gates as the basis for mass selection in a ToF instrument when investigating fullerenes. (Int. J. Mass Spectrom., 2000, 203, 111-125)
  6. A study of fullerenes using ESI FT-ICR has shown that it is indeed possible to generate fullerene ions directly from the toluene solution using electrospray, without the need for any other reagents. The literature to date has only included investigations that involved the modification of the solution to assist ionization, except for only one group that has previously managed to record an ESI spectrum from a pure toluene solution. It had been thought that only one brand of ESI source (manufactured by VG) was able to produce such results, but our results (obtained while using an Analytica of Branford Inc. ESI source) challenge this assumption. (Chem. Phys. Lett., 2000, 330, 267-274)
  7. A variety of sector and hybrid instruments (geometries of BE, BEqQ, and EB-ToF) were used to investigate hydrogenated fullerenes, utilizing EI, LSIMS, and LDI. Unimolecular fragmentation, low energy CID, and high energy CID were studied. Cage rupture via CmHn loss was observed, rather than the loss of C2 units. In contrast, the formation of fullerene fragments via the loss of ligands is often observed when investigating fullerene derivatives. Parallels with the gas phase behavior of fluorinated fullerenes were noted. (Int. J. Mass Spectrom., 2000, 195/196, 599-607)
  8. Several derivatized fullerenes, all of which bear ligands that are bound to the carbon core through a nitrogen atom, have been investigated using laser desorption/ionization time-of-flight mass spectrometry. It was found that it was possible to produce C59N following the fragmentation of these derivatives, and that it was also possible for them to undergo coalescence reactions, leading to the production of higher carbon clusters that possess a networked nitrogen atom. The loss of CN was shown to be one of the primary fragmentation routes for the heterofullerenes formed in the gas-phase. Finally, it was shown that the heterofullerenes undergo delayed ionization, in the same manner as pure fullerenes. (J. Phys. Chem. A, 2000, 104, 9171-9179)

Related references:

  1. “In-Plume Thermodynamics of the MALDI Generation of Fluorofullerene Anions,” Alexey V. Streletskii, Ilya N. Ioffe, Sotirios G. Kotsiris, Mark P. Barrow, Thomas Drewello, Steven H. Strauss, and Olga V. Boltalina, J. Phys. Chem. A, 2005, 109, pp. 714-719
  2. “Laser-Induced Fragmentation, Coalescence and Delayed Ionisation of Nitrogen-Substituted Fullerene Derivatives,” Nigel Clipston, Tracy Brown, Mark P. Barrow, Thomas Drewello, The 197th Meeting of the Electrochemical Society, Toronto, May 14th - 18th, 2000, Abstract 713
  3. “Evaluation of Electrospray Ionization as a General Tool for the Analysis of Derivatized Fullerenes,” Mark P. Barrow, Xidong Feng, James I. Wallace, Olga V. Boltalina, Roger Taylor, Peter J. Derrick, Thomas Drewello, The 197th Meeting of the Electrochemical Society, Toronto, May 14th - 18th, 2000, Abstract 711
  4. “Nitrogen Heterofullerene Formation, Fragmentation, Coalescence and Delayed Ionisation: a Study by Laser Desorption/Ionisation Time-of-Flight Mass Spectrometry (LDIToFMS),” Nigel Clipston, Tracy Brown, Yury Vasil’ev, Mark P. Barrow, Thomas Drewello, Uwe Reuther, Andreas Hirsch, Rainer Herzschuh, 15th International Mass Spectrometry Conference, Barcelona, August 27th - September 1st, 2000, Abstract PBA301
  5. “Nanoflow-Electrospray Ionization as an Effective Technique for the Characterization of Fullerenes and Derivatized Fullerenes,” Mark P. Barrow, Xidong Feng, James I. Wallace, Olga V. Boltalina, Roger Taylor, Peter J. Derrick, Thomas Drewello, 15th International Mass Spectrometry Conference, Barcelona, August 27th - September 1st, 2000, Abstract PAB502
  6. “Delayed Ionization of Fullerenes as the Cause of Interference Signals Obtained Using Reflectron Time-of-Flight Mass Spectrometry,” Mark P. Barrow and Thomas Drewello, 15th International Mass Spectrometry Conference, Barcelona, August 27th - September 1st, 2000, Abstract PAB401
  7. “Significant Interferences in the Post Source Decay Spectra of Ion-Gated Fullerene and Coalesced Carbon Cluster Ions,” Mark P. Barrow and Thomas Drewello, Int. J. Mass Spectrom., 2000, 203, pp. 111-125
  8. “Characterization of Fullerenes and Fullerene Derivatives by Nanospray,” Mark P. Barrow, Xidong Feng, James I. Wallace, Olga V. Boltalina, Roger Taylor, Peter J. Derrick, Thomas Drewello, Chem. Phys. Lett., 2000, 330, pp. 267-274
  9. “Laser-Induced Formation, Fragmentation, Coalescence and Delayed Ionization of the C59N Heterofullerene,” Nigel L. Clipston, Tracy Brown, Yury Vasil’ev, Mark P. Barrow, Rainer Herzschuh, Uwe Reuther, Andreas Hirsch, Thomas Drewello, J. Phys. Chem. A, 2000, 104, pp. 9171-9179
  10. “Unimolecular Ion Dissociation and Laser-induced Coalescence of Hydrogenated Fullerenes,” Monika Möder, Matthias Nüchter, Bernd Ondruschka, Gabor Czira, Karoly Vékey, Mark P. Barrow, Thomas Drewello, Int. J. Mass Spectrom., 2000, 195/196, pp. 599-607 (Robert Squires Memorial Issue)
  11. “Laser-Induced Fragmentation, Coalescence and Delayed Ionisation of Nitrogen-Substituted Fullerene Derivatives,” Nigel Clipston, Tracy Brown, Mark P. Barrow, Thomas Drewello, Uwe Reuther, Andreas Hirsch, Rainer Herzschuh, Dominic Gostick, Glenn Critchley, 24th Annual Meeting of the British Mass Spectrometry Society, University of Reading, September 12th - 15th, 1999
  12. “Ion Dissociation and Laser-Induced Coalescence of Hydrogenated Fullerenes,” Mark P. Barrow, Yury Vasil’ev, Andrew Bottrill, Peter J. Derrick, Monika Möder, Matthias Nüchter, Gabor Czira, Karoly Vékey, Thomas Drewello, 24th Annual Meeting of the British Mass Spectrometry Society, University of Reading, September 12th - 15th, 1999
  13. “Evaluation of Electrospray Ionization as a General Tool for the Analysis of Derivatized Fullerenes,” Mark P. Barrow, Xidong Feng, James I. Wallace, Olga V. Boltalina, Roger Taylor, Peter J. Derrick, Thomas Drewello, 24th Annual Meeting of the British Mass Spectrometry Society, University of Reading, September 12th - 15th, 1999
  14. “Laser-induced gas-phase synthesis of dimeric C70 oxides,” Mohammed S. Al-Jafari, Mark P. Barrow, Roger Taylor, Thomas Drewello, Int. J, Mass Spectrom., 1999, 184, pp. L1-L4
  15. “High-Energy CollisionInduced Dissociation of Ionised Fullerenes and Metallofullerenes Derived from Laser Desorption/Ionisation,” Andrew R. Bottrill, Mark P. Barrow, Thomas Drewello, Anastassios E. Giannakopulos, Peter J. Derrick, 23rd Annual Meeting of the British Mass Spectrometry Society, University of Warwick, September 13th - 16th, 1998
  16. “Delayed Ionisation as the Cause of Significant Interferences in the Post Source Decay (PSD) Spectra of Fullerene and Large Carbon Cluster Cations,” Mark P. Barrow and Thomas Drewello, 23rd Annual Meeting of the British Mass Spectrometry Society, University of Warwick, September 13th - 16th, 1998
  17. “Laser-Induced Coalescence and Aggregation Reactions of Fullerene Oxides,” Mark P. Barrow, Mohammed Al-Jafari, Nicole J. Tower, Roger Taylor, Thomas Drewello, 23rd Annual Meeting of the British Mass Spectrometry Society, University of Warwick, September 13th - 16th, 1998
  18. “Penta(cyclopentadienyl)-η5-cyclopentadienylmanganesetricarbonyl: structure and laser-induced conversion to fullerenes,” Mark P. Barrow, J. Kevin Cammack, Matthias Goebel, Ian M. Wasser, K. Peter C. Vollhardt, Thomas Drewello, J. Organomet. Chem., 1998, 572, pp. 135-139
  19. “C60 degrades to C120O,” Roger Taylor, Mark P. Barrow, Thomas Drewello, Chem. Commun., 1998, pp. 2497-2498
  20. “Matrix-assisted laser-induced gas-phase aggregation of C60,” Mark P. Barrow, Nicole J. Tower, Roger Taylor, Thomas Drewello, Chem. Phys. Lett., 1998, 293, pp. 302-308
  21. “Ion-Fragmentation and Coalescence Reactions of Fullerene Derivatives,” Lutz Kaseberg, Rainer Herzschuh, K.Dieter Asmus, Mark Barrow, Thomas Drewello, 45th ASMS Conference on Mass Spectrometry and Allied Topics, Palm Springs, June 1st - 5th, 1997, Abstract WPA 010