MALDI mass spectrometric determination of molecular site-specific charge localisation, and laser-induced coalescence reactivity of fullerenodendrimers

Fati, Dorina; Vasil’ev, Yury V.; Wachter, Norbert K.; Taylor, Roger; Drewello, Thomas

doi:10.1016/s1387-3806(03)00249-5

Cited by 14 publications

(17 citation statements)

References 22 publications

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“…Ionization is observed to take place via cationization in the positive mode, and deprotonation and reduction in the negative mode. Discussion of the charge‐carrying site will be carried out according to the methodology used in MALDI by Fati et al 34, 35 for amphiphilic and dendrimeric fullerene derivatives and by Zenobi and coworkers36 for donor–acceptor and donor–bridge–acceptor fullerenes.…”

Section: Discussionmentioning

confidence: 99%

Mass spectrometric characterization of 3′‐imino[60]fulleryl‐3′‐deoxythymidine by collision‐induced dissociation

Greisch

Pauw

2007

J. Mass Spectrom.

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The primary structure of 3'-imino[60]fulleryl-3'-deoxythymidine ions is studied using mass spectrometry both in the positive and negative modes. Interaction between the subunits is discussed using collision-induced dissociation (CID) spectra. Collisional activation with argon of the sodiated cations leads to the cleavage of the glycosidic bond and the transfer of a radical hydrogen from the deoxyribose to the thymine. The sodiated thymine is the only fragment observed for low collision energies in the positive mode. In the negative mode, two different ionization mechanisms take place, reduction and deprotonation in the presence of triethylamine. The 2.7 eV electron affinity of C60 and its huge cross section compared to the small cross section and predicted 0.44 eV electron affinity of the thymidine subunit most likely localize the radical electron on the fullerene. On the other hand, deprotonation of the 3'-azido-3'-deoxythymidine (AZT) is known to occur in N-3, the most acidic site of the nucleobase. Consequently, deprotonation causes the negative charge to be initially localized on the thymine. Both types of parent anions give the radical anion C60*- as fragment. The other fragments detected are the dehydrogenated 3'-imino[60]fulleryl-3'-deoxyribose anion, C60NH2-, C60N- and C60H-. Since in negative ion mass spectrometry all fragments include the [60]fullerene unit, this suggests that the fragmentation is driven by the electron affinity of the [60]fullerene, likely responsible for a charge transfer between the deprotonated thymine and the C60.

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Section: Discussionmentioning

confidence: 99%

Mass spectrometric characterization of 3′‐imino[60]fulleryl‐3′‐deoxythymidine by collision‐induced dissociation

Greisch

Pauw

2007

J. Mass Spectrom.

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“…For these compounds, conventional mass spectrometry, involving heating as a means to achieve evaporation, or the use of direct LDI, would lead to severe decomposition, practically preventing a meaningful analysis. Solvent-based MALDI experiments with these 9,10 and closely related fullerene-based dendrimers 53 have been reported recently. These investigations were focused on the screening of different matrices, the deliberate promotion of a particular ion formation mechanism and the question of charge localization in the analyte ions.…”

Section: Solvent-free Maldi Of Amphiphilic Methano[60]fullerene Derivmentioning

confidence: 94%

Application and Evaluation of Solvent-Free Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for the Analysis of Derivatized Fullerenes

Kotsiris

Vasil’ev

Streletskii

et al. 2006

Eur J Mass Spectrom (Chichester)

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A variety of derivatized fullerenes have been studied by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Of particular emphasis has been the evaluation of a recently introduced solvent-free sample/target preparation method. Solvent-free MALDI is particularly valuable in overcoming adverse solvent-related effects, such as insolubility and/or degradation of the sample. The method was applied to fullerene derivatives susceptible to decomposition under insufficiently "soft" MALDI conditions. Analytes included the hydrofullerene: C(60)H(36), fluorofullerenes: C(60)F(x) where x = 18, 36, 46, 48 and C(70)F(x) where x = 54, 56, methano-bridged amphiphilic ligand adducts to C(60) and the [4 + 2] cycloadduct of tetracene to C(60). The new solvent-free sample preparation is established as an exceedingly valuable addition to the repertoire of preparation protocols within MALDI. The MALDI mass spectra were of very high quality throughout, providing a testimony that "soft" MALDI conditions could be achieved. Using the [4 + 2] cycloadduct of tetracene to C(60) as the model analyte for direct comparison with solvent-based MALDI, the solvent-free approach led to less fragmentation and more abundant analyte ions. Applying solvent-free sample preparation, different matrix compounds have been examined for use in the MALDI of derivatized fullerenes, including sulfur, tetracyanoquinodimethane (TCNQ), 9-nitroanthracene (9-NA) and trans-2-[3-(4-tert-butylphenyl)-2-methyl-2- propenylidene]malononitrile (DCTB). DCTB was confirmed as the best performing matrix, reducing unwanted decomposition and suppression effects.

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“…The thermochemistry of this process has been detailed 36,37 and several striking examples of its superior performance with a variety of fullerene derivatives have been published. 14,32,[38][39][40][41][42] The dissociation behaviour of the radical anion was probed by LIFT which is a collision-induced/laser activation experiment on a TOF/TOF instrument. 34 The spectrum reveals that the electron resides on the C 60 moiety while the crown ether acts as ''ligand'' and is released in the dissociation (Fig.…”

Section: Negative-ion Modementioning

confidence: 99%

“…This concept has been used successfully before to localise the charge carrying moiety with derivatised fullerenes. [14][15][16] Aside from the investigation of the ion formation process, the study puts particular emphasis on the analysis of three differently sized crown ether-fullerene conjugates with the five alkali metal cations.…”

Section: Introductionmentioning

confidence: 99%

Ion formation pathways of crown ether–fullerene conjugates in the gas phase

Kellner

Nye

Gernler

et al. 2014

Phys. Chem. Chem. Phys.

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The ion formation of crown ether-[60]fullerene conjugates of the type (crown - H)-C60-H with crown = 12cr4, 15cr5 and 18cr6 has been studied with matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation mass spectrometry (ESI MS). In total five different ways of ion formation are presented, including metalation (MALDI, ESI), protonation and oxidation (both in MALDI) in the positive-ion mode and deprotonation (MALDI, ESI) and reduction (MALDI) in the negative-ion mode. In line with thermochemistry, the deprotonation and electron transfer processes involve the C60 moiety as the charge-carrying entity, while protonation and metalation occur at the crown ether. Particular emphasis has been placed on the study of metal cation attachment in MALDI varying the crown ether size in the conjugate and using different alkali metal chlorides in the target preparation. Dissociation reactions of the metalated conjugates are influenced by the interaction strength of the metal cation to the crown ether fullerene conjugate. The data confirm an increase in bond strength with smaller metal cations, supporting the notion of charge density-driven interactions.

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MALDI mass spectrometric determination of molecular site-specific charge localisation, and laser-induced coalescence reactivity of fullerenodendrimers

Cited by 14 publications

References 22 publications

Mass spectrometric characterization of 3′‐imino[60]fulleryl‐3′‐deoxythymidine by collision‐induced dissociation

Mass spectrometric characterization of 3′‐imino[60]fulleryl‐3′‐deoxythymidine by collision‐induced dissociation

Application and Evaluation of Solvent-Free Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for the Analysis of Derivatized Fullerenes

Ion formation pathways of crown ether–fullerene conjugates in the gas phase

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