Consecutive losses of two benzyl radicals from the [M + Na]+ adduct ions of di- and tri(benzyloxy)benzenes under ESI/CID conditions

Kuck, Dietmar; Heitkamp, Sandra; Sproß, Jens; Letzel, Matthias C.; Ahmed, Ishtiaq; Krohn, Karsten; Parker, Robert G.; Wang, Yulun; Robbins, Virginia J.; Ames, William; Schettler, Paul D.; Hark, Richard R.

doi:10.1016/j.ijms.2014.06.013

Cited by 8 publications

(10 citation statements)

References 80 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…My fascination with the chemistry of aromatic ions in the gas phase has never ceased, and joint insights were obtained with a number of other research groups during those decades [54–60]. Arenium ion chemistry was particularly fruitful since the synthetic approach to suitable model compounds that, as gaseous ions, would undergo “designed” isomerization and fragmentation reactions, is particularly well controllable for a synthetic organic chemist.…”

Section: Ion/neutral Complexes As Reactive Intermediates During the Fmentioning

confidence: 99%

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

Kuck

2015

The Chemical Record

Self Cite

View full text Add to dashboard Cite

Detailed insights gained from our research into the gas-phase chemistry of ionized and protonated diphenylalkanes and their congeners, obtained by extended synthesis of isotopically labeled model compounds and mass spectrometry, are presented and merged with those acquired during our development of a new family of polycyclic hydrocarbons, the centropolyindanes. Aside from a Personal Account that describes "two scientific lives in one", it is demonstrated, on the one hand, how our understanding of organic chemistry can help to shed light on the details of mass spectrometric fragmentation and to unravel, in a more fundamental way, the unimolecular reactivity of gaseous ions. On the other hand, it is shown how unexpected reactivity of related ions in solution, being subject to the very same fundamentals of organic chemistry, can lead to the construction of novel and, in part, unique three-dimensional polycyclic structures that may contribute to future research in material science. Two such apparently independent fields of organic chemistry may be seen as joint contributions of the art of science.

show abstract

Section: Ion/neutral Complexes As Reactive Intermediates During the Fmentioning

confidence: 99%

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

Kuck

2015

The Chemical Record

Self Cite

View full text Add to dashboard Cite

show abstract

“…Unfortunately, attempts to perform accurate mass measurements were unsuccessful. However, the MALDI mass spectrum also shows the characteristic losses of up to at least three tentacle residues from both the [M + Na] + and [M + K] + molecular ions [ 44 – 46 ]. In contrast to the MALDI mass spectrum, the high-resolution ESI-(+) mass spectrum of TBTQ-(OAcG) 6 (see Figure S11 and Table S2) exhibits a sole peak group with the maximum component at m / z 1505.9690 and Δ( m / z ) = 0.5, indicating the presence of doubly charged ions.…”

Section: Resultsmentioning

confidence: 99%

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Liu¹,

Wang²,

Li³

et al. 2020

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

A sugar-functionalized water-soluble tribenzotriquinacene derivative bearing six glucose residues, TBTQ-(OG) 6 , was synthesized and its interaction with C60 and C70-fullerene in co-organic solvents and aqueous solution was investigated by fluorescence spectroscopy and ultraviolet-visible spectroscopy. The association stoichiometry of the complexes TBTQ-(OG) 6 with C60 and TBTQ-(OG) 6 with C70 was found to be 1:1 with binding constants of K a = (1.50 ± 0.10) × 105 M−1 and K a = (2.20 ± 0.16) × 105 M−1, respectively. The binding affinity between TBTQ-(OG) 6 and C60 was further verified by Raman spectroscopy. The geometry of the complex of TBTQ-(OG) 6 with C60 deduced from DFT calculations indicates that the driving force of the complexation is mainly due to the hydrophobic effect and to host–guest π–π interactions. Hydrophobic surface simulations showed that TBTQ-(OG) 6 and C60 forms an amphiphilic supramolecular host–guest complex, which further assembles to microspheres with diameters of 0.3–3.5 μm, as determined by scanning electron microscopy.

show abstract

“…This agrees with the observation of the elimination of benzaldehyde in minor relative amounts from ions [6 þ Na] þ and [8 þ Na] þ and in quite high relative abundance from ions [7 þ Na] þ , as another characteristic feature of sodiated pyrogallol ions. Based on the results of our previous study, 14 we assume that the phloroglucinol dibenzyl ether moieties : the expected peak at m/z 600 is almost absent.…”

Section: Cid Mass Spectra Of the [M þ Na] þ Molecular Ions Of 13-dipmentioning

confidence: 94%

“…A similar, somewhat more complex scenario was elucidated for the [M þ Na] þ molecular ions of 1,2,4-trihydroxybenzene tribenzyl ether. 14 In the present work, we give an overview on further examples of the characteristic two-fold or even multiple mass spectrometric loss of benzyl radicals from the [M þ Na] þ ions of pyrogallol-derived oligobenzyl ethers. In particular, we wanted to check whether, and to which extent, functional groups and/or structural variations affect the otherwise dominating loss of benzyl groups.…”

Section: Introductionmentioning

confidence: 99%

Consecutive loss of two benzyl radicals from the [M + Na]⁺ adduct ions of pyrogallol tribenzyl ether and its derivatives

Kuck

Heitkamp

Letzel

et al. 2017

Eur J Mass Spectrom (Chichester)

Self Cite

View full text Add to dashboard Cite

The electrospray ionization-collision-induced dissociation mass spectra of nine pyrogallol tribenzyl ethers, 2-10, and a catechol dibenzyl ether, 11, that bear various functional groups or larger structural extensions have been studied with respect to the occurrence of a highly characteristic consecutive loss of two benzyl radicals from the sodiated molecular ions, [M + Na]. It is shown that this specific fragmentation reaction strongly dominates other fragmentation routes, such as loss of carbon monoxide, formaldehyde and water. In addition, elimination of benzaldehyde occurs as a minor fragmentation channel in most cases. In contrast to these aryl-benzyl ethers, the consecutive two-fold loss of CH is suppressed in the [M + Na] ions of dibenzyl ethers derived from multiply benzylated gallocatechin and catechin, where the elimination of benzyl alcohol prevails the primary fragmentation almost completely. The secondary fragmentation of the [M + Na] ions, which also comprises the two-fold loss of CH, as well as a remarkable primary fragmentation of a flavene-based congener leading to particularly stable sodium-free chromylium product ions is also presented. † Deceased.

show abstract

Consecutive losses of two benzyl radicals from the [M + Na]+ adduct ions of di- and tri(benzyloxy)benzenes under ESI/CID conditions

Cited by 8 publications

References 80 publications

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Consecutive loss of two benzyl radicals from the [M + Na]⁺ adduct ions of pyrogallol tribenzyl ether and its derivatives

Contact Info

Product

Resources

About

Consecutive losses of two benzyl radicals from the [M + Na]+ adduct ions of di- and tri(benzyloxy)benzenes under ESI/CID conditions

Cited by 8 publications

References 80 publications

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

Consecutive loss of two benzyl radicals from the [M + Na]+ adduct ions of pyrogallol tribenzyl ether and its derivatives

Contact Info

Product

Resources

About

Consecutive loss of two benzyl radicals from the [M + Na]⁺ adduct ions of pyrogallol tribenzyl ether and its derivatives