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RationaleFree fatty acids and lipid classes containing fatty acid esters are major components of lipidome. In the absence of a chemical derivatization step, FA anions do not yield all of the structural information that may be of interest under commonly used collision‐induced dissociation (CID) conditions. A line of work that avoids condensed‐phase derivatization takes advantage of gas‐phase ion/ion chemistry to charge invert FA anions to an ion type that provides the structural information of interest using conventional CID. This work was motivated by the potential for significant improvement in overall efficiency for obtaining FA chain structural information. MethodsA hybrid triple quadrupole/linear ion‐trap tandem mass spectrometer that has been modified to enable the execution of ion/ion reaction experiments was used to evaluate the use of 4,4′,4″‐tri‐tert‐butyl‐2,2′:6′,2″‐terpyridine (ttb‐Terpy) as the ligand in divalent magnesium complexes for charge inversion of FA anions. ResultsMg(ttb‐Terpy)22+complexes provide significantly improved efficiency in producing structurally informative products from FA ions relative to Mg(Terpy)22+complexes, as demonstrated for straight‐chain FAs, branched‐chain FAs, unsaturated FAs, and cyclopropane‐containing FAs. It was discovered that most of the structurally informative fragmentation from [FA‐H + Mg(ttb‐Terpy)]+results from the loss of a methyl radical from the ligand followed by radical‐directed dissociation (RDD), which stands in contrast to the charge‐remote fragmentation (CRF) believed to be operative with the [FA‐H + Mg(Terpy)]+ions. ConclusionsThis work demonstrates that a large fraction of product ions from the CID of ions of the form [FA‐H + Mg(ttb‐Terpy)]+are derived from RDD of the FA backbone, with a very minor fraction arising from structurally uninformative dissociation channels. This ligand provides an alternative to previously used ligands for the structural characterization of FAs via CRF.
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Electrically Driven Dynamics of Few‐Chain NbSe 3
An in situ transmission electron microscopy study of few‐chain NbSe3encapsulated within the hollow core of carbon nanotubes is presented, where the tube/chain system is subjected to applied axial electrical currents. Electromigration and thermal excitation forces result in collective and individual chain dynamics, with concomitant radial deformations of the encapsulating tubes.
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- Award ID(s):
- 1807233
- PAR ID:
- 10117914
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- physica status solidi (b)
- Volume:
- 256
- Issue:
- 12
- ISSN:
- 0370-1972
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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