Mining the NIST Mass Spectral Library Reveals the Extent of Sodium Assisted Inductive Cleavage in Collision-Induced Fragmentation

Ludwig, Marcus; Broeckling, Corey D.; Dorrestein, Pieter C.; Dührkop, Kai; Schymanski, Emma L.; Böcker, Sebastian; Nothias, Louis‐Félix

doi:10.26434/chemrxiv.12114987

Cited by 2 publications

(2 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Assigned composition of ions observed during fragmentation of PES-oligomer ion with m / z 775 are listed in Figure 5 B and are formed via a charge remote 1,5-H rearrangement over the ester group as described by Wesdemiotis et al 50 or via the charge migration fragmentation mechanism. 51 …”

Section: Results and Discussionmentioning

confidence: 99%

Probing Polyester Branching by Hybrid Trapped Ion-Mobility Spectrometry–Tandem Mass Spectrometry

Voeten

Put²,

Jordens

et al. 2021

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Trapped ion-mobility spectrometry combined with quadrupole time-of-flight mass spectrometry (TIMS-QTOFMS) was evaluated as a tool for resolving linear and branched isomeric polyester oligomers. Solutions of polyester samples were infused directly into the ion source employing electrospray ionization (ESI). TIMS-MS provides both mobility and m / z data on the formed ions, allowing construction of extracted-ion mobilograms (EIMs). EIMs of polyester molecules showed multimodal patterns, indicating conformational differences among isomers. Subsequent TIMS-MS/MS experiments indicated mobility differences to be caused by (degree of) branching. These assignments were supported by liquid chromatography-TIMS-MS/MS analysis, confirming that direct TIMS-MS provided fast (500 ms/scan) distinction between linear and branched small oligomers. Observing larger oligomers (up to 3000 Da) using TIMS required additional molecular charging to ensure ion entrapment within the mobility window. Molecular supercharging was achieved using m -nitrobenzyl alcohol (NBA). The additional charges on the oligomer structures enhanced mobility separation of isomeric species but also added to the complexity of the obtained fragmentation mass spectra. This complexity could be partly reduced by post-TIMS analyte-decharging applying collision-induced dissociation (CID) prior to Q1 with subsequent isolation of the singly charged ions for further fragmentation. The as-obtained EIM profiles were still quite complex as larger molecules possess more possible structural isomers. Nevertheless, distinguishing between linear and symmetrically branched oligomers was possible based on measured differences in collisional cross sections (CCSs). The established TIMS-QTOFMS approach reliably allows branching information on isomeric polyester molecules up to 3000 Da to be obtained in less than 1 min analysis time.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Probing Polyester Branching by Hybrid Trapped Ion-Mobility Spectrometry–Tandem Mass Spectrometry

Voeten

Put²,

Jordens

et al. 2021

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

show abstract

“…These are additional challenges associated with the identification pipeline of metabolic fingerprinting and footprinting studies that need to be accounted for when identifying features generated from in vitro models. In the present work, strategies for accurate identification also included spiking experiments on samples and process blanks, as well as accounting for sodium-assisted inductive cleavage in collision-induced fragmentation mechanisms in tandem MS experiments 46 , respectively. These compounds were identified with a confidence level of 2 26,27 (Figures S25 and S26) because no chemical standards were used for comparison (Table 1).…”

Section: Metabolic Fingerprints and Sample Classificationmentioning

confidence: 99%

Mass Spectrometry-Based Metabolic Fingerprinting Contributes to Unveil the Role of RSUME in Renal Cell Carcinoma Cell Metabolism

et al. 2020

View full text Add to dashboard Cite

Clear cell renal cell carcinoma (ccRCC) is a heterogeneous disease with 50−80% patients exhibiting mutations in the von Hippel−Lindau (VHL) gene. RSUME (RWD domain (termed after three major RWD-containing proteins: RING fingercontaining proteins, WD-repeat-containing proteins, and yeast DEAD (DEXD)-like helicases)-containing protein small ubiquitinrelated modifier (SUMO) enhancer) acts as a negative regulator of VHL function in normoxia. A discovery-based metabolomics approach was developed by means of ultraperformance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (MS) for fingerprinting the endometabolome of a human ccRCC cell line 786-O and three other transformed cell systems (n = 102) with different expressions of RSUME and VHL. Cross-validated orthogonal projection to latent structures discriminant analysis models were built on positive, negative, and a combination of positive-and negative-ion mode MS data sets. Discriminant feature panels selected by an iterative multivariate classification allowed differentiating cells with different expressions of RSUME and VHL. Fifteen identified discriminant metabolites with level 1, including glutathione, butyrylcarnitine, and acetylcarnitine, contributed to understand the role of RSUME in ccRCC. Altered pathways associated with the RSUME expression were validated by biological and bioinformatics analyses. Combined results showed that in the absence of VHL, RSUME is involved in the downregulation of the antioxidant defense system, whereas in the presence of VHL, it acts in rerouting energy-related pathways, negatively modulating the lipid utilization, and positively modulating the fatty acid synthesis, which may promote deposition in droplets.

show abstract

Mining the NIST Mass Spectral Library Reveals the Extent of Sodium Assisted Inductive Cleavage in Collision-Induced Fragmentation

Cited by 2 publications

References 15 publications

Probing Polyester Branching by Hybrid Trapped Ion-Mobility Spectrometry–Tandem Mass Spectrometry

Probing Polyester Branching by Hybrid Trapped Ion-Mobility Spectrometry–Tandem Mass Spectrometry

Mass Spectrometry-Based Metabolic Fingerprinting Contributes to Unveil the Role of RSUME in Renal Cell Carcinoma Cell Metabolism

Contact Info

Product

Resources

About