Electrospray ionization tandem mass spectrometry of the star‐shaped propoxylated diethylenetriamine polyols

Abstract

The collision-induced dissociation of the protonated five-arm star propoxylated diethylenetriamine polyols was studied under electrospray conditions. Two product ion series were detected because of the cleavage of the C-N bonds in the initiator moiety. No backbone fragmentation of the polyether chains was observed, which allowed to explore the initiation and side-chain propagation process of the oligomers. On the basis of MS/MS spectra, it is probable that the rate of the initiation is larger than that of the chain propagation. The propylene oxide repeat units attach to the five arms with approximately the same probability. Furthermore, it was found that the collision energy necessary to obtain 50% fragmentation (CE50) was linearly dependent on the molecular weight of the polyols.

Tandem Mass Spectrometry for Polymeric Structure Analysis: A Comparison of Two Common MALDI–ToF/ToF Techniques

“…As polymer synthesis techniques advance to enable more complex and controlled macromolecular architecture, so too must the analytical techniques used to probe such architecture. Tandem mass spectrometry has been utilized in tackling this challenge, showing success in probing microstructure, end‐group determination, backbone modifications, branching, and other macromolecular structures . The field of “polymeromics” is expanding; however, this is not as well developed as neighboring fields such as proteomics and petroleomics.…”

“…Tandem mass spectrometry has been utilized in tackling this challenge, showing success in probing microstructure, [1][2][3][4][5][6][7] end-group determination, [8][9][10][11][12][13] backbone modifications, [14] branching, [15,16] and other macromolecular structures. [17][18][19] The field of "polymeromics" is expanding [20,21] ; however, this is not as well developed as neighboring fields such as proteomics and petroleomics. Polymer science has yet to fully embrace these more complex forms of mass spectroscopic analysis, while the field of mass spectrometry has had comparatively very little technique development for polymer samples.…”

Tandem Mass-Remainder Analysis of Industrially Important Polyether Polyols

“…The chemical structures of different types of polyether polyols are shown in the Supporting Information ( Figure S1). The unambiguous structural elucidation of these complex polymer systems including multi arm (star) polyether polymers or copolymers runs into difficulties even when using sophisticated MS/MS techniques as demonstrated in a few reports [15,21,22]. Recently, we have provided a simple algorithm, called Mass-remainder analysis (MARA) and its improved method, the Multistep Mass-remainder analysis (M-MARA) for the processing and assessment of complex mass spectra [23][24][25][26].…”

Retention Time and Optimal Collision Energy Advance Structural Annotation Relied on LC–MS/MS: An Application in Metabolite Identification of an Antidementia Agent Namely Echinacoside

“…The quantitative structure−retention relationship (QSRR) model 3 is the most frequently recommended to advance structural annotation. Moreover, the collision cross section (CCS) acquired from ion mobility MS (IM-MS) 4 and CE 50 that is termed as the collision energy (CE) at which the survival yield is 50% 5 has been favored as eligible molecular descriptors (MDs) in holistic manners as well. However, these approaches cannot exactly tackle the determinant bottleneck of HR-MS/ MS which is the configuration of an entire structure via linking those substructures.…”