<b>Convenient visualization of high‐resolution tandem mass spectra of synthetic polymer ions using Kendrick mass defect analysis – the case of polysiloxanes</b>

Mertz

Delmée

et al. 2016

Plasma Process. Polym.

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Highlighting an actual plasma copolymerization remains difficult when using infrared or x‐ray photoelectron spectroscopies as they provide no evidence of the formation of covalent bonds between the precursors. The combination of high resolution mass spectrometry and mass defect analysis is proposed to characterize plasma (co)polymers of alkyl and perfluorinated acrylates. The mass spectra of the coatings are readily turned into Kendrick mass defect plots unambiguously demonstrating the occurrence of plasma co‐oligomers, as suspected from their thermal behavior. Requiring a proper calibration only, the mass defect analysis elegantly transforms an abstruse mass spectrum of plasma polymer in simple point series and constitutes a user‐friendly method for data mining.

Section: Resultsmentioning

confidence: 99%

The Definitive Evidence of a Plasma Copolymerization of Alkyl and Perfluorinated Acrylates Using High Resolution Mass Spectrometry and Mass Defect Analysis

Mertz

Delmée

et al. 2016

Plasma Process. Polym.

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“…28) The associated DMS-based KMD plot (Fig. 5E) satisfactorily separates some product ion series 24) but two clouds remain unresolved ( Me z n / Me z n -CH 4 and H b n + /J n 2+ , in red) in spite of different end-groups and charge states owing to some errors in the measurements of m / z and a limited variation of their KMD values. On the contrary, the expansion of the KMD dimension results in a complete removal of all the interferences in the KMD plot calculated with DMS/6 as the base unit (Fig.…”

Section: Resultsmentioning

confidence: 83%

“…24) Similarly, this last part extends the concept of fractional base units to the MS/MS stage by offering a re-analysis of partially unresolved data published elsewhere. 24,28) The ESI-CAD mass spectrum of a (methyl, methoxy)-ended poly(dimethylsiloxane) (PDMS) 25-mer adducted with ammonium ion is depicted in Fig. 5A (recorded with an orthogonal acceleration TOF Qstar Elite, Applied Biosystems SCIEX, Concord, ON, Canada).…”

Section: Resultsmentioning

confidence: 92%

“…Using the neutral expelled during collision activated dissociation (CAD) as the base unit also provides useful alignments in the KMD plots from the tandem mass spectra of polymer ions. 24) All these alternative base units make sense from a chemical point of view but in the course of the manipulation of KMD plots, the idea of a fractional base unit chemically senseless but mathematically acceptable has just arisen. Instead of the repeat unit of a polymer backbone, a fraction of this repeat unit ( i.e.…”

Section: Introductionmentioning

confidence: 99%

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Improving the Resolution of Kendrick Mass Defect Analysis for Polymer Ions with Fractional Base Units

Sato

2017

Mass Spectrometry

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The concept of a fractional base unit for the Kendrick mass defect (KMD) analysis of polymer ions is introduced for the first time. A fraction of the ethylene oxide (EO) repeat unit (namely EO/8) has been used for the KMD analysis of a poly(ethylene oxide) and found to amplify the variations of KMD between monoisotopic and 13C isotopes, producing an isotopically resolved KMD plot at full scale when the KMD plot computed with EO is fuzzy. The expansion of the KMD dimension using a fractional base unit has then been successfully used to unequivocally discriminate all the distributions from a blend of poly(ethylene oxide)s in a high resolution KMD plot calculated with EO/3 as base unit. Extending the concept of fractional base units to other repeat units, the visualization of the co-oligomers from a poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer has been dramatically improved using a fraction of the propylene oxide repeat unit (namely PO/3) in an oligomer and isotope resolved plot. High resolution KMD plots were eventually calculated from tandem mass spectra of poly(dimethylsiloxane) ions using a fraction of the dimethylsiloxane (DMS) unit (namely DMS/6) with clearer point alignments and a discrimination of all the product ion series, out of reach of the KMD analysis using DMS. Versatile and producing high resolution KMD plots, the introduction of fractional base units is believed to be a major step towards the implementation of the KMD analysis as a routine data mining tool for mass spectrometry in polymer chemistry.

“…In these studies, using monomer A as the Kendrick base, polymers with the same number of B units but a differing number of A units appeared as a horizontal series of points, whereas polymers with differing number of B units but the same number of A units exhibited a diagonal trend (Figure S2D, Supporting Information). Similarly, KMD plots were found to be very beneficial to analyze MS/MS data of synthetic polymers where series of fragments essentially differ from each other in terms of terminations, as exemplified for polysiloxanes . Overall, KMD proved very helpful for graphical ranking of mass spectral data that exhibit distributions of signals, which is also typically the case of MS/MS patterns used to decrypt messages encoded in digital polymers.…”

Section: Introductionmentioning

confidence: 93%

Convenient Graphical Visualization of Messages Encoded in Sequence‐Defined Synthetic Polymers Using Kendrick Mass Defect Analysis of their MS/MS Data

Poyer

Macro Chemistry & Physics

Sato

et al. 2018

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Kendrick mass defect (KMD) analysis is shown here to be a convenient method to read binary messages encoded in the structure of two types of sequence‐defined synthetic polymers, namely, polyurethanes and poly(alkoxyamine phosphodiester)s. KMD analysis allows graphical ranking of mass data obtained for species containing repeating units. This is performed on MS/MS data in which distribution of fragments reveals the comonomer sequence of digital macromolecules. Choosing one coding monomer as the base unit, KMD computation of MS/MS data leads to stair‐like plots where flat steps correspond to that monomer selected as the base unit while oblique steps reveal the other monomer. To correct for any point misalignments resulting from slight inaccuracy of fragment mass measurement, fractional base units are used to perform resolution‐enhanced KMD (RE‐KMD) analysis. As the length of the chain increased, a procedure aiming at correct aliased points is also implemented to achieve continuous, more convenient, stair‐like plots.