Molecular level differentiation between end‐capped and intramolecular azofunctional oligo(ε‐caprolactone) positional isomers through liquid chromatography multistage mass spectrometry

Peptu, Cristian; Brink, Oscar F. van den; Harabagiu, Valeria; Simionescu, Bogdan C.; Kowalczuk, Marek; Silberring, Jerzy

doi:10.1002/pola.26019

Cited by 5 publications

(2 citation statements)

References 41 publications

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“…MS/MS fragmentation studies were further employed to confirm the structures of CDCL main products. The fragmentation of CDCL derivatives proceeds similarly to other CD-oligoester derivatives [ 19 , 20 , 45 , 46 ], having two main pathways: the cleavage of the 1,4-glycosidic bond of β-CD [ 53 , 54 , 55 ] and the cleavage of the ester bonds from the CL attached to the β-CD molecule [ 56 , 57 , 58 ]. Oligocaprolactone fragmentation can occur either on the acyl side through 1-3 hydrogen rearrangements ( Scheme 2 A— a series ) or on the alkyl side through 1-4 hydrogen rearrangements of the ester bond ( Scheme 2 A— b series ).…”

Section: Resultsmentioning

confidence: 99%

Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry

Peptu¹,

Blaj²,

Balan-Porcăraşu³

et al. 2022

Polymers

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Cyclodextrins have previously been proven to be active in the catalysis of cyclic ester ring-opening reactions, hypothetically in a similar way to lipase-catalyzed reactions. However, the way they act remains unclear. Here, we focus on β-cyclodextrin’s involvement in the synthesis and characterization of β-cyclodextrin-oligocaprolactone (CDCL) products obtained via the organo-catalyzed ring-opening of ε-caprolactone. Previously, bulk or supercritical carbon dioxide polymerizations has led to inhomogeneous products. Our approach consists of solution polymerization (dimethyl sulfoxide and dimethylformamide) to obtain homogeneous CDCL derivatives with four monomer units on average. Oligomerization kinetics, performed by a matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) optimized method in tandem with 1H NMR, revealed that monomer conversion occurs in two stages: first, the monomer is rapidly attached to the secondary OH groups of β-cyclodextrin and, secondly, the monomer conversion is slower with attachment to the primary OH groups. MALDI MS was further employed for the measurement of the ring-opening kinetics to establish the influence of the solvents as well as the effect of organocatalysts (4-dimethylaminopyridine and (–)-sparteine). Additionally, the mass spectrometry structural evaluation was further enhanced by fragmentation studies which confirmed the attachment of oligoesters to the cyclodextrin and the cleavage of dimethylformamide amide bonds during the ring-opening process.

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Section: Resultsmentioning

confidence: 99%

Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry

Peptu¹,

Blaj²,

Balan-Porcăraşu³

et al. 2022

Polymers

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“…In such situations, the structural characterization is performed by fragmentation experiments called tandem MS (MS/MS). Detection and interpretation of the fragmentation spectra ions allows reconstruction of the primary structure (connectivity) of the selected polymer architecture in the case of polyesters [ 26 , 27 , 28 , 29 ]. Such fragmentation studies were applied in the case of CD modified with 3-OH-butyrates [ 15 , 25 ] obtained by ROP of β-butyrolactone catalyzed by (−)-sparteine.…”

Section: Introductionmentioning

confidence: 99%

Structural Architectural Features of Cyclodextrin Oligoesters Revealed by Fragmentation Mass Spectrometry Analysis

et al. 2018

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Cyclodextrins (CDs) were used in the present study for the ring-opening oligomerization (ROO) of l-lactide (LA) in order to synthesize biodegradable products with possible applications in pharmaceutical and medical fields. The practical importance of ROO reactions may reside in the possibility of synthesizing novel CD derivatives with high purity due to the dual role played by CDs, the role of the initiator through the hydroxylic groups, and the role of the catalyst by monomer inclusion in the CD cavity. The analyzed compounds were CDs modified with oligolactides obtained through ROO reactions of l-lactide in dimethylformamide. The resulting CD isomeric mixtures were investigated using classical characterization techniques such as gel permeation chromatography and nuclear magnetic resonance. Moreover, advanced mass spectrometry (MS) techniques were employed for the determination of the average number of monomer units attached to the cyclodextrin and the architecture of the derivatives (if the monomer units were attached as a single chain or as multiple chains). Thus, fragmentation studies effectuated on two different instruments (ESI Q-TOF and MALDI TOF) allowed us to correlate the size of the oligolactide chains attached to the CD with the observed fragmentation patterns.

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Liquid Chromatography‐Electrospray Ionization Mass Spectrometry of Synthetic Polymers

Charles

Altuntaş

2015

Encyclopedia of Analytical Chemistry

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Production of increasingly sophisticated functional macromolecules and development of new polymerization processes have placed a severe demand on analytical methodologies for accurate characterization of synthetic polymers. With regard to the variety of heterogeneities found in polymer samples, where molecules can be distributed in terms of molar mass, chemical composition, functionality, molecular architecture, and concentration, development of multidimensional approaches is mandatory. The large orthogonality of liquid chromatography (LC) and mass spectrometric (MS) techniques, both largely employed individually in the field of synthetic polymers, makes their coupling very attractive. Because of its unrivaled softness that ensures molecule integrity upon ionization and of its ability to accommodate a flowing liquid, electrospray is the ideal ionization source to interface them. However, the electrospray process also raises some constraints on the composition of the liquid phase from which molecules have to be transferred in the gas phase as ions to be mass detected. This article reviews the capabilities and limitations of various on‐line LC‐ESI‐MS couplings involving most commonly used chromatographic techniques for synthetic polymer separation in the liquid phase, namely size‐exclusion chromatography (SEC), liquid chromatography at critical conditions (LCCCs), and gradient polymer elution chromatography (GPEC).

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Molecular level differentiation between end‐capped and intramolecular azofunctional oligo(ε‐caprolactone) positional isomers through liquid chromatography multistage mass spectrometry

Cited by 5 publications

References 41 publications

Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry

Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry

Structural Architectural Features of Cyclodextrin Oligoesters Revealed by Fragmentation Mass Spectrometry Analysis

Liquid Chromatography‐Electrospray Ionization Mass Spectrometry of Synthetic Polymers

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