Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid
In this study, low molecular weight poly(δ-valerolactone) (PVL) was synthesized through bulk-ring openings polymerization of δ-valerolactone with boric acid (B(OH)3) as a catalyst and benzyl alcohol (BnOH) as an initiator. The resulting homopolymer was characterized with the aid...
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MDPI AG
2018-08-01
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| Series: | Molecules |
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| author | Khadar Duale Magdalena Zięba Paweł Chaber Dany Jeanne Di Fouque Antony Memboeuf Cristian Peptu Iza Radecka Marek Kowalczuk Grażyna Adamus |
| author_facet | Khadar Duale Magdalena Zięba Paweł Chaber Dany Jeanne Di Fouque Antony Memboeuf Cristian Peptu Iza Radecka Marek Kowalczuk Grażyna Adamus |
| author_sort | Khadar Duale |
| collection | DOAJ |
| description | In this study, low molecular weight poly(δ-valerolactone) (PVL) was synthesized through bulk-ring openings polymerization of δ-valerolactone with boric acid (B(OH)3) as a catalyst and benzyl alcohol (BnOH) as an initiator. The resulting homopolymer was characterized with the aid of nuclear magnetic resonance (NMR) and mass spectrometry (MS) techniques to gain further understanding of its molecular structure. The electrospray ionization mass spectrometry (ESI-MS) spectra of poly(δ-valerolactone) showed the presence of two types of homopolyester chains—one terminated by benzyl ester and hydroxyl end groups and one with carboxyl and hydroxyl end groups. Additionally, a small amount of cyclic PVL oligomers was identified. To confirm the structure of PVL oligomers obtained, fragmentation of sodium adducts of individual polyester molecules terminated by various end groups was explored in ESI-MSn by using collision induced dissociation (CID) techniques. The ESI-MSn analyses were conducted both in positive- and negative ion mode. The comparison of the fragmentation spectra obtained with proposed respective theoretical fragmentation pathways allowed the structure of the obtained oligomers to be established at the molecular level. Additionally, using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), it was proven that regardless of the degree of oligomerization, the resulting PVL samples were a mixture of two types of linear PVL oligomers differing in end groups and containing just a small amount of cyclic oligomers that tended to be not visible at higher molar masses. |
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| publishDate | 2018-08-01 |
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| series | Molecules |
| spelling | doaj.art-820b9f27c1d74f34bba94668f13eeedd2022-12-21T23:01:36ZengMDPI AGMolecules1420-30492018-08-01238203410.3390/molecules23082034molecules23082034Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric AcidKhadar Duale0Magdalena Zięba1Paweł Chaber2Dany Jeanne Di Fouque3Antony Memboeuf4Cristian Peptu5Iza Radecka6Marek Kowalczuk7Grażyna Adamus8Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, M. Curie-Sklodowska St., 41-819 Zabrze, PolandCentre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, M. Curie-Sklodowska St., 41-819 Zabrze, PolandCentre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, M. Curie-Sklodowska St., 41-819 Zabrze, PolandCEMCA, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, 29238 Brest CEDEX 3, FranceCEMCA, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, 29238 Brest CEDEX 3, FrancePolymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845-41 Bratislava 45, SlovakiaSchool of Biology, Chemistry and Forensic Science, Faculty of Science and Engineering, University of Wolverhampton, Wolverhampton WV1 1SB, UKCentre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, M. Curie-Sklodowska St., 41-819 Zabrze, PolandCentre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, M. Curie-Sklodowska St., 41-819 Zabrze, PolandIn this study, low molecular weight poly(δ-valerolactone) (PVL) was synthesized through bulk-ring openings polymerization of δ-valerolactone with boric acid (B(OH)3) as a catalyst and benzyl alcohol (BnOH) as an initiator. The resulting homopolymer was characterized with the aid of nuclear magnetic resonance (NMR) and mass spectrometry (MS) techniques to gain further understanding of its molecular structure. The electrospray ionization mass spectrometry (ESI-MS) spectra of poly(δ-valerolactone) showed the presence of two types of homopolyester chains—one terminated by benzyl ester and hydroxyl end groups and one with carboxyl and hydroxyl end groups. Additionally, a small amount of cyclic PVL oligomers was identified. To confirm the structure of PVL oligomers obtained, fragmentation of sodium adducts of individual polyester molecules terminated by various end groups was explored in ESI-MSn by using collision induced dissociation (CID) techniques. The ESI-MSn analyses were conducted both in positive- and negative ion mode. The comparison of the fragmentation spectra obtained with proposed respective theoretical fragmentation pathways allowed the structure of the obtained oligomers to be established at the molecular level. Additionally, using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), it was proven that regardless of the degree of oligomerization, the resulting PVL samples were a mixture of two types of linear PVL oligomers differing in end groups and containing just a small amount of cyclic oligomers that tended to be not visible at higher molar masses.http://www.mdpi.com/1420-3049/23/8/2034Poly(delta-valerolactone)delta-valerolactonespectrometrybiodegradable polymersmetal free catalystMALDIESI-MSring-openings polymerizations (ROP)biocatalystbiodegradable aliphatic polyestersMS/MS studies |
| spellingShingle | Khadar Duale Magdalena Zięba Paweł Chaber Dany Jeanne Di Fouque Antony Memboeuf Cristian Peptu Iza Radecka Marek Kowalczuk Grażyna Adamus Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid Molecules Poly(delta-valerolactone) delta-valerolactone spectrometry biodegradable polymers metal free catalyst MALDI ESI-MS ring-openings polymerizations (ROP) biocatalyst biodegradable aliphatic polyesters MS/MS studies |
| title | Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid |
| title_full | Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid |
| title_fullStr | Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid |
| title_full_unstemmed | Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid |
| title_short | Molecular Level Structure of Biodegradable Poly(Delta-Valerolactone) Obtained in the Presence of Boric Acid |
| title_sort | molecular level structure of biodegradable poly delta valerolactone obtained in the presence of boric acid |
| topic | Poly(delta-valerolactone) delta-valerolactone spectrometry biodegradable polymers metal free catalyst MALDI ESI-MS ring-openings polymerizations (ROP) biocatalyst biodegradable aliphatic polyesters MS/MS studies |
| url | http://www.mdpi.com/1420-3049/23/8/2034 |
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