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ESI-MS reveals the influence of hydrophilicity and architecture on the water-soluble degradation product patterns of biodegradable homo- and copolyesters of 1,5-dioxepan-2-one and epsilon-caprolactone
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-7790-8987
Centre of Polymer and Carbon Materials, Polish Academy of Sciences.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
Centre of Polymer and Carbon Materials, Polish Academy of Sciences.
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2008 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 41, no 10, 3547-3554 p.Article in journal (Refereed) Published
Abstract [en]

The hydrolytic degradation process and degradation product patterns of biodegradable homo- and copolyesters of 1,5-dioxepan-2-one (DXO) and epsilon-caprolactone (CL) were monitored by electrospray ionization mass spectrometry (ESI-MS). The degradation product patterns were compared to mass loss, molecular weight changes, copolymer composition, and pH changes after various hydrolysis times. Water-soluble oligomers up to heptadecamer were identified after hydrolysis of hydrophilic PDXO, while only oligomers up to hexamer were detected after hydrolysis of the more hydrophobic PCL. The product pattern of DXO-CL-DXO triblock copolymer mainly consisted of DXO-based oligomers, whereas the CL/DXO multiblock copolymer degradation product pattern contained DXO and CL oligomers as well as oligomers containing both DXO and CL units. The DXO-rich oligomers, however, dominated the product patterns. ESI-MS gave valuable insights into the hydrolysis process of hydrophobic and hydrophilic polyesters and showed that hydrophilicity of the polymer as well as copolymer architecture both greatly influenced the water-soluble degradation product patterns.

Place, publisher, year, edition, pages
2008. Vol. 41, no 10, 3547-3554 p.
Keyword [en]
ring-opening polymerization, molecular-weight products, mass-spectrometry, copolymers, polyesters, oligomers, acids
National Category
Polymer Chemistry Polymer Technologies
URN: urn:nbn:se:kth:diva-17545DOI: 10.1021/ma800365mISI: 000256058000025ScopusID: 2-s2.0-45749126984OAI: diva2:335589

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-05-30Bibliographically approved
In thesis
1. Controlled Degradation of Polyester-Ethers Revealed by Mass Spectrometry Techniques
Open this publication in new window or tab >>Controlled Degradation of Polyester-Ethers Revealed by Mass Spectrometry Techniques
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The use of degradable biomedical materials in e.g. tissue engineering and controlled drug delivery has changed medical science during recent decades. The key question is to adapt the material with respect to mechanical properties, surface characteristics, and degradation profile to suit its intended application. Products formed during the degradation of bioresorbable materials are generally considered non-toxic and they are excreted from the human body. However, large amounts of specific degradation products such as hydroxyacids and oligomers may induce a pH decrease and a subsequent inflammatory response at the implantation site.


In this study, macromolecular design and a combination of cross-linking and adjusted hydrophilicity are utilized as tools to control and tailor the degradation rate and the subsequent release of degradation products from polyester-ethers. A series of different homo- and copolymers of e-caprolactone (CL) and 1,5-dioxepan-2-one (DXO) were synthesized and their hydrolytic degradation was monitored in aqueous media at 37 °C for up to 546 days. The low and medium molar mass degradation products released during hydrolysis were monitored by various mass spectrometry techniques. The materials studied included linear DXO/CL triblock and multiblock copolymers, PCL and PDXO linear homopolymers, and cross-linked homo- and random copolymers of CL/DXO where 2,2’-bis-(ε-caprolactone-4-yl) propane (BCP) was used as a cross-linking agent.


The results show that macromolecular engineering and controlled hydrophilicity of cross-linked networks are useful tools for customizing the release rate of acidic degradation products. Thereby, the formation of local acidic environments is prevented and the risk of inflammatory responses in the body is reduced.

Abstract [sv]

Läkarvetenskapen har under de senaste årtiondena förändrats genom användandet av nedbrytbara biomedicinska material inom t.ex. vävnadsersättning och kontrollerad läkemedelsfrisättning. Nyckeln är att anpassa materialets mekaniska egenskaper, ytegenskaper och nedbrytningsprofil för den tilltänkta tillämpningen. Produkterna som bildas under nedbrytningen av bioresorberbara material anses generellt vara icke-toxiska och utsöndras ur människokroppen, men stora mängder specifika nedbrytningsprodukter som t.ex. hydroxysyror kan orsaka en pH-sänkning och därmed en inflammatorisk reaktion vid implantationsplatsen.


I detta arbete används makromolekylär design och en kombination av tvärbindning och anpassad hydrofilicitet som verktyg för att kontrollera och skräddarsy nedbrytningshastigheten och den efterföljande frisättningen av nedbrytningsprodukter från polyester-etrar. En serie av olika homo- och sampolymerer av e-kaprolakton (CL) och 1,5-dioxepan-2-on (DXO) syntetiserades och deras hydrolytiska nedbrytning studerades i vattenlösning vid 37 °C i upp till 546 dagar. De låg- och medelmolekylära nedbrytningsprodukterna som frisattes under hydrolysen analyserades med olika masspektrometritekniker. Materialen som undersöktes inkluderade linjära DXO/CL triblock- och multiblocksampolymerer, linjära PCL och PDXO homopolymerer, samt tvärbundna homo- och slumpvisa sampolymerer av CL och DXO där 2,2’-bis(e-kaprolakton-4-yl)propan (BCP) användes som tvärbindare.


Resultaten visar att makromolekylär design och tvärbundna nätverk med kontrollerad hydrofilicitet är användbara verktyg för att skräddarsy frisättningshastigheten av sura nedbrytningsprodukter. Därmed kan bildandet av lokalt sura miljöer förhindras och risken för inflammatoriska reaktioner i kroppen minskas.


Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 59 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2008:57
Degradation products, biocompatibility, -caprolactone, 1, 5-dioxepan-2-one, 6-hydroxyhexanoic acid, 3-(2-hydroxyethoxy)propanoic acid, oligomers
National Category
Polymer Chemistry
urn:nbn:se:kth:diva-4898 (URN)978-91-7415-098-8 (ISBN)
Public defence
2008-09-26, F3, KTH, Lindstedtsvägen 26, Stockholm, 10:00 (English)
QC 20100812Available from: 2008-09-17 Created: 2008-09-17 Last updated: 2010-08-12Bibliographically approved

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