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Publications (7 of 7) Show all publications
Stamm, A., Biundo, A., Schmidt, B., Brücher, J., Lundmark, S., Olsén, P., . . . Syrén, P.-O. (2019). A retrobiosynthesis-based route to generate pinene-derived polyesters. ChemBioChem (Print), 20, 1664-1671
Open this publication in new window or tab >>A retrobiosynthesis-based route to generate pinene-derived polyesters
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2019 (English)In: ChemBioChem (Print), ISSN 1439-4227, E-ISSN 1439-7633, Vol. 20, p. 1664-1671Article in journal (Refereed) Published
Abstract [en]

Significantly increased production of biobased polymers is aprerequisite to replace petroleum-based materials towardsreaching a circular bioeconomy. However, many renewablebuilding blocks from wood and other plant material are notdirectly amenable for polymerization, due to their inert backbonesand/or lack of functional group compatibility with thedesired polymerization type. Based on a retro-biosyntheticanalysis of polyesters, a chemoenzymatic route from (@)-apinenetowards a verbanone-based lactone, which is furtherused in ring-opening polymerization, is presented. Generatedpinene-derived polyesters showed elevated degradation andglass transition temperatures, compared with poly(e-decalactone),which lacks a ring structure in its backbone. Semirationalenzyme engineering of the cyclohexanone monooxygenasefrom Acinetobacter calcoaceticus enabled the biosynthesis ofthe key lactone intermediate for the targeted polyester. As aproof of principle, one enzyme variant identified from screeningin a microtiter plate was used in biocatalytic upscaling,which afforded the bicyclic lactone in 39% conversion in shakeflask scale reactions.

National Category
Polymer Chemistry
Research subject
Biotechnology
Identifiers
urn:nbn:se:kth:diva-260797 (URN)10.1002/cbic.201900046 (DOI)000477916100008 ()2-s2.0-85066903140 (Scopus ID)
Note

QC 20191008

Available from: 2019-09-30 Created: 2019-09-30 Last updated: 2019-10-08Bibliographically approved
Farhat, W., Stamm, A., Robert-Monpate, M., Biundo, A. & Syrén, P.-O. (2019). Biocatalysis for terpene-based polymers. Zeitschrift für Naturforschung C - A Journal of Biosciences, 74(3-4), 90-99
Open this publication in new window or tab >>Biocatalysis for terpene-based polymers
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2019 (English)In: Zeitschrift für Naturforschung C - A Journal of Biosciences, ISSN 0939-5075, E-ISSN 1865-7125, Vol. 74, no 3-4, p. 90-99Article in journal (Refereed) Published
Abstract [en]

Accelerated generation of bio-based materials is vital to replace current synthetic polymers obtained from petroleum with more sustainable options. However, many building blocks available from renewable resources mainly contain unreactive carbon-carbon bonds, which obstructs their efficient polymerization. Herein, we highlight the potential of applying biocatalysis to afford tailored functionalization of the inert carbocyclic core of multicyclic terpenes toward advanced materials. As a showcase, we unlock the inherent monomer reactivity of norcamphor, a bicyclic ketone used as a monoterpene model system in this study, to afford polyesters with unprecedented backbones. The efficiencies of the chemical and enzymatic Baeyer-Villiger transformation in generating key lactone intermediates are compared. The concepts discussed herein are widely applicable for the valorization of terpenes and other cyclic building blocks using chemoenzymatic strategies.

Place, publisher, year, edition, pages
WALTER DE GRUYTER GMBH, 2019
Keywords
biocatalysis, biopolymers, oxidoreductases, polyesters, terpenes
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-246249 (URN)10.1515/znc-2018-0199 (DOI)000459670900006 ()30789828 (PubMedID)2-s2.0-85061735936 (Scopus ID)
Note

QC 20190402

Available from: 2019-04-02 Created: 2019-04-02 Last updated: 2019-04-04Bibliographically approved
Stamm, A., Tengdelius, M., Schmidt, B., Engström, J., Syrén, P.-O., Fogelström, L. & Malmström, E. (2019). Chemo- enzymatic pathways toward pinene- based renewable materials. Green Chemistry, 21(10), 2720-2731
Open this publication in new window or tab >>Chemo- enzymatic pathways toward pinene- based renewable materials
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2019 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 21, no 10, p. 2720-2731Article in journal (Refereed) Published
Abstract [en]

Sobrerol methacrylate (SobMA) was synthesized and subsequently polymerized using different chemical and enzymatic routes. Sobrerol was enzymatically converted from -pinene in a small model scale by a Cytochrome P450 mutant from Bacillus megaterium. Conversion of sobrerol into SobMA was performed using both classical ester synthesis, i.e., acid chloride-reactions in organic solvents, and a more green approach, the benign lipase catalysis. Sobrerol was successfully esterified, leaving the tertiary alcohol and ene to be used for further chemistry. SobMA was polymerized into PSobMA using different radical polymerization techniques, including free radical (FR), controlled procedures (Reversible Addition Fragmentation chain-Transfer polymerization, (RAFT) and Atom Transfer Radical Polymerization (ATRP)) as well as by enzyme catalysis (horseradish peroxidase-mediated free radical polymerization). The resulting polymers showed high glass-transition temperatures (T-g) around 150 degrees C, and a thermal degradation onset above 200 degrees C. It was demonstrated that the T-g could be tailored by copolymerizing SobMa with appropriate methacrylate monomers and that the Flory-Fox equation could be used to predict the T-g. The versatility of PSobMA was further demonstrated by forming crosslinked thin films, either using the ene'-functionality for photochemically initiated thiol-ene'-chemistry, or reacting the tertiary hydroxyl-group with hexamethoxymethylmelamine, as readily used for thermally curing coatings systems.

National Category
Polymer Technologies Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-252972 (URN)10.1039/c9gc00718k (DOI)000468627800016 ()2-s2.0-85066853137 (Scopus ID)
Note

QC 20190812

Available from: 2019-08-12 Created: 2019-08-12 Last updated: 2019-08-12Bibliographically approved
Fogelström, L., Stamm, A., Tengdelius, M., Syrén, P.-O. & Malmström, E. (2019). New chemo-enzymatic pathways for sustainable terpene-based polymeric materials. Paper presented at National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL. Abstracts of Papers of the American Chemical Society, 257
Open this publication in new window or tab >>New chemo-enzymatic pathways for sustainable terpene-based polymeric materials
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2019 (English)In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 257Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-257595 (URN)000478860502626 ()
Conference
National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL
Note

QC 20190919

Available from: 2019-09-19 Created: 2019-09-19 Last updated: 2019-09-19Bibliographically approved
Malmström, E., Fogelström, L., Stamm, A., Tengdelius, M., Biundo, A. & Syrén, P.-O. (2019). Sustainable terpene-based polymeric materials. Paper presented at 257th National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL. Abstracts of Papers of the American Chemical Society, 257
Open this publication in new window or tab >>Sustainable terpene-based polymeric materials
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2019 (English)In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 257Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-257660 (URN)000478861204618 ()
Conference
257th National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL
Note

QC 20190903

Available from: 2019-09-03 Created: 2019-09-03 Last updated: 2019-09-03Bibliographically approved
Stamm, A., Svendsen, A., Skjold-Jørgensen, J., Vissing, T., Berts, I. & Nylander, T. (2017). The Triolein/Aqueous Interface and Lipase Activity Studied by Spectroscopic Ellipsometry and Coarse Grained Simulations. Chemistry and Physics of Lipids
Open this publication in new window or tab >>The Triolein/Aqueous Interface and Lipase Activity Studied by Spectroscopic Ellipsometry and Coarse Grained Simulations
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2017 (English)In: Chemistry and Physics of Lipids, ISSN 0009-3084, E-ISSN 1873-2941Article in journal (Refereed) Published
Abstract [en]

In spite of the importance of the triglyceride aqueous interface for processes like emulsification, surfactant interactions and lipase activity, relatively little is known about this interface compared to that between alkanes and water. Here, the contact between triolein and water was investigated in terms of water inclusion in the oil phase and orientation of the molecules at the interface. Coarse grained models of triglycerides in contact with water were constructed and correlated with experimental results of the changes in thickness and refractive index, obtained using spectroscopic ellipsometry of spin-coated triolein films. The topography of the layer was revealed by atomic force microscopy. Dry triolein and triolein sample after equilibration with water was also compared structurally using small-angle X-ray scattering. Additionally, the kinetics of adsorption/activity of three different variants of the Thermomyces lanugimosus lipase (TLL) was investigated. The results show that uptake of water in the triolein phase leads to increase in thickness of the layer. The observed increase of thickness was further enhanced by an active lipase but reduced when an inactive mutant of the enzyme was applied.

Place, publisher, year, edition, pages
Elsevier, 2017
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-217367 (URN)10.1016/j.chemphyslip.2017.10.011 (DOI)
Note

QC 20171211

Available from: 2017-11-10 Created: 2017-11-10 Last updated: 2017-12-11Bibliographically approved
Engström, J., Stamm, A., Tengdelius, M., Syrén, P.-O., Fogelström, L. & Malmström, E.Cationic latexes of bio‐based hydrophobicmonomer Sobrerol methacrylate (SobMA).
Open this publication in new window or tab >>Cationic latexes of bio‐based hydrophobicmonomer Sobrerol methacrylate (SobMA)
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(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-241457 (URN)
Note

QC 20190123

Available from: 2019-01-22 Created: 2019-01-22 Last updated: 2019-01-23Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0001-8727-2102

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