Details
| Original language | English |
|---|---|
| Pages (from-to) | 3446-3452 |
| Number of pages | 7 |
| Journal | CHEMCATCHEM |
| Volume | 8 |
| Issue number | 22 |
| Early online date | 31 Aug 2016 |
| Publication status | Published - 23 Nov 2016 |
| Externally published | Yes |
Abstract
A three-step enzymatic reaction sequence for the synthesis of poly-ϵ-caprolactone (PCL) was designed running in a fed-batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone and further oxidation to ϵ-caprolactone (ECL) by means of a Baeyer–Villiger monooxygenase. As a third step, lipase-catalyzed hydrolysis of the lactone to 6-hydroxyhexanoic acid (6-HHA) was designed. With this biocatalytic multistep process reported herein, severe substrate surplus and product inhibition could be circumvented by the fed-batch operation by adding the cyclohexanol substrate and by in situ product removal of ECL by hydrolysis, respectively. Up to 283 mm product concentration of 6-HHA was reached in the fed-batch operated process without loss in productivity within 20 h. After extraction and subsequent polymerization catalyzed by Candida antarctica lipase B, analysis of the unfractionated polymer revealed a bimodal distribution of the polymer population, which reached a mass average molar mass (Mw) value of approximately 63 000 g mol−1 and a dispersity (Mw/Mn) of 1.1 for the higher molecular weight population, which thus revealed an alternative route to the conventional synthesis of PCL.
Keywords
- enzymatic cascade, enzymes, oxidoreductases, polymerization, ϵ-caprolactone
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
- Chemistry(all)
- Inorganic Chemistry
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In: CHEMCATCHEM, Vol. 8, No. 22, 23.11.2016, p. 3446-3452.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - A Fed-Batch Synthetic Strategy for a Three-Step Enzymatic Synthesis of Poly-ϵ-caprolactone
AU - Scherkus, Christian
AU - Schmidt, Sandy
AU - Bornscheuer, Uwe T.
AU - Gröger, Harald
AU - Kara, Selin
AU - Liese, Andreas
PY - 2016/11/23
Y1 - 2016/11/23
N2 - A three-step enzymatic reaction sequence for the synthesis of poly-ϵ-caprolactone (PCL) was designed running in a fed-batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone and further oxidation to ϵ-caprolactone (ECL) by means of a Baeyer–Villiger monooxygenase. As a third step, lipase-catalyzed hydrolysis of the lactone to 6-hydroxyhexanoic acid (6-HHA) was designed. With this biocatalytic multistep process reported herein, severe substrate surplus and product inhibition could be circumvented by the fed-batch operation by adding the cyclohexanol substrate and by in situ product removal of ECL by hydrolysis, respectively. Up to 283 mm product concentration of 6-HHA was reached in the fed-batch operated process without loss in productivity within 20 h. After extraction and subsequent polymerization catalyzed by Candida antarctica lipase B, analysis of the unfractionated polymer revealed a bimodal distribution of the polymer population, which reached a mass average molar mass (Mw) value of approximately 63 000 g mol−1 and a dispersity (Mw/Mn) of 1.1 for the higher molecular weight population, which thus revealed an alternative route to the conventional synthesis of PCL.
AB - A three-step enzymatic reaction sequence for the synthesis of poly-ϵ-caprolactone (PCL) was designed running in a fed-batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone and further oxidation to ϵ-caprolactone (ECL) by means of a Baeyer–Villiger monooxygenase. As a third step, lipase-catalyzed hydrolysis of the lactone to 6-hydroxyhexanoic acid (6-HHA) was designed. With this biocatalytic multistep process reported herein, severe substrate surplus and product inhibition could be circumvented by the fed-batch operation by adding the cyclohexanol substrate and by in situ product removal of ECL by hydrolysis, respectively. Up to 283 mm product concentration of 6-HHA was reached in the fed-batch operated process without loss in productivity within 20 h. After extraction and subsequent polymerization catalyzed by Candida antarctica lipase B, analysis of the unfractionated polymer revealed a bimodal distribution of the polymer population, which reached a mass average molar mass (Mw) value of approximately 63 000 g mol−1 and a dispersity (Mw/Mn) of 1.1 for the higher molecular weight population, which thus revealed an alternative route to the conventional synthesis of PCL.
KW - enzymatic cascade
KW - enzymes
KW - oxidoreductases
KW - polymerization
KW - ϵ-caprolactone
UR - http://www.scopus.com/inward/record.url?scp=85027956629&partnerID=8YFLogxK
U2 - 10.1002/cctc.201600806
DO - 10.1002/cctc.201600806
M3 - Article
AN - SCOPUS:85027956629
VL - 8
SP - 3446
EP - 3452
JO - CHEMCATCHEM
JF - CHEMCATCHEM
SN - 1867-3880
IS - 22
ER -