Light-controlled enzymatic synthesis of γ-CD using a recyclable azobenzene template.

Autor:	Sørensen J; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk., Hansen EL; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk., Larsen D; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk., Elmquist MA; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk., Buchleithner A; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk., Florean L; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk., Beeren SR; Department of Chemistry, Technical University of Denmark Kemitorvet Building 207 Kongens Lyngby 2800 Denmark sopbee@kemi.dtu.dk.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2023 Jun 29; Vol. 14 (28), pp. 7725-7732. Date of Electronic Publication: 2023 Jun 29 (Print Publication: 2023).
DOI:	10.1039/d3sc01997g
Abstrakt:	Cyclodextrins (CDs) are important molecular hosts for hydrophobic guests in water and extensively employed in the pharmaceutical, food and cosmetic industries to encapsulate drugs, flavours and aromas. Compared with α- and β-CD, the wide-scale use of γ-CD is currently limited due to costly production processes. We show how the yield of γ-CD in the enzymatic synthesis of CDs can be increased 5-fold by adding a tetra- ortho -isopropoxy-substituted azobenzene template irradiated at 625 nm (to obtain the cis -( Z )-isomer) to direct the synthesis. Following the enzymatic reaction, the template can then be readily recovered from the product mixture for use in subsequent reaction cycles. Heating induces thermal cis -( Z ) to trans -( E ) relaxation and consequent dissociation from γ-CD whereupon the template can then be precipitated by acidification. For this study we designed and synthesised a set of three water-soluble azobenzene templates with different ortho -substituents and characterised their photoswitching behaviour using UV/vis and NMR spectroscopy. The templates were tested in cyclodextrin glucanotransferase-mediated dynamic combinatorial libraries (DCLs) of cyclodextrins while irradiating at different wavelengths to control the cis / trans ratios. To rationalise the behaviour of the DCLs, NMR titrations were carried out to investigate the binding interactions between α-, β- and γ-CD and the cis and trans isomers of each template. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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