| 1. |
- Colak, Burcu, et al.
(author)
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Impact of the Molecular Environment on Thiol-Ene Coupling For Biofunctionalization and Conjugation
- 2016
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In: Bioconjugate chemistry. - : American Chemical Society (ACS). - 1043-1802 .- 1520-4812. ; 27:9, s. 2111-2123
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Journal article (peer-reviewed)abstract
- Thiol-ene radical coupling is increasingly used for the biofunctionalization of biomaterials and the formation of 3D hydrogels enabling cell encapsulation. Indeed, thiol-ene chemistry presents interesting features that are particularly attractive for platforms requiring specific reactions of peptides or proteins, in particular, in situ, during cell culture or encapsulation. Despite such interest, little is known about the factors impacting thiol-ene chemistry in situ, under biologically relevant conditions. Here we explore some of the molecular parameters controlling photoinitiated thiol-ene couplings with a series of alkenes and thiols, including peptides, in buffered conditions. H-1 NMR and HPLC were used to quantify the efficiency of couplings and the impact of the pH of the buffer, as well as the molecular structure and local microenvironment close to alkenes and thiols to be coupled. Some of these observations are supported by molecular dynamics and quantum mechanics calculations. An important finding of our work is that the plc of thiols (and its variation upon changes in molecular structure) have a striking impact on coupling efficiencies. Similarly, positively charged and aromatic amino acids are found to have some impact on thiol-ene couplings. Hence, our study demonstrates that molecular design should be carefully selected in order to achieve high biofunctionalization levels in biomaterials with peptides or promote the efficient formation of peptide-based hydrogels.
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| 2. |
- Tan, Khooi Y., et al.
(author)
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Study of thiol-ene chemistry on polymer brushes and application to surface patterning and protein adsorption
- 2016
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In: Polymer Chemistry. - 1759-9954 .- 1759-9962. ; 7:4, s. 979-990
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Journal article (peer-reviewed)abstract
- Polymer brushes are attractive polymeric coatings for biomedical applications such as tissue engineering, biosensor design and the purification of biological samples. In order to confer bioactivity to these coatings, their functionalisation with biomolecules, proteins and peptides, is required. In this respect, thiol-ene coupling offers interesting features as it is regioselective, efficient and can be controlled by photo-irradiation to allow surface patterning. The efficiency of thiol-ene and the related thiol-yne couplings to poly(glycidyl methacrylate) brushes was quantified. The impact of the structure of thiols to be tethered and reaction conditions on the brush loading and the kinetics of reaction were investigated. Thiol-ene reactions were then used to pattern brushes via direct irradiation through a mask or via reactive micro-contact printing. The resulting patterns were used to control albumin adsorption and the formation of protein patterns.
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