TEMPO driven thiol–ene reaction for the preparation of polymer functionalized silicon wafers
- 12 April 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in New Journal of Chemistry
- Vol. 45 (20), 9118-9129
- https://doi.org/10.1039/d1nj00561h
Abstract
TEMPO driven thiol–ene reaction was utilized to prepare silicon (Si) wafers modified with a variety of polymer brushes, such as poly(N-isopropyl acrylamide), polystyrene, poly(isobornyl acrylate), poly(acrylic acid), and functionalized cysteine. In order to confirm the functionalization of Si wafers using TEMPO driven thiol–ene reaction, initially model reactions were performed between 3-mercaptopropyltriethoxysilane with various enes such as n-butyl acrylate, N,N′-dimethylacrylamide, divinyl sulfone, 1-dodecene, and vinyltriethoxysilane. The model reactions exhibited quantitative conversion under methanol, tetrahydrofuran, and chloroform at 35 °C. For polymer functionalization of Si wafers, thiol and ene functionalized polymers have been prepared by reversible addition fragmentation chain-transfer (RAFT) and high-temperature polymerization. The synthesized thiol and ene functionalized polymers were characterized using 1H NMR spectroscopy, UV-visible spectroscopy, size exclusion chromatography (SEC), dynamic light scattering, and zeta potential analysis. The ene functionalized monomers, for example, cysteine functionalized with ene (Cys-Ene) and 3-mercapopropyltriethoxysilane functionalized with ene (MPTES-Ene) were prepared by the reaction between cysteine/3-mercaptopropyltriethoxysilane with 1,4-bis(acryloyloxy)butane under mild reaction conditions again through thiol–ene chemistry initiated by TEMPO at 35 °C for 16 h. The synthesized Cys-Ene and MPTES-Ene have been characterized by 1H and 13C NMR spectroscopy. Furthermore, thiol/ene-functionalized Si wafers (Si–SH/Si–Ene) were prepared using thiol (MPTES) and ene (MPTES-Ene) functionalized silanizing agents. Finally, thiol/ene functionalized polymers and ene functionalized cysteine were conjugated on thiol/ene functionalized Si wafers under mild reaction conditions. The polymer/cysteine functionalized Si wafers have been characterized through contact angle measurement, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The antifouling characteristic of Si wafer functionalized with cysteine was studied using fluorescence microscopy after treatment with albumin–fluorescein isothiocyanate conjugate.Keywords
Funding Information
- Science and Engineering Research Board (SB/S3/CE/061/2015)
This publication has 54 references indexed in Scilit:
- Biocompatible and Bioactive Surface Modifications for Prolonged In Vivo EfficacyChemical Reviews, 2011
- Biofunctionalization on Alkylated Silicon Substrate Surfaces via “Click” ChemistryJournal of the American Chemical Society, 2010
- Ultralow‐Fouling, Functionalizable, and Hydrolyzable Zwitterionic Materials and Their Derivatives for Biological ApplicationsAdvanced Materials, 2010
- Thiol–Ene Click ChemistryAngewandte Chemie, 2010
- Emerging applications of stimuli-responsive polymer materialsNature Materials, 2010
- Thiol−Ene Reaction for the Synthesis of Multifunctional Branched OrganosilanesOrganometallics, 2008
- Enhanced reactivity of monovinyl acrylates characterized by secondary functionalities toward photopolymerization and Michael addition: Contribution of intramolecular effectsJournal of Polymer Science Part A: Polymer Chemistry, 2008
- Robust, Efficient, and Orthogonal Synthesis of Dendrimers via Thiol-ene “Click” ChemistryJournal of the American Chemical Society, 2008
- Synthesis and characterization of well-defined polymer brushes grafted from silicon surface via surface reversible addition–fragmentation chain transfer (RAFT) polymerizationMaterials Letters, 2007
- Reversible conformational behavior of poly(acrylic acid) LB film with changes in pH, ionic strength and timeColloids and Surfaces A: Physicochemical and Engineering Aspects, 2006