Polymer Brushes via Surface-Initiated Electrochemically Mediated ATRP: Role of a Sacrificial Initiator in Polymerization of Acrylates on Silicon Substrates

Abstract

Silicon wafers as semiconductors are essential components of integrated circuits in electronic devices. For this reason, modification of the silicon surface is an important factor in the manufacturing of new hybrid materials applied in micro- and nanoelectronics. Herein, copolymer brushes of hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) and hydrophobic poly(tert-butyl acrylate) (PtBA) were grafted from silicon wafers via simplified electrochemically mediated atom transfer radical polymerization (seATRP) according to a surface-initiated approach. The syntheses of PHEA-b-PtBA copolymers were carried out with diminished catalytic complex concentration (successively 25 and 6 ppm of Cu). In order to optimize the reaction condition, the effect of the addition of a supporting electrolyte was investigated. A controlled increase in PHEA brush thickness was confirmed by atomic force microscopy (AFM). Various other parameters including contact angles and free surface energy (FSE) for the modified silicon wafer were presented. Furthermore, the effect of the presence of a sacrificial initiator in solution on the thickness of the grafted brushes was reported. Successfully fabricated inorganic–organic hybrid nanomaterials show potential application in biomedicine and microelectronics devices, e.g., biosensors.

A New Protocol for Ash Wood Modification: Synthesis of Hydrophobic and Antibacterial Brushes from the Wood Surface

“…Ag 0 wire (99.9%, Alfa Aesar, Kandel, Germany) was purified with an aqueous solution of NaCl at 95 • C and washed with acetone. Brominated silicon wafers were synthesized according to previously reported procedure [66]. Bacterial representative strains, media, and culture conditions: Escherichia coli ATCC 10536 (E. coli) and Staphylococcus aureus ATCC 6538 (S. aureus) were used as a part of collection of Department of Biotechnology and Bioinformatics, Faculty of Chemistry, Rzeszow University of Technology, Poland.…”

Red is the new green: Dry wine‐based miniemulsion as eco‐friendly reaction medium for sustainable atom transfer radical polymerization

“…Reversible deactivation radical polymerization (RDRP) techniques, which include atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain‐transfer (RAFT) polymerization, and nitroxide‐mediated polymerization (NMP) are powerful tools for the synthesis of macromolecules with complex architectures and predefined properties 1 . The key feature of RDRP techniques include the ability to polymerize a wide spectrum of monomers in a whole range of reaction media, for example, untreated water, 2 organic solvents, 3 ionic liquids 4 or heterogenous media 5 . Naturally, the development of RDRP techniques is accompanied by the implementation of sustainability and green chemistry into the polymerization procedures.…”

Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures

“…Classical SI-ATRP requires the utilization of high amounts of copper-based catalyst, which is unfavorable in the case of biomedical and electronic applications of the brushes. In response to that, many researchers have moved their attention to SI-ATRP with a ppm concentration of copper catalyst [8,9] or SI-ATRP catalyzed by less harmful metal catalysts [10]. Moreover, recent progress in SI-RDRPs resulted in the development of photoinduced SI-ATRP, which may not only use low concentrations of metal-based catalyst [11,12] but also enables polymer brush synthesis using microliter volumes of reaction Polymers 2021, 13, 4458 2 of 16 mixture [13].…”