Synthesis of dual-functional poly(6-azidohexylmethacrylate) brushes by a RAFT agent carrying carboxylic acid end groups

Abstract

Novel types of dual‐functional surface‐attached polymer brushes were developed by interface‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization of 6‐azidohexylmethacrylate using the surface‐immobilized RAFT agent and the free initiator. The interface‐mediated RAFT polymerization produced silicon substrate coated with dual‐functional (azido groups from monomer and carboxylic acid groups from RAFT agent) poly(6‐azidohexylmethacrylate) [poly (AHMA)] with a grafting density as high as 0.59 chains/nm2. Dual‐functional polymer brushes can represent an attractive chemical platform to deliberately introduce other molecular units at specific sites. The azido groups of the poly(AHMA) brushes can be modified with alkyl groups via click reaction, known for their DNA hybridization, while the carboxylic acid end groups can be reacted with amine groups via amide reaction, known for their antifouling properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1696–1706

Micro-patterned polymer brushes by a combination of photolithography and interface-mediated RAFT polymerization for DNA hybridization

“…21 Briefly, t-BOC protected AUD molecules were coupled to the Si-H surface by using UV radiation. The RAFT agent immobilization on the Si-H surface was carried out according to our previously reported method.…”

“…21 Briefly, the silicon wafers were sliced into rectangular strips of about 1 cm × 2 cm. 21 Briefly, the silicon wafers were sliced into rectangular strips of about 1 cm × 2 cm.…”

“…21 In the first step of production, 6-azido-1hexanol was acquired via the reaction of 6-chloro-1-hexanol (0.7 g, 5.12 mmol) and NaN 3 (3.9 g, 60 mmol) at 110°C for 72 h. In the second step, 6-azido-1-hexanol (1.0 g, 6.98 mmol) was reacted with methacryloyl chloride (1.05 g, 10.04 mmol) at 0°C for 2.5 h. AHMA was kept at 4°C until it was used for the polymerization step. 21 In the first step of production, 6-azido-1hexanol was acquired via the reaction of 6-chloro-1-hexanol (0.7 g, 5.12 mmol) and NaN 3 (3.9 g, 60 mmol) at 110°C for 72 h. In the second step, 6-azido-1-hexanol (1.0 g, 6.98 mmol) was reacted with methacryloyl chloride (1.05 g, 10.04 mmol) at 0°C for 2.5 h. AHMA was kept at 4°C until it was used for the polymerization step.…”

“…21 In a typical reaction, the micro-patterned Si-TTC5 substrate, the solvent THF (10 mL), the initiator AIBN (3.0 mg, 0.018 mmol), the free RAFT agent TTC5 (76.2 mg, 0.3 mmol), and the monomer AHMA (1.2 g, 5.99 mmol) were placed in a Schlenk flask (25 mL) under an argon atmosphere. 21 In a typical reaction, the micro-patterned Si-TTC5 substrate, the solvent THF (10 mL), the initiator AIBN (3.0 mg, 0.018 mmol), the free RAFT agent TTC5 (76.2 mg, 0.3 mmol), and the monomer AHMA (1.2 g, 5.99 mmol) were placed in a Schlenk flask (25 mL) under an argon atmosphere.…”

Glycopolymer brushes with specific protein recognition property

“…AIBN (Acros, Geel, Belgium, 98%) was crystallized from methanol twice and stored at −20 °C. t ‐BOC protected 1‐amino‐10‐undecene ( t ‐BOC‐AUD), BSPA (Supporting Information Scheme S1, Figures S1 and S2), and PFA (Supporting Information Scheme S2 and Figures S3–S5) were synthesized as described in the literature.…”