Homopolymer nanobowls with a controlled size and denting degree. Issue 9 (2nd February 2022)

• Record Type: Journal Article
• Authors: Wu, Tong; Sun, Hui; Jiang, Jinhui; Lin, Sha; Fan, Liujie; Hong, Kai; Sun, Qingmei; Hu, Yong; Zhu, Yunqing; Du, Jianzhong
• Is Part Of: Polymer chemistry. Volume 13:Issue 9(2022)
• Page Start: 1236
• Page End: 1242
• Publication Date: 2022-02-02
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/d1py01613j
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : The homopolymer poly( N -([2, 2′-bipyridyl]-4-yl)acrylamide) (PBPy) can self-assemble into nanobowls with a controlled size and denting degree under different conditions. Abstract : Homopolymer nanobowls hold promising potential applications in many fields because of their designability, large specific surface area and high packing density. However, it is still challenging to prepare nanobowls with a controlled size (diameter D ) and denting degree (including relative opening width W / D and relative concave depth H / D ). Herein, we propose a strategy for preparing such nanobowls with controlled D, W / D, and H / D values by self-assembly of a homopolymer, poly( N -([2, 2′-bipyridyl]-4-yl)acrylamide) (PBPy), that was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. In the homopolymer PBPy, the bipyridine (BPy) pendants are functional moieties that exhibit intramolecular π–π stacking and hydrogen bonding, as well as coordination with Fe 2+ ions. To control the size and denting degree of nanobowls, the initial concentration of PBPy ( C ini ), self-assembly temperature ( T s ), solution pH, and molar ratio of Fe 2+ to BPy were tuned. It was confirmed that relatively uniform nanobowls can be prepared at a C ini of 0.2 mg mL −1 because of moderate π–π stacking and hydrogen bonding interactions. D and W / D increase with T s as it affects the intermolecular interactions. H / D increases but W / D decreases with the hydrophilicity of PBPy and hydrogen bonding that can be promoted by decreasing the solution pH. Additionally, Fe 2+ ions are added to manipulate the denting degree more effectively than pH, as they can coordinate with BPy moieties and water to form [Fe(BPy) x (H2 O) y ] 2+ (0 ≤ x + y ≤ 6). This not only causes additional coordination among polymer chains but also enhances the hydrophilicity of PBPy and hydrogen bonding interactions. Overall, this study provides fresh insights for preparing nanobowls with a controlled size and denting degree.