Molecular Imaging Center, Key Laboratory of Nuclear Medicine, Ministry of Health, Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine , Wuxi 214063 , People's Republic of China.
Biomacromolecules. 2019 Mar 11;20(3):1455-1463. doi: 10.1021/acs.biomac.9b00051. Epub 2019 Feb 21.
Nonconjugated red fluorescent polymers have been increasingly studied to improve the biocompatibility and penetration depth over conventional fluorescent materials. However, the accessibility of such polymers remains challenging due to the scarcity of nonconjugated fluorophores and lacking relevant mechanism of red-shifted fluorescence. Herein, we discovered that the combination of hydrogen bonding and π-π stacking interactions provides nonconjugated poly(amide-imide) with a large bathochromic shift (>100 nm) from blue-green fluorescence to red emission. The amphiphilic PEGylated poly(amide-imide) derived from in situ PEGylation self-assembled into nanovesicles in water, which isolated the aminosuccinimide fluorophore from the solvents and suppressed the hydrogen bonds formation between aminosuccinimide fluorophores and water. Therefore, the fluorescence of PEGylated poly(amide-imide) in water was soundly retained. Furthermore, the strong hydrogen bonding and hydrophobic interactions with water provided PEGylated poly(amide-imide) with a reversible thermoresponsiveness and presented a concentration-dependent behavior. Finally, accompanied by the excellent biostability and photostability, PEGylated poly(amide-imide) exhibited as a good candidate for cell imaging.
非共轭红色荧光聚合物已被广泛研究,以提高传统荧光材料的生物相容性和穿透深度。然而,由于非共轭荧光团的稀缺性和缺乏相关的红移荧光机制,此类聚合物的可及性仍然具有挑战性。在此,我们发现氢键和π-π堆积相互作用的结合为非共轭聚(酰胺-酰亚胺)提供了从蓝绿光荧光到红光发射的大红移 (>100nm)。由原位 PEG 化衍生的两亲性 PEG 化聚(酰胺-酰亚胺)在水中自组装成纳米囊泡,将氨甲酰亚胺荧光团与溶剂隔离,并抑制氨甲酰亚胺荧光团与水之间氢键的形成。因此,PEG 化聚(酰胺-酰亚胺)在水中的荧光得到了很好的保留。此外,与水的强氢键和疏水相互作用使 PEG 化聚(酰胺-酰亚胺)具有可逆的温敏性,并呈现出浓度依赖性行为。最后,伴随着出色的生物稳定性和光稳定性,PEG 化聚(酰胺-酰亚胺)表现出作为细胞成像的良好候选物。