Synthesis of a Thermal-Responsive Dual-Modal Supramolecular Probe for Magnetic Resonance Imaging and Fluorescence Imaging,Macromolecular Rapid Communications

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Synthesis of a Thermal-Responsive Dual-Modal Supramolecular Probe for Magnetic Resonance Imaging and Fluorescence Imaging
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2021-07-17 , DOI: 10.1002/marc.202100248
Mi Zhou ₁ , Li Li ₁ , Wensheng Xie ₂ , Zejian He ₁ , Jie Li ₁

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Dual-modal imaging can integrate the advantages of different imaging technologies, which could improve the accuracy and efficiency of clinical diagnosis. Herein, a novel amphiphilic thermal-responsive copolymer obtained from three types of monomers, N-isopropyl acrylamide, 2-(acetoacetoxy) ethyl methacrylate, and propargyl methacrylate, by RAFT copolymerization, is reported. It can be grafted with β-cyclodextrin and aggregation-induced emission (AIE) luminogens tetraphenylethylene by click chemistry and Biginelli reaction. The multifunctional supramolecular polymer (P4) can be constructed by host–guest inclusion between the copolymer and the Gd-based contrast agent (CA) modified by adamantane [Ad-(DOTA-Gd)]. And it can form vesicles with a bilayer structure in aqueous which will enhance the AIE and magnetic resonance imaging effects. As fluorescent thermometer, P4 can enter HeLa cells for intracellular fluorescence imaging (FI) and is sensitive to temperature with detection limit value of 1.5 °C. As magnetic resonance CA, P4 exhibits higher relaxation compared to Magnevist, which can prolong the circulation time in vivo. In addition, Gd³⁺ in the polymer can be quickly released from the body by disassembly that reduced the biological toxicity. This work introduces new synthetic ideas for dual-modal probe, which has great potential for clinical diagnostic applications in bioimaging.

中文翻译：

用于磁共振成像和荧光成像的热响应双模态超分子探针的合成

双模态成像可以综合不同成像技术的优点，提高临床诊断的准确性和效率。在此，报道了一种由N-异丙基丙烯酰胺、甲基丙烯酸 2-（乙酰乙酰氧基）乙酯和甲基丙烯酸炔丙酯三种单体通过 RAFT 共聚获得的新型两亲热响应共聚物。它可以通过点击化学和 Biginelli 反应与β-环糊精和聚集诱导发光 (AIE) 发光剂四苯基乙烯接枝。多功能超分子聚合物（P4) 可以通过共聚物和由金刚烷 [Ad-(DOTA-Gd)] 改性的基于 Gd 的造影剂 (CA) 之间的主客体包含来构建。并且它可以在水中形成具有双层结构的囊泡，这将增强AIE和磁共振成像效果。作为荧光温度计，P4可以进入HeLa细胞进行细胞内荧光成像（FI），对温度敏感，检测限为1.5°C。作为磁共振CA，P4与Magnevist相比表现出更高的弛豫，可以延长体内循环时间。此外，Gd ³⁺聚合物可以通过分解迅速从体内释放出来，降低了生物毒性。这项工作为双模态探针引入了新的合成思路，在生物成像的临床诊断应用中具有巨大的潜力。

更新日期：2021-08-20

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