Fluorescent metallacycle-cored polymers via covalent linkage and their use as contrast agents for cell imaging
Fluorescent metallacycle-cored polymers via covalent linkage and their use as contrast agents for cell imaging
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通过共价键连接的荧光金属环核聚合物及其作为细胞成像造影剂的用途
DOI：
10.1073/pnas.1612898113
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发表时间：
2016-09
影响因子：
11.1
通讯作者：
Peter J. Stanga
中科院分区：
文献类型：
--
作者：
Mingming Zhang;Shuya Li;Xuzhou Yan;Zhixuan Zhou;Manik Lal Saha;Yu-Cai Wang;Peter J. Stanga
荧光聚合物具有亮度高、对微环境不敏感、生物相容性好等优点，在生物成像中发挥着重要作用。在这篇文章中，我们使用四亚苯基（TPE）衍生物，在聚集状态下作为荧光团，并通过共价键的TPE为基础的菱形Pt（II）金属杂环合成荧光聚合物。由于单体的共价键诱导聚集、TPE衍生物的聚集诱导发射特性以及基于Pt（II）的金属-配体相互作用的整合，这些聚合物与其相应的前体相比表现出增强的发射，使其可用作优异的细胞成像剂。考虑到菱形Pt（II）金属杂环的潜在抗癌活性，这些聚合物可作为治疗诊断剂用于生物成像和癌症治疗。超分子单体的共价连接为构建动态聚合物材料提供了一种强有力的策略，该动态聚合物材料的性质可以通过选择单体或选择功能性连接体来容易地调节。在这种策略中，超分子单体的稳定性和用于连接单体的反应是至关重要的，因为这样的单体通常是动态的，并且可以在连接过程中分解，导致产物的混合物。因此，虽然非共价相互作用已被广泛地引入到金属配体结构中以制备金属超分子聚合物，但通过共价键连接的金属配体核聚合物却很少报道。本文中，我们使用烷基胺与N-羟基琥珀酰亚胺活化的羧酸之间的温和、高效的酰胺化反应来连接菱形金属乳糖10的侧氨基官能团，得到金属酰环核聚合物P1和P2，其在低浓度下进一步产生纳米颗粒，并随着浓度增加转化为网络结构。此外，这些聚合物表现出增强的发射，并表现出更好的量子产率比金属乳糖10在甲醇和甲醇/水（1/9，体积/体积），由于聚集诱导的发射性能的四苯乙烯基吡啶供体，它作为前体的金属乳糖10。这些聚合物的荧光特性进一步用于细胞成像，并且它们在静脉注射后在肺细胞中显示出显著的富集。考虑到菱形Pt（II）金属杂环的抗癌活性，这种类型的荧光金属杂环核聚合物可以具有潜在的应用于肺癌治疗。
Significance Fluorescent polymers play an important role in bioimaging due to their improved brightness, inertness to microenvironment, and good biocompatibility. In this article, we used tetraphenylene (TPE) derivatives that give strong fluorescence emission in an aggregated state as fluorophores and synthesized fluorescent polymers via the covalent linkage of TPE-based rhomboidal Pt(II) metallacycles. Due to the integration of covalent linkage-induced aggregation of the monomers, the aggregation-induced emission character of TPE derivatives together with Pt(II)-based metal−ligand interactions, these polymers exhibit enhanced emission compared with their corresponding precursors, making them applicable as excellent cell imaging agents. Considering the potential anticancer activity of rhomboidal Pt(II) metallacycles, these polymers may serve as theranostic agents for both bioimaging and cancer therapy. The covalent linkage of supramolecular monomers provides a powerful strategy for constructing dynamic polymeric materials whose properties can be readily tuned either by the selection of monomers or the choice of functional linkers. In this strategy, the stabilities of the supramolecular monomers and the reactions used to link the monomers are crucial because such monomers are normally dynamic and can disassemble during the linking process, leading to mixture of products. Therefore, although noncovalent interactions have been widely introduced into metallacycle structures to prepare metallosupramolecular polymers, metallacycle-cored polymers linked by covalent bonds have been rarely reported. Herein, we used the mild, highly efficient amidation reaction between alkylamine and N-hydroxysuccinimide-activated carboxylic acid to link the pendent amino functional groups of a rhomboidal metallacycle 10 to give metallacycle-cored polymers P1 and P2, which further yielded nanoparticles at low concentration and transformed into network structures as the concentration increased. Moreover, these polymers exhibited enhanced emission and showed better quantum yields than metallacycle 10 in methanol and methanol/water (1/9, vol/vol) due to the aggregation-induced emission properties of a tetraphenylethene-based pyridyl donor, which serves as a precursor for metallacycle 10. The fluorescence properties of these polymers were further used in cell imaging, and they showed a significant enrichment in lung cells after i.v. injection. Considering the anticancer activity of rhomboidal Pt(II) metallacycles, this type of fluorescent metallacycle-cored polymers can have potential applications toward lung cancer treatment.
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影响因子：
18.3
作者：
Oliveri CG;Ulmann PA;Wiester MJ;Mirkin CA
通讯作者：
Mirkin CA
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影响因子：
18.3
作者：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
5.2
作者：
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通讯作者：
Cammidge, Andrew N.
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影响因子：
15
作者：
Chen, Li-Jun;Ren, Yuan-Yuan;Yang, Hai-Bo
通讯作者：
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