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Ionic aggregation-induced emission dye with bulky counterions for preparation of bright near-infrared polymeric nanoparticles†
Nanoscale ( IF 5.8 ) Pub Date : 2019-07-01 00:00:00 , DOI: 10.1039/c9nr04085d
Nagappanpillai Adarsh 1, 2, 3, 4, 5 , Andrey S. Klymchenko 1, 2, 3, 4, 5
Affiliation  

Dyes exhibiting aggregation-induced emission (AIE) are attractive building blocks for the preparation of bright fluorescent nanomaterials. AIEgens are especially efficient in pure dye aggregates, whereas they are much less explored as dopants in NPs built of hydrophobic polymers. Here, we describe an approach that combines cationic AIEgens with bulky hydrophobic counterions (fluorinated tetraphenylborates) that enables preparation of small and bright AIEgen-loaded polymeric NPs. To this end, we synthesised a cationic tetraphenylethylene (TPE) derivative and studied its salts with counterions of different sizes and hydrophobicities. In organic solvent/water mixtures, all these salts exhibited typical AIE behaviour, whereas only salts with bulky hydrophobic counterions exhibited strongly red-shifted emission in the near-infrared (NIR) region. Encapsulation of these salts into poly(methyl methacrylate-co-methacrylic acid) (PMMA-MA) NPs revealed that bulky counterions ensure (i) formation of small (∼50 nm) AIEgen-loaded polymeric NPs; (ii) good fluorescence quantum yield (up to 30%); and (iii) NIR emission reaching 700 nm. By contrast, AIEgens with small inorganic anions (perchlorate and hexafluorophosphate) blended with PMMA-MA produced large aggregates with emission in the far-red region. Single-particle microscopy revealed that our 50 nm AIEgen-loaded PMMA-MA NPs were 6-fold brighter than the NIR emitting quantum dots (QD705). These NPs feature low cytotoxicity and compatibility with live cell imaging, in contrast to large aggregates of AIEgens with small inorganic counterions that failed to internalize into the cells. The present work shows that combination of cationic AIEgens with bulky counterions opens new routes for the preparation of bright polymer-based nanomaterials.

中文翻译:

带有大抗衡离子的离子聚集诱导发射染料,用于制备明亮的近红外聚合物纳米粒子

表现出聚集诱导发射(AIE)的染料是制备亮荧光纳米材料的有吸引力的组成部分。AIEgens在纯染料聚集体中特别有效,而作为疏水性聚合物构建的NP中的掺杂剂,AIEgens却少得多。在这里,我们描述了一种将阳离子AIEgen与庞大的疏水性抗衡离子(氟化四苯基硼酸酯)结合在一起的方法,该方法能够制备小而明亮的AIEgen负载聚合物NP。为此,我们合成了阳离子四苯基乙烯(TPE)衍生物,并研究了其盐与不同大小和疏水性的抗衡离子的关系。在有机溶剂/水混合物中,所有这些盐都表现出典型的AIE行为,而只有具有庞大疏水性抗衡离子的盐才在近红外(NIR)区域表现出强烈的红移发射。合作-甲基丙烯酸)(PMMA-MA)NPs显示,庞大的抗衡离子可确保(i)形成小的(〜50 nm)载有AIEgen的聚合物NPs;(ii)良好的荧光量子产率(高达30%);(iii)NIR发射达到700 nm。相比之下,具有小的无机阴离子(高氯酸根和六氟磷酸根)与PMMA-MA混合的AIEgens产生了大的聚集体,并在远红色区域发射了光。单粒子显微镜显示,我们的50 nm AIEgen负载的PMMA-MA NP比发射NIR的量子点(QD705)亮6倍。这些NP具有较低的细胞毒性和与活细胞成像的相容性,这与AIEgens的大量聚集体和无机小抗衡离子无法内化到细胞中形成鲜明对比。
更新日期:2019-07-01
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