Abstract

In this paper we give the overview of our latest results on the complexation between polyelectrolytes and oppositely charged low-molar mass species, proteins, homopolymers and block copolymers. First, we review the results on the study of the interaction of polythiophene-based polycations with phosphonium and ammonium pendants and their complexation with negatively charged multivalent species followed by fluorescence quenching. We proved that multivalent solutes bind to polyelectrolyte stronger than to previously studied polythiophene, thus, allowing for their application as luminescence sensors. Secondly, we investigated the co-assembly of polyanion with double hydrophilic block copolymer composed of polycationic block and neutral hydrophilic block and followed the complex formation by quenching of fluorescence of the indicator attached to the end of polyanion chain. We discovered that the formed interpolyelectrolyte (IPEC) core of core/shell micelles remains dynamical even after equilibrium was reached thus making such systems suitable materials for targeted delivery of multivalent species. In addition, the formation of micelles with fluid cores was observed as a result of self-assembly of di- and triblock polyelectrolytes containing a hydrophobic block with low glass transition temperature and a positively charged block. We proved their ability to encapsulate and release hydrophobic species from the soft core upon dilution. Moreover, we confirmed their ability to complex with multivalent negatively charged species. The morphology of the formed complex strongly depends on ionic strength: the aggregates formed by micelles bonded at the periphery disrupt with increasing salt concentration and a part of multivalent ions releases into solution. Finally, the multilayered nanoparticles with both soft hydrophobic and IPEC layers were designed by co-assembly between core/shell micelles with a soft core and a positively charged shell, and block polyelectrolyte composed of polyanion and neutral hydrophilic blocks. We showed that the morphology of the particles and the charge of IPEC layer of such multicompartment nanostructures can be controlled by the ratio of oppositely charged monomeric units.

中文翻译：

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水溶液中聚电解质和聚电解质间复合物的综合多维表征

摘要

在本文中，我们概述了我们关于聚电解质与带相反电荷的低摩尔质量物质、蛋白质、均聚物和嵌段共聚物之间络合的最新结果。首先，我们回顾了基于聚噻吩的聚阳离子与磷和铵悬垂物相互作用的研究结果，以及它们与带负电荷的多价物质络合后荧光猝灭的研究结果。我们证明，多价溶质与聚电解质的结合比与先前研究的聚噻吩的结合更强，因此可以将它们用作发光传感器。第二，我们研究了聚阴离子与由聚阳离子嵌段和中性亲水嵌段组成的双亲水嵌段共聚物的共组装，并通过淬灭附着在聚阴离子链末端的指示剂的荧光来跟踪复合物的形成。我们发现，形成的核/壳胶束的聚电解质 (IPEC) 核即使在达到平衡后仍保持动态，从而使此类系统成为适合多价物质靶向递送的材料。此外，由于包含具有低玻璃化转变温度的疏水嵌段和带正电荷的嵌段的二嵌段和三嵌段聚电解质的自组装，观察到具有流体核的胶束的形成。我们证明了它们能够在稀释后从软核中封装和释放疏水物质。而且，我们证实了它们与多价带负电荷的物质复合的能力。形成的复合物的形态在很大程度上取决于离子强度：由键合在外围的胶束形成的聚集体随着盐浓度的增加而破裂，并且一部分多价离子释放到溶液中。最后，通过将具有软核和带正电壳的核/壳胶束与由聚阴离子和中性亲水嵌段组成的嵌段聚电解质共同组装，设计出具有软疏水层和 IPEC 层的多层纳米粒子。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制 形成的复合物的形态在很大程度上取决于离子强度：由键合在外围的胶束形成的聚集体随着盐浓度的增加而破裂，并且一部分多价离子释放到溶液中。最后，通过将具有软核和带正电壳的核/壳胶束与由聚阴离子和中性亲水嵌段组成的嵌段聚电解质共同组装，设计出具有软疏水层和 IPEC 层的多层纳米粒子。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制 形成的复合物的形态在很大程度上取决于离子强度：由键合在外围的胶束形成的聚集体随着盐浓度的增加而破裂，并且一部分多价离子释放到溶液中。最后，通过将具有软核和带正电壳的核/壳胶束与由聚阴离子和中性亲水嵌段组成的嵌段聚电解质共同组装，设计出具有软疏水层和 IPEC 层的多层纳米粒子。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制 随着盐浓度的增加，由键合在外围的胶束形成的聚集体破裂，并且部分多价离子释放到溶液中。最后，通过将具有软核和带正电壳的核/壳胶束与由聚阴离子和中性亲水嵌段组成的嵌段聚电解质共同组装，设计出具有软疏水层和 IPEC 层的多层纳米粒子。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制 随着盐浓度的增加，由键合在外围的胶束形成的聚集体破裂，并且部分多价离子释放到溶液中。最后，通过将具有软核和带正电壳的核/壳胶束与由聚阴离子和中性亲水嵌段组成的嵌段聚电解质共同组装，设计出具有软疏水层和 IPEC 层的多层纳米粒子。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制 由聚阴离子和中性亲水嵌段组成的嵌段聚电解质。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制 由聚阴离子和中性亲水嵌段组成的嵌段聚电解质。我们表明，这种多隔室纳米结构的粒子形态和 IPEC 层的电荷可以通过带相反电荷的单体单元的比例来控制.