Osypova A, Magnin D, Sibret P, Aqil A, Jérôme C, Dupont-Gillain C, Pradier C-M, Demoustier-Champagne S, Landoulsi J
Institute of Condensed Matter and Nanosciences, Bio & Soft Matter, Université catholique de Louvain, Croix du Sud 1 (L7.04.01), 1348, Louvain-la-Neuve, Belgium.
Soft Matter. 2015 Nov 7;11(41):8154-64. doi: 10.1039/c5sm01545f.
In this paper, we describe the successful construction, characteristics and interaction with proteins of stimuli-responsive thin nanostructured films prepared by layer-by-layer (LbL) sequential assembly of PNIPAM-containing polyelectrolytes and PAH. PAA-b-PNIPAM block copolymers were synthesized in order to benefit from (i) the ionizable properties of PAA, to be involved in the LbL assembly, and (ii) the sensitivity of PNIPAM to temperature stimulus. The impact of parameters related to the structure and size of the macromolecules (their molecular weight and the relative degree of polymerization of PAA and PNIPAM), and the interaction with proteins under physico-chemical stimuli, such as pH and temperature, are carefully investigated. The incorporation of PAA-b-PNIPAM into multilayered films is shown to be successful whatever the block copolymer used, resulting in slightly thicker films than the corresponding (PAA/PAH)n film. Importantly, the protein adsorption studies demonstrate that it is possible to alter the adsorption behavior of proteins on (PAA-b-PNIPAM/PAH)n surfaces by varying the temperature and/or the pH of the medium, which seems to be intimately related to two key factors: (i) the ability of PNIPAM units to undergo conformational changes and (ii) the structural changes of the film made of weak polyelectrolytes. The simplicity of construction of these PNIPAM block copolymer-based LbL coatings on a large range of substrates, combined with their highly tunable features, make them ideal candidates to be employed for various biomedical applications requiring the control of protein adsorption.
在本文中，我们描述了通过含PNIPAM的聚电解质与PAH的逐层（LbL）顺序组装制备的刺激响应性薄纳米结构薄膜的成功构建、特性及其与蛋白质的相互作用。合成了PAA-b-PNIPAM嵌段共聚物，以便受益于：（i）PAA的可电离特性，参与LbL组装；（ii）PNIPAM对温度刺激的敏感性。仔细研究了与大分子的结构和尺寸相关的参数（它们的分子量以及PAA和PNIPAM的相对聚合度），以及在物理化学刺激（如pH和温度）下与蛋白质的相互作用。无论使用何种嵌段共聚物，将PAA-b-PNIPAM掺入多层膜中都被证明是成功的，所得到的膜比相应的（PAA/PAH）n膜略厚。重要的是，蛋白质吸附研究表明，通过改变介质的温度和/或pH，可以改变蛋白质在（PAA-b-PNIPAM/PAH）n表面的吸附行为，这似乎与两个关键因素密切相关：（i）PNIPAM单元发生构象变化的能力；（ii）由弱聚电解质制成的膜的结构变化。这些基于PNIPAM嵌段共聚物的LbL涂层在多种基材上构建简单，且具有高度可调谐的特性，使其成为各种需要控制蛋白质吸附的生物医学应用的理想候选材料。
