Two-Dimensional Self-Assembled Structures of Highly Ordered Bioactive Crystalline-Based Block Copolymers
Two-Dimensional Self-Assembled Structures of Highly Ordered Bioactive Crystalline-Based Block Copolymers
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DOI：
10.1021/acs.macromol.7b01453
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发表时间：
2017-11-14
期刊：
影响因子：
5.5
通讯作者：
Stenzel, Martina H.
中科院分区：
文献类型：
--
作者：
Ganda, Sylvia;Dulle, Martin;Stenzel, Martina H.
从材料设计的角度来看，大自然在精确地生成材料方面的复杂性提供了学习的机会，以便实现具有明确定义的结构、有序的周期性和稳定性的功能材料的受控生成。受红细胞和血小板的二维性和表面化学的启发，我们试图实施由基于两亲性碳水化合物的结晶-卷曲嵌段共聚物的结晶和相分离诱导的力，以诱导自组装产生二维（2D）层状血小板结构。随着目前通过嵌段共聚物的结晶驱动自组装（CDSA）产生功能性2D血小板结构，将现有系统转变为生物相容性和生物活性系统是强制性的，以便将其功能性和适用性提升到另一个水平。在这项研究中，我们介绍了结晶驱动的自组装的n-果糖功能化的结晶线圈嵌段共聚物具有聚（ε-己内酯）作为可结晶的核心形成块。通过微调的电晕长度和组合物，我们得到了2D血小板范围在纳米（183 nm，长度）到微米尺寸范围（2-4 μ m，长度）之间的尺度，后者具有固有的高度有序的核心晶体结构的正交单晶体观察通过电子显微镜技术和选区电子衍射（SAED）实验。我们发现，通过添加游离聚合物，片晶结构外延生长，形成超大的六边形2D片晶（约100 μ m）。19-21 μ m），在类似于活性聚合物生长的过程中。这些血小板的种子生长表明记忆效应，为进一步的分层自组装和功能化提供了平台。整体方法提出了一种简单的策略，在制造越来越重要的胶体稳定的仿生二维结构的特征和功能特性。
Viewing from the material design perspective, the sophistication of nature in generating materials with great precision provides opportunities to learn from in order to achieve the controlled generation of functional materials with well-defined architectures, ordered periodicity, and stability. Inspired by the two-dimensionality and surface chemistry of red blood cells and blood platelets, we attempted to implement the forces induced by crystallization and phase separation of amphiphilic carbohydrate-based crystalline-coil block copolymers to induce self-assembly generating two-dimensional (2D) lamellar platelet structures. With the current generation of functional 2D platelet structures via crystallization-driven self-assembly (CDSA) of block copolymers, transitioning the existing system into a biocompatible and bioactive system is mandatory in order to bring their functionality and applicability to another level. In this study, we introduce the crystallization-driven self-assembly of n-fructose-functionalized crystalline-coil block copolymers featuring poly(e-caprolactone) as the crystallizable core-forming block. By fine-tuning the corona length and composition, we obtained 2D platelets ranging in the scale between nanometer (183 nm, length) to micrometer size range (2-4 mu m, length), with the latter featuring intrinsically highly ordered core-crystalline structure of orthorhombic single crystals as observed by the means of electron microscopy techniques and selected-area electron diffraction (SAED) experiment. We discovered the platelet structures to grow epitaxially through the addition of free polymer, forming supersized hexagonal 2D platelets (ca. 19-21 mu m), in a process akin to the growth of living polymers. The seeded growth of these platelets suggests a memory effect, providing a platform for further hierarchical self-assembly and functionalization. The overall approach presents a facile strategy in fabricating the increasingly important colloidally stable bioinspired 2D structures with characteristic features and functional properties.