Molecular Nanoparticles Are Unique Elements for Macromolecular Science: From 鈥淣anoatoms鈥?to Giant Molecules

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• 作者：Wen-Bin Zhang ; Xinfei Yu ; Chien-Lung Wang ; Hao-Jan Sun ; I-Fan Hsieh ; Yiwen Li ; Xue-Hui Dong ; Kan Yue ; Ryan Van Horn ; Stephen Z. D. Cheng
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：February 25, 2014
• 年：2014
• 卷：47
• 期：4
• 页码：1221-1239
• 全文大小：1150K
• 年卷期：v.47,no.4(February 25, 2014)
• ISSN：1520-5835

文摘

In this Perspective, we present a unique approach to the design and synthesis of giant molecules based on 鈥渘anoatoms鈥?for engineering structures across multiple length scales and controlling their macroscopic properties. Herein, 鈥渘anoatoms鈥?refer to shape-persistent molecular nanoparticles (MNPs) with precisely defined chemical structures and surface functionalities that can serve as elemental building blocks for the precision synthesis of giant molecules by methods such as sequential 鈥渃lick鈥?approach. Typical 鈥渘anoatoms鈥?include those MNPs based on fullerenes, polyhedral oligomeric silsesquioxanes, polyoxometalates, and folded globular proteins. The resulting giant molecules are precisely defined macromolecules. They include, but are not limited to, giant surfactants, giant shape amphiphiles, and giant polyhedra. Giant surfactants are polymer tail-tethered 鈥渘anoatoms鈥?where the two components have drastic chemical differences to impart amphiphilicity. Giant shape amphiphiles not only are built up by covalently bonded MNPs of distinct shapes where the self-assembly is driven by chemical interactions but also are largely influenced by the packing constraints of each individual shape. Giant polyhedra are either made of a large MNP or by deliberately placing 鈥渘anoatoms鈥?at the vertices of a polyhedron. In general, giant molecules capture the essential structural features of their small-molecule counterparts in many ways but possess much larger sizes. They are recognized in certain cases as size-amplified versions of those counterparts, and often, they bridge the gap between small molecules and traditional macromolecules. Highly diverse, thermodynamically stable and metastable hierarchal structures are commonly observed in the bulk, thin film, and solution states of these giant molecules. Controlled structural variations by precision synthesis further reveal a remarkable sensitivity of their self-assembled structures to the primary chemical structures. Unconventional nanostructures can be obtained in confined environments or through directed self-assembly. All the results demonstrate that MNPs are unique elements for macromolecular science, providing a versatile platform for engineering nanostructures that are not only scientifically intriguing but also technologically relevant.