Su Lu, Feng Yingle, Wei Kongchang, Xu Xuyang, Liu Rongying, Chen Guosong
The State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Institute for Complex Molecular Systems, Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Eindhoven 5600, The Netherlands.
Chem Rev. 2021 Sep 22;121(18):10950-11029. doi: 10.1021/acs.chemrev.0c01338. Epub 2021 Aug 2.
Carbohydrates are the most abundant and one of the most important biomacromolecules in Nature. Except for energy-related compounds, carbohydrates can be roughly divided into two categories: Carbohydrates as matter and carbohydrates as information. As matter, carbohydrates are abundantly present in the extracellular matrix of animals and cell walls of various plants, bacteria, fungi, etc., serving as scaffolds. Some commonly found polysaccharides are featured as biocompatible materials with controllable rigidity and functionality, forming polymeric biomaterials which are widely used in drug delivery, tissue engineering, etc. As information, carbohydrates are usually referred to the glycans from glycoproteins, glycolipids, and proteoglycans, which bind to proteins or other carbohydrates, thereby meditating the cell-cell and cell-matrix interactions. These glycans could be simplified as synthetic glycopolymers, glycolipids, and glycoproteins, which could be afforded through polymerization, multistep synthesis, or a semisynthetic strategy. The information role of carbohydrates can be demonstrated not only as targeting reagents but also as immune antigens and adjuvants. The latter are also included in this review as they are always in a macromolecular formulation. In this review, we intend to provide a relatively comprehensive summary of carbohydrate-based macromolecular biomaterials since 2010 while emphasizing the fundamental understanding to guide the rational design of biomaterials. Carbohydrate-based macromolecules on the basis of their resources and chemical structures will be discussed, including naturally occurring polysaccharides, naturally derived synthetic polysaccharides, glycopolymers/glycodendrimers, supramolecular glycopolymers, and synthetic glycolipids/glycoproteins. Multiscale structure-function relationships in several major application areas, including delivery systems, tissue engineering, and immunology, will be detailed. We hope this review will provide valuable information for the development of carbohydrate-based macromolecular biomaterials and build a bridge between the carbohydrates as matter and the carbohydrates as information to promote new biomaterial design in the near future.
碳水化合物是自然界中含量最丰富且最重要的生物大分子之一。除了与能量相关的化合物外，碳水化合物大致可分为两类：作为物质的碳水化合物和作为信息的碳水化合物。作为物质，碳水化合物大量存在于动物的细胞外基质以及各种植物、细菌、真菌等的细胞壁中，起到支架作用。一些常见的多糖具有生物相容性材料的特性，其刚性和功能可控，可形成聚合物生物材料，广泛应用于药物递送、组织工程等领域。作为信息，碳水化合物通常指糖蛋白、糖脂和蛋白聚糖中的聚糖，它们与蛋白质或其他碳水化合物结合，从而介导细胞间和细胞与基质间的相互作用。这些聚糖可简化为合成糖聚合物、糖脂和糖蛋白，可通过聚合、多步合成或半合成策略获得。碳水化合物的信息作用不仅可表现为靶向试剂，还可作为免疫抗原和佐剂。由于后者通常以大分子形式存在，因此也包含在本综述中。在本综述中，我们旨在对2010年以来基于碳水化合物的大分子生物材料进行较为全面的总结，同时强调基本认识以指导生物材料的合理设计。将讨论基于资源和化学结构的碳水化合物大分子，包括天然存在的多糖、天然衍生的合成多糖、糖聚合物/糖树枝状大分子、超分子糖聚合物以及合成糖脂/糖蛋白。将详细阐述包括递送系统、组织工程和免疫学在内的几个主要应用领域中的多尺度结构 - 功能关系。我们希望本综述能为基于碳水化合物的大分子生物材料的发展提供有价值的信息，并在作为物质的碳水化合物和作为信息的碳水化合物之间架起一座桥梁，以促进在不久的将来进行新的生物材料设计。
