石墨炔基复合材料及其在生物小分子检测中的应用

Surface-and interface-regulated graphdiyne-based composites and their applications in the detection of small biological signaling molecules

石墨炔(graphdiyne,GDY)是一种由sp和sp2两种杂化碳构成的新型碳同素异形体,具有独特的sp-sp^(2)碳原子、均匀的孔隙和高度的π共轭结构,不仅能够提供特定反应的活性位点,而且可以有效锚定多种元素,实现高选择性催化的目的.石墨炔及其复合材料在生物信号小分子检测方面取得了一系列进展,但目前依然缺少相关综述.本文综述了近年来石墨炔及其复合材料在生物小分子检测领域的应用,讨论了石墨炔复合材料的发展及其在生物小分子检测中的最新研究进展;简单介绍了石墨炔基复合材料相关的结构、电子和光学等物理化学特性,总结了石墨炔复合材料的表界面调控策略;系统总结和分析了石墨炔复合材料在生物小分子检测领域的应用,聚焦于过氧化氢分子、葡萄糖分子、多巴胺分子和活细胞生物信号小分子的研究.最后,对石墨炔基复合材料及其在生物小分子检测应用的未来发展作了展望,特别提出开发更多的表界面工程策略以实现石墨炔基复合材料物化特性的精准调控,开拓其在其他重要信号分子的检测应用及实现多信号分子的同时检测,以及推动其在活体分析上的应用.

Graphdiyne(GDY)is a novel diacetylene carbon allotrope with a two-dimensional(2D)planar network structure consisting of sp^(2) and sp carbon atoms.Since its successful fabrication on the surface of a copper foil during experimentation,GDY has been gaining increasing attention owing to its highπ-conjunction,wide interplanar spacing,tunable electronic properties,interesting structure,and excellent physicochemical stability.To date,extensive research efforts have been channeled toward theoretical prediction and synthesis methods and the applications of GDY and its derivatives in the fields of batteries,catalysts,biosensing,and biomedicine.Specifically,the unique properties of GDY,including a large hydrophobic planar network,specific surface area,and binding energies,render it an excellent compound for other functional materials or molecules to achieve high catalytic performance in the fields of biosensing and bioelectric chemistry.However,despite the great advances in GDY,reviews on the achievements are limited.The current review summarizes the recent advances of GDY and its derivatives in the sensing of small biological signaling molecules,focusing on the strategies for tailoring the surface and interface of the materials.The review also explores the relationship between the physicochemical properties of the materials and their sensing performance.The main contents of this review are as follows:First,we explain the structure and optical and electrical properties of GDY materials and describe the theoretical and experimental investigations on the basic properties of GDY.Owing to the unique structures of GDY,including its three-dimensional network pores and highπ-conjunction,GDY can be facilely combined with other functional materials to improve catalytic ability,which is beneficial for achieving high sensitivity for sensing small molecules.Next,we discuss the functionalization strategies of GDY.The presence of carbon–carbon triple bonds in GDY allows it to be doped with metallic and nonmetallic species,including nitrogen,boron,phosphorus,copper,and palladium.Heteroatom doping can efficiently tune the electronic structures of GDY,which can enhance the sensing performance of GDY and its derivatives toward small biological signaling molecules.Moreover,the applications of GDY and its derivatives in sensing small biological signaling molecules are discussed and analyzed.We focus on the sensing mechanism and performance enhancement of GDY and its derivatives toward glucose,dopamine,ascorbic acid,uric acid,hydrogen peroxide,and nitric oxide.Moreover,we raise the key issues that need to be addressed in the future.Great research progress has been made on the synthesis of GDY-based materials and their applications.However,GDY-based materials and their sensing applications are still not well understood.For instance,to date,only GDY has been successfully synthesized.Other structures of graphynes have only been predicted through theoretical studies.Establishing other structures of graphynes in a controllable and scalable manner is highly difficult,but such techniques can produce structures with rich active sites and enhanced catalytic ability.Moreover,heteroatom doping can modify the physicochemical,electrical,and structural properties of GDY-based materials.Nevertheless,precisely doping heteroatoms on the GDY surface in a controllable manner remains a great challenge.With the remarkable advances in the exploration of new and practical synthesis methods,the interfacial reaction processes and the effects of the structure-activity relationship on the sensing performance of GDY-based materials can be elucidated.This can help expand the knowledge of biochemical and bioelectric applications related to GDY and its derivatives.