Readily available cyclodextrins (CDs) with an inherent hydrophobic internal cavity and hydrophilic external surface are macrocyclic entities that display a combination of molecular recognition and complexation properties with vital implications for host–guest supramolecular chemistry. While the host–guest chemistry of CDs has been widely recognized and led to their exploitation in a variety of important functions over the last five decades, these naturally occurring macrocyclic systems have emerged only recently as promising macrocyclic molecules to fabricate environmentally benign functional nanomaterials. This review surveys the development in the field paying special attention to the synthesis and emerging uses of various unmodified CD–metal complexes and CD–inorganic nanoparticle systems and identifies possible future directions. The association of a hydrophobic cavity of CDs with metal ions or various inorganic nanoparticles is a very appealing strategy for controlling the inorganic subunits properties in the very competitive water environment. In this review we provide the most prominent examples of unmodified CDs’ inclusion complexes with organometallic guests and update the research in this field from the past decade. We discuss also the coordination flexibility of native CDs to metal ions in CD-based metal complexes and summarize the progress in the synthesis and characterization of CD–metal complexes and their use in catalysis and sensing as well as construction of molecular magnets. Then we provide a comprehensive overview of emerging applications of native CDs in materials science and nanotechnology. Remarkably, in the past few years CDs have appeared as attractive building units for the synthesis of carbohydrate metal–organic frameworks (CD–MOFs) in a combination of alkali-metal cations. The preparation of this new class of highly porous materials and their applications in the separation of small molecules, the loading of drug molecules, as well as efficient host templates in the construction of nanomaterials with the desired functionality, including the first-in-class devices including sensors and memristors, are highlighted. Finally, CDs as well-known “green” molecular hosts have also been used as ideal functional molecules to improve the solubility, stability, and bioavailability of inorganic nanoparticles. In this regard, we demonstrate various strategies for the preparation of native CDs-modified inorganic nanomaterials such as metal, metal oxide, and semiconductor and magnetic nanoparticles, aiming to take advantage of both the controlled properties of the inorganic core and the controlled properties of the coating molecules. The functionalization of a CD hydrophobic cavity with an inorganic nanoparticle is very prospective for the development of novel catalytic systems and new tools for highly selective and sensitive sensing platforms for various targets.

中文翻译：

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天然环糊精与金属离子和无机纳米粒子的相互作用：化学和材料科学的肥沃景观

具有固有的疏水性内腔和亲水性外表面的现成的环糊精（CD）是大环实体，显示出分子识别和络合特性的组合，对宿主-客体超分子化学具有重要意义。在过去的五十年中，CD的宿主-客体化学得到了广泛认可，并导致了其在多种重要功能中的开发，但这些天然存在的大环系统直到最近才作为有前途的大环分子制造出对环境无害的功能纳米材料而出现。这篇综述调查了该领域的发展，特别注意了各种未修饰的CD-金属络合物和CD-无机纳米粒子系统的合成和新兴用途，并确定了未来的可能方向。CD的疏水腔与金属离子或各种无机纳米粒子的缔合是一种非常吸引人的策略，用于在竞争激烈的水环境中控制无机亚基的性能。在这篇综述中，我们提供了未改性CD与有机金属客体的包合配合物的最著名例子，并更新了过去十年中该领域的研究。我们还讨论了基于CD的金属配合物中天然CD对金属离子的配位灵活性，并总结了CD-金属配合物的合成和表征及其在催化和传感以及分子磁体构造中的应用进展。然后，我们提供了本机CD在材料科学和纳米技术中新兴应用的全面概述。值得注意的是 在过去的几年中，CD成为了结合碱金属阳离子的碳水化合物金属-有机骨架（CD-MOF）合成的有吸引力的构建单元。这类新型的高度多孔材料的制备及其在小分子分离，药物分子负载以及在构建具有所需功能的纳米材料（包括一流设备）中的高效宿主模板中的应用其中包括传感器和忆阻器。最后，作为著名的“绿色”分子主体的CD也已用作理想的功能分子，以改善无机纳米颗粒的溶解度，稳定性和生物利用度。在这方面，我们展示了各种制备天然CD修饰的无机纳米材料（例如金属，金属氧化物，以及半导体和磁性纳米粒子，旨在同时利用无机核的受控特性和涂层分子的受控特性。具有无机纳米粒子的CD疏水腔的功能化对于开发新型催化系统和针对各种目标的高度选择性和灵敏感测平台的新工具具有非常广阔的前景。