text: Polyrotaxane is a type of mechanically interlocked molecule consisting of strings and rings, in which multiple rings are threaded onto a molecular axle and prevented from dethreading by two bulky end groups. As oligomeric or polymeric species of rotaxanes, polyrotaxanes are also capable of converting energy input to molecular movements because the ring motions can be controlled by external stimulus. Polyrotaxanes have attracted much attention for decades, because they can help build functional molecular machines with complicated molecular structure.
  Although there are no covalent bonds between the axes and rings, polyrotaxanes are stable due to the high free activation energy (Gibbs energy) needed to be overcome to withdraw rings from the axes. Also, rings are capable of shuttling along and rotating around the axes freely, which leads to a huge amount of internal degree of freedom of polyrotaxanes. Due to this topologically interlocked structure, polyrotaxanes have many different mechanical, electrical, and optical properties compared to conventional polymers.
  Additionally the mechanically interlocked structures can be maintained in slide-ring materials, which are a type supramolecular network synthesized by crosslinking the rings (called figure-of-eight crosslinking) in different polyrotaxanes. In slide-ring materials, crosslinks of rings can pass along the axes freely to equalize the tension of the threading polymer networks, which is similar to pulleys. With this specific structure, slide-ring materials can be fabricated highly stretchable engineering materials due to their different mechanical properties.
  If the rings and axes are biodegradable and biocompatible, the polyrotaxanes can also be used for biomedical application, such as gene/drug delivery. The advantage of polyrotaxanes over other biomedical polymers, such as polysaccharides, is that because the interlocked structures are maintained by bulky stoppers at the ends of the strings, if the bulky stoppers are removed, such as removed by a chemical stimulus, rings dethread from the axes. The drastic structural change can be used for programmed drug or gene delivery, in which the drug or gene can be released with the rings when the stoppers are cut off at the specific destination.