Catenane in the context of Jean-Pierre Sauvage

A rotaxane (from Latin rota 'wheel' and axis 'axle') is a mechanically interlocked molecular architecture consisting of a dumbbell-shaped molecule which is threaded through a macrocycle (see graphical representation). The two components of a rotaxane are kinetically trapped since the ends of the dumbbell (often called stoppers) are larger than the internal diameter of the ring and prevent dissociation (unthreading) of the components since this would require significant distortion of the covalent bonds.

Much of the research concerning rotaxanes and other mechanically interlocked molecular architectures, such as catenanes, has been focused on their efficient synthesis or their utilization as artificial molecular machines. However, examples of rotaxane substructure have been found in naturally occurring peptides, including: cystine knot peptides, cyclotides or lasso-peptides such as microcin J25.

Sir James Fraser Stoddart, FRS FRSE HonFRSC (24 May 1942 – 30 December 2024) was a British-American chemist who was Chair Professor in Chemistry at the University of Hong Kong. He was the Board of Trustees Professor of Chemistry and head of the Stoddart Mechanostereochemistry Group in the Department of Chemistry at Northwestern University in the United States. He worked in the area of supramolecular chemistry and nanotechnology. Stoddart developed highly efficient syntheses of mechanically-interlocked molecular architectures such as molecular Borromean rings, catenanes and rotaxanes utilising molecular recognition and molecular self-assembly processes. He demonstrated that these topologies can be employed as molecular switches. His group has even applied these structures in the fabrication of nanoelectronic devices and nanoelectromechanical systems (NEMS). His efforts were recognized by numerous awards, including the 2007 King Faisal International Prize in Science. He shared the Nobel Prize in Chemistry together with Ben Feringa and Jean-Pierre Sauvage in 2016 for the design and synthesis of molecular machines.

In chemistry, mechanically interlocked molecular architectures (MIMAs) are molecules that are connected as a consequence of their topology. This connection of molecules is analogous to keys on a keychain loop. The keys are not directly connected to the keychain loop but they cannot be separated without breaking the loop. On the molecular level, the interlocked molecules cannot be separated without the breaking of the covalent bonds that comprise the conjoined molecules; this is referred to as a mechanical bond. Examples of mechanically interlocked molecular architectures include catenanes, rotaxanes, molecular knots, and molecular Borromean rings. Work in this area was recognized with the 2016 Nobel Prize in Chemistry to Bernard L. Feringa, Jean-Pierre Sauvage, and J. Fraser Stoddart.

The synthesis of such entangled architectures has been made efficient by combining supramolecular chemistry with traditional covalent synthesis, however mechanically interlocked molecular architectures have properties that differ from both "supramolecular assemblies" and "covalently bonded molecules". The terminology "mechanical bond" has been coined to describe the connection between the components of mechanically interlocked molecular architectures. Although research into mechanically interlocked molecular architectures is primarily focused on artificial compounds, many examples have been found in biological systems including: cystine knots, cyclotides or lasso-peptides such as microcin J25 which are proteins, and a variety of peptides.