Rotaxane


Also found in: Dictionary, Wikipedia.

rotaxane

[rō′tak‚sān]
(organic chemistry)
A compound with two or more independent portions not bonded to each other but linked by a linear portion threaded through a ring and maintained in this position by bulky end groups.

Rotaxane

 

any of a group of chemical compounds composed of a linear molecular chain passing through a chainlike molecular ring. The compound is so arranged that the bulky end groups of the linear chain prevent the ring from slipping off.

Figure 1

The structural representation of a rotaxane molecule is shown in Figure 1, where R and R’ are radicals and the ring is a cyclic macromolecule.

The simplest type of rotaxane structure is shown in Figure 2, where η = 25–29. (This type of linear molecule will not fit within a smaller ring, that is, where η < 25; where n > 29, the stability of the rotaxane molecule is limited and the ring slips off the linear molecule.) The entities that form rotaxanes, that is, the linear and cyclic molecules, are bonded mechanically rather than chemically in what is called a topological bond.

Figure 2

Chemical compounds with topological bonding also include catenanes, wherein the cyclic macromolecules are joined in a fashion suggesting chain links. Figure 3 shows the structure of one of the synthesized catenanes. Rotaxanes and catenanes are obtained either by random formation in accordance with statistical laws (statistical synthesis) or by directed synthesis. The first statistical synthesis of rotaxanes was carried out by I. Harrison and S. Harrison (1967, United States); directed synthesis was first achieved by G. Schill and H. Zollenkopf (1969,

Figure 3

Federal Republic of Germany). Molecules of compounds constructed without chemical bonds occur in both organic and inorganic nature. Rotaxane and catenane forms of deoxyribonucleic acid (DNA) have been discovered.

REFERENCES

Schill, G., E. Logemann, and W. Vetter. “Ozonolytischer Abbau eines Catensins” Augewandte Chemie, 1972, vol. 84, no. 23, p. 1144.
Schill, G. Katenany, rotaksany i uzly. Moscow, 1973. (Translated from English.)
Kostianovskii, R. G. Katenany iklatraty. Moscow, 1966.

R. G. KOSTIANOVSKII

Mentioned in ?
References in periodicals archive ?
The group has even created rotaxanes where a single wheel can jump between two discrete locations on an axle, acting as a molecular switch that could encode digital information.
Heath's and Kuekes' teams said the rotaxane molecules, sandwiched between metal electrodes, functioned as logic gates.
The rings would still move mostly at random, but on average the gates would tend to push them in a specific direction, from one rotaxane to the next.
It's big enough to let molecules in and out, but small enough so that the switchable rotaxane molecules can block the hole," says Zink.
Dr Steve Goldup, Associate Professor of Supramolecular Chemistry, and his team have developed a catalyst with significantly enhanced properties based on a rotaxane, in which a gold catalyst is embedded in the cavity formed by threading a ring shaped molecule around a dumbell shaped axle.
Topics addressed include bioactive macrocyclic peptides and peptide mimics, macrocycles by ring-closure metathesis, supramolecular macrocycle synthesis by H-bonding assembly, cucurbiturils, tetra-urea calixarenes, shape-persistent macrocycles based on acetylenic scaffolding, supramolecular 3D architectures by metal-directed assembly of synthetic macrocycles, new properties and reactions in self-assembly M6L4 coordination cages, anion-binding macrocycles, and rotaxane and catenane synthesis.
This project aims at the development of a new class of hydrogen evolving catalysts based on mechanically interlocked rotaxane architectures.
Chapters cover modification reactions of cyclodextrins and the chemistry of modified cyclodextrins, polymers involving cyclodextrin moieties, cyclodextrin catalysis, chromatographic studies of molecular and chiral recognition, application of cyclodextrins for enantioseparations, crystallographic study of cyclodextrins and their inclusion complexes, microcalorimetry, NMR (nuclear magnetic resonance) of cyclodextrins and their complexes, other physiochemical methods, modeling of cyclodextrins and their complexes, rotaxane and catenane structures involving cyclodextrins, large-ring cyclodextrins, pharmaceutical applications, cyclodextrins in dispersed systems, and non-pharmaceutical applications.
Each of the valves is an organic molecule known as a rotaxane (SN: 2/7/04,p.
To weigh in on this controversy, Blanco and his team modeled a rotaxane atom by atom.
who is one of the experimenters, explains that in these prototypes, electrodes sprawl across several million rotaxane molecules.
Leigh, and Aden Murphy of the University of Manchester in England created a rotaxane with a ring-shaped molecule as the bead, a peptide as the string, and bulky chemical groups as the knots on the ends.