(1/10) A reversible synthetic rotary molecular motor.

The circumrotation of a submolecular fragment in either direction in a synthetic molecular structure is described. The movement of a small ring around a larger one occurs through positional displacements arising from biased Brownian motion that are kinetically captured and then directionally released. The sense of rotation is governed solely by the order in which a series of orthogonal chemical transformations is performed. The minimalist nature of the [2]catenane flashing ratchet design permits certain mechanistic comparisons with the Smoluchowski-Feynman ratchet and pawl. Even when no work has to be done against an opposing force and no net energy is used to power the motion, a finite conversion of energy is intrinsically required for the molecular motor to undergo directional rotation. Nondirectional rotation has no such requirement.  (+info)

(2/10) Chemical peristalsis.

Molecules that emulate in part the remarkable capabilities of protein motors were recently chemically synthesized. A promising approach is based on physically interlocked macromolecular complexes such as rotaxanes and catenanes. Using the latter, Leigh et al. [Leigh, D. A., Wong, J. K. Y., Dehez, F. & Zerbetto, F. (2003) Nature 424, 174-179] constructed a molecular rotor in which two small rings are induced by pulses of light to move unidirectionally around a third, larger ring. The mechanism is similar to that by which a peristaltic pump operates. Unlike macroscopic peristalsis, however, in which a traveling wave forces material through a series of one-way valves, the chemical peristaltic mechanism does not directly cause the small rings to move but only alters the energetics, with the motion itself arising by thermal activation over energy barriers. Engines operating by this mechanism are "Brownian" motors. Here we describe a minimal two-state mechanism for a catenane-based molecular motor. Although fluctuations caused by equilibrium processes cannot drive directed motion, nonequilibrium fluctuations, whether generated externally or by a far-from-equilibrium chemical reaction, can drive rotation even against an external torque. We discuss a possible architecture for input and output of information and energy between the motor and its environment and give a simple expression for the maximum thermodynamic efficiency. The proposed Brownian motor mechanism is consistent with the high efficiency observed by Yasuda et al. [Yasuda, Y., Noji, H., Kinoshita, K. & Yoshida, M. (1998) Cell 93, 1117-1124] for the F(1)-ATP synthase operating as an ATP-powered molecular rotor.  (+info)

(3/10) Amplification of acetylcholine-binding catenanes from dynamic combinatorial libraries.

Directed chemical synthesis can produce a vast range of molecular structures, but the intended product must be known at the outset. In contrast, evolution in nature can lead to efficient receptors and catalysts whose structures defy prediction. To access such unpredictable structures, we prepared dynamic combinatorial libraries in which reversibly binding building blocks assemble around a receptor target. We selected for an acetylcholine receptor by adding the neurotransmitter to solutions of dipeptide hydrazones [proline-phenylalanine or proline-(cyclohexyl)alanine], which reversibly combine through hydrazone linkages. At thermodynamic equilibrium, the dominant receptor structure was an elaborate [2]-catenane consisting of two interlocked macrocyclic trimers. This complex receptor with a 100 nM affinity for acetylcholine could be isolated on a preparative scale in 67% yield.  (+info)

(4/10) Bovine mitochondrial peroxiredoxin III forms a two-ring catenane.

A crystal structure is reported for the C168S mutant of a typical 2-Cys peroxiredoxin III (Prx III) from bovine mitochondria at a resolution of 3.3 A. Prx III is present as a two-ring catenane comprising two interlocking dodecameric toroids that are assembled from basic dimeric units. Each ring has an external diameter of 150 A and encompasses a central cavity that is 70 A in width. The concatenated dodecamers are inclined at an angle of 55 degrees, which provides a large contact surface between the rings. Dimer-dimer contacts involved in toroid formation are hydrophobic in nature, whereas the 12 areas of contact between interlocked rings arise from polar interactions. These two major modes of subunit interaction provide important insights into possible mechanisms of catenane formation.  (+info)

(5/10) Dynamic donor-acceptor [2]catenanes.

Donor-acceptor [2]catenanes based on cyclobis(paraquat-p-phenylene) as the pi-acceptor ring have been used prominently in the construction of functional molecular devices. We report here their thermodynamically controlled synthesis from isolated pi-donor and pi-acceptor rings under the catalytic influence of tetra butylammonium iodide. The initial nucleophilic attack of iodide ion, which opens up the pi-acceptor ring, is followed by complexation to the pi-donor ring and the subsequent catenation of the pi-donor ring by the pi-acceptor ring [2]catenane. The reaction is general in scope and proceeds in high yields, without giving rise to side-products.  (+info)

(6/10) A bistable poly[2]catenane forms nanosuperstructures.


(7/10) A pseudocatenane structure formed between DNA and A cyclic bisintercalator.


(8/10) [2]Catenanes decorated with porphyrin and [60]fullerene groups: design, convergent synthesis, and photoinduced processes.