Structural properties of contractile gels based on light-driven molecular motors: a small-angle neutron and X-ray study.

The detailed structure of active polymer gels built by integrating light-driven rotary molecular motors as reticulation units in polymer networks is discussed as a function of gel composition. Upon light-irradiation, the collective rotation of molecular motors is translated into the macroscopic contraction of the gels through polymer chains twisting. The major role of the characteristic ratio c/c* (c* being the overlap concentration of the polymer-motor conjugates before crosslinking) on the contraction efficiency is exploited. Combined small-angle neutron and X-ray scattering experiments reveal the importance of heterogeneities in the macroscopic contraction process: the mesh size of the network increases under irradiation in the whole range of c/c*, an increase that is maximal for c/c* = 1; i.e. at higher contraction efficiency. Furthermore, the mesh size of the network reaches equilibrium within a short period of time, while the heterogeneities increase in size untill the end of the contraction process. Finally, the significant motorized twisting of polymer chains within the network allows to foresee the design of new storage energy systems.

Optoregulated force application to cellular receptors using molecular motors.

Progress in our understanding of mechanotransduction events requires noninvasive methods for the manipulation of forces at molecular scale in physiological environments. Inspired by cellular mechanisms for force application (i.e. motor proteins pulling on cytoskeletal fibers), we present a unique molecular machine that can apply forces at cell-matrix and cell-cell junctions using light as an energy source. The key actuator is a light-driven rotatory molecular motor linked to polymer chains, which is intercalated between a membrane receptor and an engineered biointerface. The light-driven actuation of the molecular motor is converted in mechanical twisting of the entangled polymer chains, which will in turn effectively "pull" on engaged cell membrane receptors (e.g., integrins, T cell receptors) within the illuminated area. Applied forces have physiologically-relevant magnitude and occur at time scales within the relevant ranges for mechanotransduction at cell-friendly exposure conditions, as demonstrated in force-dependent focal adhesion maturation and T cell activation experiments. Our results reveal the potential of nanomotors for the manipulation of living cells at the molecular scale and demonstrate a functionality which at the moment cannot be achieved by other technologies for force application.

Mechanical behaviour of contractile gels based on light-driven molecular motors.

The networking of individual artificial molecular motors into collective actuation systems is a promising approach for the design of active materials working out of thermodynamic equilibrium. Here, we report the first mechanical studies on active polymer gels built by integrating light-driven rotary molecular motors as reticulation units in polymer networks. We correlate the volume ratio before and after light irradiation with the change of the elastic modulus, and we reveal the universal maximum mechanical efficiency of such gels related to their critical overlap concentration before chemical reticulation. We also show the major importance of heterogeneities in the macroscopic contraction process and we confirm that these materials can increase their internal energy by the motorized winding of their polymer chains.

Dual-light control of nanomachines that integrate motor and modulator subunits.

A current challenge in the field of artificial molecular machines is the synthesis and implementation of systems that can produce useful work when fuelled with a constant source of external energy. The first experimental achievements of this kind consisted of machines with continuous unidirectional rotations and translations that make use of 'Brownian ratchets' to bias random motions. An intrinsic limitation of such designs is that an inversion of directionality requires heavy chemical modifications in the structure of the actuating motor part. Here we show that by connecting subunits made of both unidirectional light-driven rotary motors and modulators, which respectively braid and unbraid polymer chains in crosslinked networks, it becomes possible to reverse their integrated motion at all scales. The photostationary state of the system can be tuned by modulation of frequencies using two irradiation wavelengths. Under this out-of-equilibrium condition, the global work output (measured as the contraction or expansion of the material) is controlled by the net flux of clockwise and anticlockwise rotations between the motors and the modulators.

Dibromoindium(III) cations as a π-Lewis acid: characterization of [IPr·InBr2][SbF6] and its catalytic activity towards alkynes and alkenes.

[IPr·InBr2][SbF6] (2) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) has been synthesized and characterized in the solid state. This complex proved to be a very active catalyst for hydroarylations, transfer hydrogenations, and cycloisomerizations.