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Daisy chain architectures, made by the self-complementary threading of an axle covalently linked to a macrocycle, represent a particularly intriguing family of supramolecular and mechanically interlocked (macro)molecules. In this review, we discuss their recent history, their modular chemical structures, and the various synthetic strategies to access them. We also detail how their internal sliding motions can be controlled and how their integration within polymers can amplify that motions up to the macroscopic scale. This overview of the literature demonstrates that the peculiar structure and dynamics of daisy chains have already strongly influenced the research on artificial molecular machines, with the potential to be implemented from nanometric switchable devices to mechanically active soft-matter materials.
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In this paper, potentially-gelling binary systems are investigated by DSC, X-ray and Electron microscopy in order to assess their gel status and the role of the Hansen solubility parameter. The low molecular weight organogelator is a Triarylamine Trisamide (TATA) while the solvents consist of a series of halogeno-ethanes and of toluene. Temperature-concentration phase diagrams are mapped out from DSC traces. They reveal the existence of one or more TATA/solvent molecular compounds. The X-ray data, that display different diffraction patterns depending on the solvent and the temperature, show the existence of different molecular structures, and thus confirm the outcome of the T-C phase diagram. Tentative molecular organizations are also discussed in light of previous results obtained in the solid state. The morphology by TEM on dilute systems, and TEM on more concentrated systems highlight the degree of physical cross-links, which leads one to regard some systems as pseudo-gels.
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The unidirectional rotation of chemically crosslinked light-driven molecular motors is shown to progressively shift the swelling equilibrium of hydrogels. The concentration of molecular motors and the initial strand density of the polymer network are key parameters to modulate the macroscopic contraction of the material, and both parameters can be tuned using polymer chains of different molecular weights. These findings led to the design of optimized hydrogels revealing a half-time contraction of approximately 5â min. Furthermore, under inhomogeneous stimulation, the local contraction event was exploited to design useful bending actuators with an energy output 400 times higher than for previously reported self-assembled systems involving rotary motors. In the present configuration, we measure that a single molecular motor can lift up loads of 200 times its own molecular weight.
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A unidirectional light-driven rotary motor was looped in a figure-of-eight molecule by linking two polymer chains between its stator and rotor parts. By properly tuning the size of these linkers, clockwise rotation of the motor under UV light was shown to create conformationally strained twists between the polymer chains, and in this tensed conformation, the energy stored in the molecular object was sufficient to trigger the reverse rotation of the motor back to its fully relaxed state. The functioning principle of this motorized molecular device appears very similar to that of macroscopic whirligig crafts used by children for fun. In addition, we found that in its out-of-equilibrium tensed state, the fluorescence emission of the molecular motor increased by 500% due to the mechanical constraints imposed by the polymer chains on its conjugated core. Finally, by calculating the apparent thermal energies of activation for the backward rotations at different levels of twisting, we quantitatively determined a lower estimate of the work generated by this rotary motor, from which a torque and a force were extracted, thus answering a long-term open question in this field of research.
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Fenômenos Mecânicos , Proteínas Motores Moleculares , Criança , Humanos , Polímeros , TorqueRESUMO
Precise control over molecular movement is of fundamental and practical importance in physics, biology, and chemistry. At nanoscale, the peculiar functioning principles and the synthesis of individual molecular actuators and machines has been the subject of intense investigations and debates over the past 60 years. In this review, we focus on the design of collective motions that are achieved by integrating, in space and time, several or many of these individual mechanical units together. In particular, we provide an in-depth look at the intermolecular couplings used to physically connect a number of artificial mechanically active molecular units such as photochromic molecular switches, nanomachines based on mechanical bonds, molecular rotors, and light-powered rotary motors. We highlight the various functioning principles that can lead to their collective motion at various length scales. We also emphasize how their synchronized, or desynchronized, mechanical behavior can lead to emerging functional properties and to their implementation into new active devices and materials.
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A hydrophobic light-driven rotary motor is functionalized with two 18-crown-6 macrocycles and incorporated into phospholipid bilayers. In the presence of this molecular construct, fluorescence assays and patch clamp experiments show the formation of selective alkali ion channels through the membrane. Further, they reveal a strongly accelerated ion transport mechanism under light irradiation. This increase of the fractional ion transport activity (up to 400%) is attributed to the out-of-equilibrium actuation dynamics of the light-driven rotary motors, which help to overcome the activation energy necessary to achieve translocation of alkali ions between macrocycles along the artificial channels.
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A S6-symmetric triarylamine-based macrocycle (i.e., hexaaza[16]paracyclophane), decorated with six lateral amide functions, is synthesized by a convergent and modular strategy. This macrocycle is shown to undergo supramolecular polymerization in o-dichlorobenzene, and its nanotubular structure is elucidated by a combination of spectroscopy and microscopy techniques, together with X-ray scattering and molecular modeling. Upon sequential oxidation, a spectroelectrochemical analysis of the supramolecular polymer suggests an extended electronic delocalization of charge carriers both within the macrocycles (through bond) and between the macrocycles along the stacking direction (through space).
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Despite their intrinsic hydrolysable character, imine bonds can become remarkably stable in water when self-assembled in amphiphilic micellar structures. In this work, we systematically studied some of these structures and the influence of various parameters that can be used to take control of their hydrolysis, including pH, concentration, the position of the imine function in the amphiphilic structure, relative lengths of the linked hydrophilic and hydrophobic moieties. Thermodynamic and kinetic data led us to the rational design of stable imines in water, partly based on the location of the imine function within the hydrophobic part of the amphiphile and on a predictable quantitative term that we define as the total hydrophilic-lipophilic balance (HLB). In addition, we show that such stable systems are also stimuli-responsive and therefore, of potential interest in trapping and releasing micellar components on demand.
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Iminas , Micelas , Hidrólise , Interações Hidrofóbicas e Hidrofílicas , ÁguaRESUMO
Amphiphilic imines prepared by condensation of a hydrophobic fragrance aldehyde with a hydrophilic amine derived from a poly(propylene oxide) and poly(ethylene oxide) diblock copolymer were investigated as cleavable surfactant profragrances in applications of functional perfumery. In water, the cleavable surfactants assemble into micelles that allow solubilization of perfume molecules that are not covalently attached to the surfactant. Dynamic headspace analysis on a glass surface showed that solubilized perfume molecules evaporated in a similar manner in the presence of the cleavable surfactant as compared with a non-cleavable reference surfactant. Under application conditions, the cleavable surfactant imine hydrolysed to release the covalently linked fragrance aldehyde. The profragrances were stable during storage in aqueous media, and upon dilution showed a blooming effect for the hydrolytical fragrance release and a more balanced performance of a solubilized perfume by retaining the more volatile fragrances and boosting the evaporation of the less volatile fragrances.
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Perfumes , Tensoativos , Interações Hidrofóbicas e Hidrofílicas , Micelas , OdorantesRESUMO
The self-assembly of chiral supramolecular polymers is an intricate process that spans a wide range of length scales. Circular dichroism techniques are ideal to study this process as they provide information on the molecular scale but are at the same time also sensitive probes of the long-range interactions that control the growth and morphology of these polymers. As yet, Electronic Circular Dichroism that uses electronic transitions as a probe has by far been the method of choice while Vibrational Circular Dichroism, which uses vibrational transitions to probe structure, is much less employed. Here, we report experimental and theoretical studies of the self-assembly of helical supramolecular polymers of (S)-triarylamine tris-amides ((S)-TATA) in which both techniques are applied in concert. Theoretical studies based on quantum chemical calculations and on simplified models that allow for extrapolation to "infinitely" long polymers provide a solid basis for interpreting results from each of the two techniques that on their own would appear to be contradictory. In the particular case of (S)-TATA it is shown that upon equilibration the initially formed fibers undergo a conformational transition that becomes only "visible" by the combination of the two techniques. Our studies thus show that combining electronic and vibrational domains offers a unique and complementary means to probe these polymers, precisely because they are sensitive to different aspects of molecular and polymeric structure.
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Triarylamine molecules and triarylamine-based covalent polymers have been extensively investigated for more than 60 years in academics and industry because of their intriguing electronic and optical characteristics. However, despite the profusion of studies made on these derivatives, only very recently have the first examples of supramolecular polymers based on the triarylamine motif been described in the literature. Specifically, our research group has shown that, by adding supplementary hydrogen bonding moieties such as amide functions in their periphery, it becomes possible to tightly pack triarylamine molecules in columnar supramolecular stacks presenting a collinear arrangement of their central nitrogen atoms. These supramolecular polymers can self-assemble into various soft hierarchical structures such as helical fibers, nanorods, nanospheres, and nanoribbons in the sol and in the gel states, into liquid-crystalline mesophases, and into highly organized supramolecular frameworks and single crystals thereof. Interestingly, the associated supramolecular polymerization mechanism involves a nucleation step of high activation energy, which requires the flattening of the triarylamine core. Because of this singularity and although dependent on the precise chemical nature of the building blocks, it has been demonstrated that their supramolecular polymerization can be triggered by original tools, such as light irradiation or electrochemistry, and that it can display autocatalytic growth behaviors, remarkably strong amplifications of chirality, and complex and competing thermodynamic and kinetic self-assembly pathways. Further, from a functional point of view, it has been highlighted that a partial oxidation of the triarylamine molecules results in an enhanced through-space delocalization of the charge carriers along the π-π stacked supramolecular polymers, a feature that confers to these nanowires exceptional transport properties. Upon increasing the charge carrier concentration, the electronic nature of these soft materials can be switched from semiconducting to metallic behavior, and the presence of highly delocalized unpaired electrons in supramolecular polaronic band structures has been further exploited to implement plasmonic properties within subwavelength organic interconnects and microscopic optical waveguides. Finally, by making use of the unusual dynamics and functions of triarylamine-based nanostructures, it becomes possible to precisely address their self-construction within confined environments or within nano- and micrometer scale devices. This has been demonstrated for instance between nanoparticles and between electrodes, inside inorganic nanopores, and inside phospholipid bilayers, as well as at the liquid-liquid interface. Such a meeting point between bottom-up and top-down technologies is of high interest to envision further developments and applications for this entirely new class of supramolecular polymers, which combine a unique relationship between their structures, their dynamics, and their subsequent emerging functional properties.
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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.
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Dilute solutions of electronically active molecules capable of irradiation-driven supramolecular self-assembly are studied by dynamic light scattering. We detect unusual well-defined oscillations in the long time range of the homodyne intensity correlation function for all solutions that were irradiated with white light prior to the measurements. The oscillation effect is attributed to the local laser-induced heating of the samples due to strongly enhanced absorption manifested by the supramolecular filaments. It is found that the oscillation frequency depends on the irradiation time, solution concentration, and the incident laser power, but is independent of the scattering angle. These observations are explained with a semi-quantitative theory relating the oscillation effect to thermo-gravitational convection flows generated by laser beam. The results suggest that the presence of such homodyne oscillations could be a sensitive probe for aggregation in many complex systems.
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Happy Birthday! In their editorial, Paolo Samorì and Nicolas Giuseppone introduce our Virtual Collection honoring Professor Jean-Marie Lehn on the occasion of his 80th birthday. This anniversary represents just an excellent excuse to celebrate a most remarkable chemist who has always been far ahead of his time, thanks to a unique combination of scientific visions, creativity, breadth, drive, and dedication.
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C3 -Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π-π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude.
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Upon cooling in solution, chiral triarylamine tris-amide unimers produce organogels by stacking into helical supramolecular polymers, which subsequently bundle into larger fibers. Interestingly, circular dichroism, vibrational circular dichroism, and AFM imaging of the chiral self-assemblies revealed that monocolumnar P-helical fibrils formed upon fast cooling, whereas bundled M-superhelical fibers formed upon slow cooling. The mechanistic study of this structural bifurcation reveals the presence of a strong memory effect, reminiscent of a complex stepwise combination of primary and secondary nucleation-growth processes. These results highlight the instrumental role of sequential self-assembly processes to control supramolecular architectures of multiple hierarchical order.
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The condensation of aldehydes and amines in water to give amphiphilic imines can lead to a particular autocatalytic behavior known as autopoiesis, in which the closed micellar structure made by the amphiphile at the mesoscale can accelerate the condensation of its constituents. Herein, through a combination of analytical tools, including diffusion ordered spectroscopy (DOSY) as well as light, neutron, and X-ray scattering techniques, the thermodynamic and kinetic parameters were probed at both the level of dynamic covalent imine bond formation and the level of the resulting micellar self-assemblies. It was found that the autopoietic behavior was the result of a combination of several parameters, including solubilization of hydrophobic building blocks, template effect at the core-shell interface, and growth/division cycles of the micellar objects.
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Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation-growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature.
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The implementation of artificial molecular machines in polymer science is an important objective that challenges chemists and physicists in order to access an entirely new class of smart materials. To design such systems, the amplification of a mechanical actuation from the nanoscale up to a macroscopic response in the bulk material is a central issue. In this article we show that bistable [c2]daisy chain rotaxanes (i.e., molecular muscles) can be linked into main-chain Upy-based supramolecular polymers. We then reveal by an in depth quantitative study that the pH actuation of the mechanically active rotaxane at the nanoscale influences the physical reticulation of the polymer chains by changing the supramolecular behavior of the Upy units. This nanoactuation within the local structure of the main chain polymer results in a mechanically controlled sol-gel transition at the macroscopic level.
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The implementation of molecular machines in polymer science is of high interest to transfer mechanical motions from nanoscale to macroscale in order to access new kinds of active devices and materials. Toward this objective, thermodynamic and topological aspects need to be explored for reaching efficient systems capable of producing a useful work. In this paper we describe the branched polymerization of pH-sensitive bistable [c2] daisy chain rotaxanes by using copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition ("click chemistry"). With this cross-linked topology, the corresponding materials in the form of chemical gels can be contracted and expanded over a large variation of volume (â¼50%) by changing the protonation state of the system. HR-MAS 1H NMR and neutron scattering experiments reveal that this macroscopic response of the gels results from the synchronized actuation of the mechanical bonds at the molecular level.