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We describe the thermodynamics of a solution of rotaxanes which can change their length from a short state of length L to a long state of length qL in response to their surrounding environment. We call these rotaxanes "adaptive." We show that such a system can exhibit both isotropic and nematic liquid crystalline phases. The system shows several interesting kinds of behaviour. First we predict that the fraction of short-length rotaxanes increases linearly with concentration and is a maximum at the critical concentration that marks the isotropic to nematic transition. Second, the critical concentration shows a minimum at a certain value of q. Our model suggests that the effect of adaptive length changes is most dramatic at small q and where the long state is slightly favoured. [ABSTRACT FROM AUTHOR]

We examine a simple model of rotaxane structure, with 3 asymmetric rings interacting via repulsive power-law forces. This interlocked molecule exhibits conformational isomerisation which is different from that of molecules whose connectedness is through covalent bonds. The rings are free to translate along and rotate around the axle, and hence weak interaction forces between the rings can lead to distinct rotamer states. We use energy minimisation to determine these states exactly, and show that there can be transitions from asymmetric to symmetric states by varying the bond lengths. We also use classical statistical mechanics to show the effect of thermal noise. [ABSTRACT FROM AUTHOR]

Laser-induced cross-linking of polyynes is successfully hindered when the polyyne is encapsulated as part of a rotaxane and therefore protected by a surrounding macrocycle. When the rotaxane is electrosprayed, however, noncovalent aggregate ions are efficiently formed. Aggregates of considerable size (including more than 50 rotaxane molecules with masses beyond 100k Da) and charge states (up to 13 charges and beyond) have been observed. Either protons or sodium cations act as the charge carriers. These aggregates are not formed when the individual components of the rotaxane, i.e., the macrocycle or the polyyne, are separately electrosprayed. This underlines the structural importance of the rotaxane for the aggregate formation. Straightforward force field calculations indicate that the polyyne thread hinders the folding of the macrocycles, which facilitates the bonding interaction between the two components. [ABSTRACT FROM AUTHOR]

We describe the thermodynamics of a solution of rotaxanes which can change their length from a short state of length L to a long state of length qL in response to their surrounding environment. We call these rotaxanes "adaptive." We show that such a system can exhibit both isotropic and nematic liquid crystalline phases. The system shows several interesting kinds of behaviour. First we predict that the fraction of short-length rotaxanes increases linearly with concentration and is a maximum at the critical concentration that marks the isotropic to nematic transition. Second, the critical concentration shows a minimum at a certain value of q. Our model suggests that the effect of adaptive length changes is most dramatic at small q and where the long state is slightly favoured.

We use steady-state and nanosecond time-resolved photoluminescence spectroscopy to investigate the evolution of packing interactions in dilute solutions of a sulfonated poly(diphenylenevinylene) lithium salt and its cyclodextrin-threaded polyrotaxanes as a function of the threading ratio (TR) when increasing the temperature from 10 to 40°C. Contrary to the expectation of a temperature-induced increase of packing and aggregation, supported by previous Raman studies identifying a temperature-induced reduction in the inter-phenyl torsion angles, we find clear spectral (photoluminescence blue-shift and narrowing) and dynamic (shorter lifetimes and reduced weight of the long-lived components) signatures of a reduction of interchain interactions for the polyelectrolytes at higher temperatures with TR up to 1.3. [ABSTRACT FROM AUTHOR]

Polyrotaxanes (PR) have attracted great interest due to their unique mechanical properties, exhibiting the pulley effect, via their slide-ring topological structure. Flexible and functional composite materials consisting of PR and inorganic particles, particularly those with plasma-surface modifications, have also shown higher toughness, even with large amounts of inorganic particles present. In this study, we verified the effect of neat PR and its composites with graphene nanoplates or carbon nanofibers by measuring acoustic emission (AE). Simultaneous AE and tensile measurements were tested several times for each sample, and AE signals during elongation were acquired. It revealed that the conventional fixed cross-linked elastomer materials showed AE signals in the entire tensile region, while the movable-cross-linked materials of PR showed almost no AE signal counts. This suggests that neat PR had almost no microscopic fracture before final breakage via the pulley effect. PR composites with plasma-surface-modified fillers showed a lower number of AE signals than that with unmodified fillers. This might be due to the surface modification of fillers, which improved filler dispersibility and/or prevented a large drop in the mobility of cross-linking points. [ABSTRACT FROM AUTHOR]

The photophysics and electroluminescence (EL) of thin films of unthreaded and cyclodextrin-encapsulated poly(4,4′-diphenylenevinylene) (PDV) with potassium countercations, blended with poly(ethylene oxide) (PEO) are investigated as a function of the PEO concentration. We show that three main factors contribute to increasing the photoluminescence (PL) quantum efficiency as a result of suppressed intermolecular interactions, namely: the high degree of encapsulation of the polyrotaxanes, the relatively large countercation (e.g., compared to lithium), and the complexation of the rotaxanes with PEO. By facilitating cationic transport to the negative electrodes, PEO also leads to devices with enhanced electron injection and improved charge balance, whose operation therefore resembles that of “virtually unipolar” light-emitting electrochemical cells. This effect, together with the enhanced PL efficiency, leads to higher EL efficiency for both polyrotaxanes and unthreaded polymers, upon addition of the PEO. We show that the concurrent exploitation of the various strategies above lead to an overall EL efficiency that is approximately twice the value previously reported for Li-based PDV. A blueshift of the EL spectrum during the devices turn-on is also reported and analyzed in terms of interference and doping effects. [ABSTRACT FROM AUTHOR]

We examine a solution of non-adaptive two-state rotaxane molecules which can switch from a short state of length L to a long state of length qL, using statistical thermodynamics. This molecular switching is externally driven and can result in an isotropic-nematic phase transition without altering temperature and concentration. Here we concentrate on the limitation imposed by switching inefficiency, i.e., on the case where molecular switching is not quantitative, leading to a solution of rotaxanes in different states. We present switching diagrams that can guide in the design of rotaxanes which affect a macroscopic phase change. [ABSTRACT FROM AUTHOR]

We have investigated the dynamics of the hydrogen bonds that connect the components of a [2]rotaxane in solution. In this rotaxane, the amide groups in the benzylic-amide macrocycle and the succinamide thread are connected by four equivalent N-H···O=C hydrogen bonds. The fluctuations of these hydrogen bonds are mirrored by the frequency fluctuations of the NH-stretch modes, which are probed by means of three-pulse photon-echo peak shift spectroscopy. The hydrogen-bond fluctuations occur on three different time scales, with time constants of 0.1, 0.6, and >=200 ps. Comparing these three time scales to the ones found in liquid formamide, which contains the same hydrogen-bonded amide motif but without mechanical constraints, we find that the faster two components, which are associated with small-amplitude fluctuations in the strength of the N-H···O=C hydrogen bonds, are very similar in the liquid and the rotaxane. However, the third component, which is associated with the breaking and subsequent reformation of hydrogen bonds, is found to be much slower in the rotaxane than in the liquid. It can be concluded that the mechanical bonding in a rotaxane does not influence the amplitude and time scale of the small-amplitude fluctuations of the hydrogen bonds, but strongly slows down the complete dissociation of these hydrogen bonds. This is probably because in a rotaxane breaking of the macrocycle-axle contacts is severely hindered by the mechanical constraints. The hydrogen-bond dynamics in rotaxane-based molecular machines can therefore be regarded as liquidlike on a time scale 1 ps and less, but structurally frozen on longer (up to at least 200 ps) time scales. [ABSTRACT FROM AUTHOR]

Physical systems often respond on a timescale which is longer than that of the measurement. This is particularly true in soft matter where direct experimental measurement, for example in force spectroscopy, drives the soft system out of equilibrium and provides a non-equilibrium measure. Here we demonstrate experimentally for the first time that equilibrium physical quantities (such as the mean square displacement) can be obtained from non-equilibrium measurements via umbrella sampling. Our model experimental system is a bead fluctuating in a time-varying optical trap. We also show this for simulated force spectroscopy on a complex soft molecule-a piston-rotaxane. [ABSTRACT FROM AUTHOR]

An analytic gradient expression is formulated and implemented for the second-order Mo\ller–Plesset perturbation theory (MP2) based on the generalized hybrid orbital QM/MM method. The method enables us to obtain an accurate geometry at a reasonable computational cost. The performance of the method is assessed for various isomers of alanine dipepetide. We also compare the optimized structures of fumaramide-derived [2]rotaxane and cAMP-dependent protein kinase with experiment. [ABSTRACT FROM AUTHOR]

We use molecular dynamics simulations to investigate the effect of mechanical force on stimulus-induced deformation of rotaxane-based artificial molecular muscles. The study shows that a small external force slows down the shuttling motion and leads to longer actuation time for a muscle to reach its full extension. Further increase in the force can significantly reduce the traveling distance of the ring, leading to reduced strain output. A force larger than 28 pN can completely suppress the shuttling motion, suggesting a limit of force output of molecular muscles. [ABSTRACT FROM AUTHOR]

An array of microcantilever beams, coated with a self-assembled monolayer of bistable, redox-controllable [3]rotaxane molecules, undergoes controllable and reversible bending when it is exposed to chemical oxidants and reductants. Conversely, beams that are coated with a redox-active but mechanically inert control compound do not display the same bending. A series of control experiments and rational assessments preclude the influence of heat, photothermal effects, and pH variation as potential mechanisms of beam bending. Along with a simple calculation from a force balance diagram, these observations support the hypothesis that the cumulative nanoscale movements within surface-bound “molecular muscles” can be harnessed to perform larger-scale mechanical work. [ABSTRACT FROM AUTHOR]

Computational software workflows are emerging as all-in-one solutions to speed up the discovery of new materials. Many computational approaches require the generation of realistic structural models for property prediction and candidate screening. However, molecular and supramolecular materials represent classes of materials with many potential applications for which there is no go-to database of existing structures or general protocol for generating structures. Here, we report a new version of the supramolecular toolkit, stk, an open-source, extendable, and modular Python framework for general structure generation of (supra)molecular structures. Our construction approach works on arbitrary building blocks and topologies and minimizes the input required from the user, making stk user-friendly and applicable to many material classes. This version of stk includes metal-containing structures and rotaxanes as well as general implementation and interface improvements. Additionally, this version includes built-in tools for exploring chemical space with an evolutionary algorithm and tools for database generation and visualization. The latest version of stk is freely available at github.com/lukasturcani/stk. [ABSTRACT FROM AUTHOR]

Investigating the role of chiral-induced spin selectivity in the generation of spin correlated radical pairs in a photoexcited donor–chiral bridge–acceptor system is fundamental to exploit it in quantum technologies. This requires a minimal master equation description of both charge separation and recombination through a chiral bridge. To achieve this without adding complexity and entering in the microscopic origin of the phenomenon, we investigate the implications of spin-polarizing reaction operators to the master equation. The explicit inclusion of coherent evolution yields non-trivial behaviors in the charge and spin dynamics of the system. Finally, we apply this master equation to a setup comprising a molecular qubit attached to the donor–bridge–acceptor molecule, enabling qubit initialization, control, and read-out. Promising results are found by simulating this sequence of operations assuming realistic parameters and achievable experimental conditions. [ABSTRACT FROM AUTHOR]

Moreover, they illustrate the wide range of available tools, including crystal structure prediction (CSP) methods,[[11]] high-throughput calculations,[[13]] and machine learning (ML),[[15], [17]] and the role that databases, such as AFLOW,[19] Materials Project,[20] the Open Quantum Materials Database,[21] the Computational Materials Repository,[22] and the International Crystallographic Structure Database,[23] among many others, play in materials discovery. Tremendous advances in first-principles program packages, spectacular speed-ups in computer hardware coupled with significant algorithmic developments in crystal structure prediction, high-throughput screenings, data-mining, machine learning (ML), and artificial intelligence have made the dream of computational materials discovery a reality.[1] Recent success stories of materials that were first predicted and later verified experimentally include high-temperature superconductors,[[2], [4]] high-entropy high-hardness materials,[5] Heusler intermetallics for thermoelectrics and spintronics,[6] organic light-emitting diodes,[7] Li battery cathode materials,[8] porous materials for gas storage,[9] and carbon-boron clathrates.[10] The broad range of materials-by-design success stories with applications, including energy, quantum, structural, 2D materials, molecular crystals, molecular organic frameworks, and so on, have inspired us to devote this issue of JCP toward recent advances in this field. Parsaeifard I et al. i present a method to calculate fingerprint vectors from fingerprint distances, which measure the similarity of two structures.[27] This method is shown to automatically detect grain boundaries and the edges of carbon flakes without human input. [Extracted from the article]

Recently we described a coarse-grained model of poly(ethylene oxide) and then employed that model to study the amount of spontaneous threading of cyclic molecules by linear chains in the melt [C. A. Helfer, G. Xu, W. L. Mattice, and C. Pugh, Macromolecules 36, 10071 (2003)]. Since the amount of statistical threading at equilibrium is small, there is interest in identifying physical changes in the system that will increase the threading. We now use that coarse-grained model to investigate the effect on threading of various hypothetical (but feasible) modifications to the two-component system of macrocycles and linear chains in the melt, and different confinement geometries, that can bring about correlations in the arrangement of the rings. Our work follows on the concept of an amphiphilic approach [C. Pugh, J.-Y. Bae, J. R. Scott, and C. L. Wilkins, Macromolecules 30, 8139 (1997)] for increasing the statistical threading in homopolyrotaxane melts. We investigate whether introducing such correlations in the macrocycles can increase the spontaneous threading. This paper shows that some of our modifications can yield more than double the amount of threading seen in purely statistical mixing. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Single molecule (SM) chips could serve as the fundamental devices in quantum information processing. In this context, a chip with the non-polar SMs of squaraine-derived rotaxanes embedded in a polar poly(methyl methacrylate) matrix was realized and the SM fluorescence hysteresis induced by the electric field was observed at room temperature. Here, we presented a model considering both of the electron transfer and space charge relaxation processes to explain the fluorescence hysteresis effect, and the model-based simulations agreed reasonably well with the experimental results. [ABSTRACT FROM AUTHOR]

We review recent advances in the design, synthesis, and modeling of active fluids. Active fluids have been at the center of many technological innovations and theoretical advances over the past two decades. Research on this new class of fluids has been inspired by the fascinating and remarkably efficient strategies that biological systems employ, leading to the development of biomimetic nano- and micro-machines and swimmers. The review encompasses active fluids on both the nano- and micro-scale. We start with examples of biological active systems before we discuss how experimentalists leverage novel propulsion mechanisms to power nano- and micro-machines. We then examine how the study of these far-from-equilibrium systems has prompted the development of new simulation methods and theoretical models in nonequilibrium physics to account for their mechanical, thermodynamic, and emergent properties. Recent advances in the field have paved the way for the design, synthesis, and modeling of autonomous systems at the nano- and micro-scale and opened the door to the development of soft matter robotics. [ABSTRACT FROM AUTHOR]

We present a detailed study of the parameter dependence of force probe molecular dynamics (FPMD) simulations. Using a well studied calix[4]arene catenane dimer as a model system, we systematically vary the pulling velocity and the stiffness of the applied external potential. This allows us to investigate how the results of pulling simulations operating in the constant velocity mode (force-ramp mode) depend on the details of the simulation setup. The system studied has the further advantage of showing reversible rebinding meaning that we can monitor the opening and the rebinding transition. Many models designed to extract kinetic information from rupture force distributions work in the limit of soft springs and all quantities are found to depend solely on the so-called loading rate, the product of spring stiffness and pulling velocity. This approximation is known to break down when stiff springs are used, a situation often encountered in molecular simulations. We find that while some quantities only depend on the loading rate, others show an explicit dependence on the spring constant used in the FPMD simulation. In particular, the force versus extension curves show an almost stiffness independent rupture force but the force jump after the rupture transition does depend roughly linearly on the value of the stiffness. The kinetic rates determined from the rupture force distributions show a dependence on the stiffness that can be understood in terms of the corresponding dependence of the characteristic forces alone. These dependencies can be understood qualitatively in terms of a harmonic model for the molecular free energy landscape. It appears that the pulling velocities employed are so large that the crossover from activated dynamics to diffusive dynamics takes place on the time scale of our simulations. We determine the effective distance of the free energy minima of the closed and the open configurations of the system from the barrier via an analysis of the hydrogen-bond network with results in accord with earlier simulations. We find that the system is quite brittle in the force regime monitored in the sense that the barrier is located near to the closed state. [ABSTRACT FROM AUTHOR]

Artificial magnetic molecules can contribute to progressing toward large scale quantum computation by (a) integrating multiple quantum resources and (b) reducing the computational costs of some applications. Chemical design, guided by theoretical proposals, allows embedding nontrivial quantum functionalities in each molecular unit, which then acts as a microscopic quantum processor able to encode error protected logical qubits or to implement quantum simulations. Scaling up even further requires "wiring-up" multiple molecules. We discuss how to achieve this goal by the coupling to on-chip superconducting resonators. The potential advantages of this hybrid approach and the challenges that still lay ahead are critically reviewed. [ABSTRACT FROM AUTHOR]

Nanoscale molecular-electronic devices comprising a single molecular monolayer of bistable [2]rotaxanes sandwiched between two 40-nm metal electrodes were fabricated using imprint lithography. Bistable current-voltage characteristics with high on-off ratios and reversible switching properties were observed. Such devices may function as basic elements for future ultradense electronic circuitry. [ABSTRACT FROM AUTHOR]

The integration of molecular robots and synthetic biology allows for the creation of sophisticated behaviors at the molecular level. Similar to the synergy between bioelectronics and soft robotics, synthetic biology provides control circuitry for molecular robots. By encoding perception-action modules within synthetic circuits, molecular machines can advance beyond repeating tasks to the incorporation of complex behaviors. In particular, cell-free synthetic biology provides biomolecular circuitry independent of living cells. This research update reviews the current progress in using synthetic biology as perception-action control modules in robots from molecular robots to macroscale robots. Additionally, it highlights recent developments in molecular robotics and cell-free synthetic biology and suggests their combined use as a necessity for future molecular robot development. [ABSTRACT FROM AUTHOR]

The double excitation multi-stability and Shilnikov-type multi-pulse jumping chaotic vibrations are analyzed for the bistable asymmetric laminated composite square panel under foundation force for the first time. Based on the extended new high-dimensional Melnikov function, the explicit sufficient conditions are obtained for the existence of the Shilnikov-type multi-pulse jumping homoclinic orbits and chaotic vibrations in the bistable asymmetric laminated composite square panel, which implies that multi-pulse jumping chaotic vibrations may occur in the sense of Smale horseshoes. The extended new high-dimensional Melnikov function gives the parameters domain of the intersection for the homoclinic orbits, which illustrates the relationship among the coefficients of damping, parametric, and external excitations. Numerical simulations including the bifurcation diagrams, largest Lyapunov exponents, phase portraits, waveforms, and Poincaré sections are utilized to study the double excitation multi-pulse jumping and metastable chaotic vibrations and dynamic snap-through phenomena. The numerical results demonstrate that double excitation Shilinikov multi-pulse jumping chaotic and small metastable chaotic vibrations coexist in the bistable asymmetric laminated composite square panel. It is found that the external excitation changes the complexity of the chaos, while the parameter excitation changes the type of chaos. It is verified that the bistable asymmetric laminated composite square panel with small damping is easier to produce double excitation Shilinikov multi-pulse jumping chaotic vibrations. [ABSTRACT FROM AUTHOR]

The thermodynamic driving force in the folding of a class of oligorotaxanes is elucidated by means of molecular dynamics simulations of equilibrium isometric single-molecule force spectroscopy by atomic force microscopy experiments. The oligorotaxanes consist of cyclobis(paraquat-p-phenylene) rings threaded onto an oligomer of 1,5-dioxynaphthalenes linked by polyethers. The simulations are performed in a high dielectric medium using MM3 as the force field. The resulting force versus extension isotherms show a mechanically unstable region in which the molecule unfolds and, for selected extensions, blinks in the force measurements between a high-force and a low-force regime. From the force versus extension data the molecular potential of mean force is reconstructed using the weighted histogram analysis method and decomposed into energetic and entropic contributions. The simulations indicate that the folding of the oligorotaxanes is energetically favored but entropically penalized, with the energetic contributions overcoming the entropy penalty and effectively driving the folding. In addition, an analogy between the single-molecule folding/unfolding events driven by the atomic force microscope (AFM) tip and the thermodynamic theory of first-order phase transitions is discussed. General conditions (on the molecule and the AFM cantilever) for the emergence of mechanical instabilities and blinks in the force measurements in equilibrium isometric pulling experiments are also presented. In particular, it is shown that the mechanical stability properties observed during the extension are intimately related to the fluctuations in the force measurements. [ABSTRACT FROM AUTHOR]

We consider a system of two coupled Brownian particles fluctuating between two states. The fluctuations are produced by both equilibrium thermal and external nonthermal noise, the transition rates depending on the interparticle distance. An externally induced modulation of the transition rates acts on the internal degree of freedom (the interparticle distance) and generates reciprocating motion along this coordinate. The system moves unidirectionally due to rectification of the internal motion by asymmetric friction fluctuations and thus operates as a dimeric motor that converts input energy into net movement. The properties of the motor are primarily determined by the properties of the reciprocating engine, represented by the interparticle distance dynamics. Two main mechanisms are recognized by which the engine operates: energetic and informational. In the physically important cases where only one of the motion-inducing mechanisms is operative, exact solutions can be found for the model with linearly coupled particles. We focus on the informational mechanism, in which thermal noise is involved as a vital component and the reciprocating velocity exhibits a rich behavior as a function of the model parameters. An efficient rectification method for the reciprocating motion is also discussed. [ABSTRACT FROM AUTHOR]

In a three-component system containing dibenzo-24-crown-8 (1), diamino-dibenzo-24-crown-8 (2), and 1,2-bis(4,4′-dipyridyl)ethane (32+), axle 32+ can shuttle between wheels 1 and 2 by acid-base control, accompanying color changes from yellow to red. This system could not only be taken as a chromophoric supramolecular switch, but also exhibit a function as INHIBIT logic gate. [ABSTRACT FROM AUTHOR]

Thin films of fumaramide [2]rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a “bead and thread” configuration, were prepared by vapor deposition on both Ag(111) and Au(111) substrates. X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide [2]rotaxane adsorption on Au(111), the presence of certain out-of-plane phenyl ring and Au–O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide [2]rotaxane and the Ag(111) or Au(111) surface. [ABSTRACT FROM AUTHOR]

Uses molecular dynamics calculations in determining the mechanical resistance of a polyethylene strand subject to tension. Description of how its properties are affected by the presence of a knot; Distribution of strain energy for the knotted chains having a well-defined shape; Factors affecting the weakness of the presence of a knot.

Studies the mean field theory of interpenetrating polymer network (IPN) gels. Relevant order parameters of IPN-gels obtained as the local composition ratio fluctuations; Study of the microphase separation and volume phase transition; Existence of a common critical point at which the IPN-gel becomes critical for the phase transitions.

Silicon MEMS cantilevers coated with a 200nm thin layer of the molecular spin crossover complex [Fe(H2B(pz)2)2(phen)] (H2B(pz)2=dihydrobis(pyrazolyl)borate and phen=1,10-phenantroline) were actuated using an external magnetic field and their resonance frequency was tracked by means of integrated piezoresistive detection. The light-induced spin-state switching of the molecules from the ground low spin to the metastable high spin state at 10K led to a well-reproducible shift of the cantilever's resonance frequency (Δfr=-0.52 Hz). Control experiments at different temperatures using coated as well as uncoated devices along with simple calculations support the assignment of this effect to the spin transition. This latter translates into changes in mechanical behavior of the cantilever due to the strong spin-state/lattice coupling. A guideline for the optimization of device parameters is proposed so as to efficiently harness molecular scale movements for large-scale mechanical work, thus paving the road for nanoelectromechanical systems (NEMS) actuators based on molecular materials. [ABSTRACT FROM AUTHOR]

Starting from a given topological invariant, we argue that it is possible to construct a topological field theory with a finite number of Feynman diagrams and an amplitude of gauge invariant objects that is a function of that invariant. This is, for example, the case of the Gauss linking number and of the abelian BF models which have been already successfully applied in the statistical mechanics of polymers. In this work it is shown that a suitable generalization of the BF model can be applied also to polymer dynamics, where the polymer trajectories are not static, but change their shape during time. [ABSTRACT FROM AUTHOR]

Self-propelled nanomotors use chemical energy to produce directed motion. Like many molecular motors they suffer strong perturbations from the environment in which they move as a result of thermal fluctuations and do not rely on inertia for their propulsion. Such tiny motors are the subject of considerable research because of their potential applications, and a variety of synthetic motors have been made and are being studied for this purpose. Chemically powered self-propelled nanomotors without moving parts that rely on asymmetric chemical reactions to effect directed motion are the focus of this article. The mechanisms they use for propulsion, how size and fuel sources influence their motion, how they cope with strong molecular fluctuations, and how they behave collectively are described. The practical applications of such nanomotors are largely unrealized and the subject of speculation. Since molecular motors are ubiquitous in biology and perform a myriad of complex tasks, the hope is that synthetic motors might be able to perform analogous tasks. They may have the potential to change our perspective on how chemical dynamics takes place in complex systems. [ABSTRACT FROM AUTHOR]

A study is presented on how encapsulation of conjugated polymer chains affects the motion of photoexcitations and the formation of interchain aggregates in solid films. It is shown that threading of a poly(diphenylene vinylene) backbone inside insulating cyclodextrins (rotaxination) and/or complexation of the chains with poly(ethylene oxide) are effective means of preventing the diffusion of excitons to nonradiative defect sites. Ultrafast time-resolved photoluminescence data reveal that excitation transfer between encapsulated chains is still possible and, for the case of rotaxination, is likely to be facilitated through close packing of end groups belonging to adjacent chains. [ABSTRACT FROM AUTHOR]

We investigate the functionalization of gold anodes with azobenzene-based self-assembled monolayers (AZO-SAM) and the influence of such functionalization on the external quantum efficiency (EQE) of polyfluorene-based light-emitting diodes (LEDs). Photoluminescence and electroluminescence measurements show that the AZO-SAMs do not modify the shape of the emission spectrum of the active layer. Instead, AZO-SAMs enhance the EQE of LEDs by an order of magnitude (from 0.018% to 0.18%) and decrease the turn-on voltage from 7.9 V to 6.2 V by reducing the injection barrier at the anode, thus promoting a better balance between hole and electron populations in the active layer. [ABSTRACT FROM AUTHOR]