Stochastic atomic acceleration during the X-ray-induced fluidization of a silica glass.

The X-ray-induced, nonthermal fluidization of the prototypical SiO2 glass is investigated by X-ray photon correlation spectroscopy in the small-angle scattering range. This process is initiated by the absorption of X-rays and leads to overall atomic displacements which reach at least few nanometers at temperatures well below the glass transition. At absorbed doses of ∼5 GGy typical of many modern X-ray-based experiments, the atomic displacements display a hyperdiffusive behavior and are distributed according to a heavy-tailed, Lévy stable distribution. This is attributed to the stochastic generation of X-ray-induced point defects which give rise to a dynamically fluctuating potential landscape, thus providing a microscopic picture of the fluidization process.

Fluctuation Theorems for Heat Exchanges between Passive and Active Baths.

In addition to providing general constraints on probability distributions, fluctuation theorems allow us to infer essential information on the role played by temperature in heat exchange phenomena. In this numerical study, we measure the temperature of an out-of-equilibrium active bath using a fluctuation theorem that relates the fluctuations in the heat exchanged between two baths to their temperatures. Our setup consists of a single particle moving between two wells of a quartic potential accommodating two different baths. The heat exchanged between the two baths is monitored according to two definitions: as the kinetic energy carried by the particle whenever it jumps from one well to the other and as the work performed by the particle on one of the two baths when immersed in it. First, we consider two equilibrium baths at two different temperatures and verify that a fluctuation theorem featuring the baths temperatures holds for both heat definitions. Then, we introduce an additional Gaussian coloured noise in one of the baths, so as to make it effectively an active (out-of-equilibrium) bath. We find that a fluctuation theorem is still satisfied with both heat definitions. Interestingly, in this case the temperature obtained through the fluctuation theorem for the active bath corresponds to the kinetic temperature when considering the first heat definition, while it is larger with the second one. We interpret these results by looking at the particle jump phenomenology.

Non-Equilibrium Dissipative Assembly with Switchable Biological Functions.

Natural dissipative assembly (DSA) often exhibit energy-driven shifts in natural functions. However, creating man-made DSA that can mimic such biological activities transformation remains relatively rare. Herein, we introduce a cytomembrane-like dissipative assembly system based on chiral supramolecules. This system employs benzoyl cysteine in an out of equilibrium manner, enabling the shifts in biofunctions while minimizing material use. Specifically, aroyl-cystine derivatives primarily assemble into stable M-helix nanofibers under equilibrium conditions. These nanofibers enhance fibroblast adhesion and proliferation through stereospecific interactions with chiral cellular membranes. Upon the addition of chemical fuels, these functional nanofibers temporarily transform into non-equilibrium nanospheres, facilitating efficient drug delivery. Subsequently, these nanospheres revert to their original nanofiber state, effectively recycling the drug. The programmable function-shifting ability of this DSA establishes it as a novel, fuel-driven drug delivery vehicle. And the bioactive DSA not only addresses a gap in synthetic DSAs within biological applications but also sets the stage for innovative designs of 'living' materials.

Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction.

This work reports that the composition of a dynamic library (DL) of interconverting imines can be controlled over time in a dissipative fashion by the addition of an activated carboxylic acid used as a chemical fuel. When the fuel is added to the DL, which is initially under thermodynamic equilibrium, the composition of the mixture dramatically changes and a new, dissipative (out of equilibrium) state is reached that persists until fuel exhaustion. Thus, a transient dissipative dynamic library (DDL) is generated that, eventually, reverts back to the initial DL when the fuel is consumed, closing a DL→DDL→DL cycle. The larger the amount of added fuel, the longer the time spent by the system in the DDL state. The transimination reaction is shown to be an optimal candidate for the realization of a dissipative dynamic covalent chemistry (DDCvC).

Dissipative Formation of Covalent Basket Cages.

Living systems use chemical fuels to transiently assemble functional structures. As a step toward constructing abiotic mimics of such structures, we herein describe dissipative formation of covalent basket cage CBC 5 by reversible imine condensation of cup-shaped aldehyde 2 (i.e., basket) with trivalent aromatic amine 4. This nanosized [4+4] cage (V=5 nm3 , Mw =6150 Da) has shape of a truncated tetrahedron with four baskets at its vertices and four aromatic amines forming the faces. Importantly, tris-aldehyde basket 2 and aliphatic tris-amine 7 undergo condensation to give small [1+1] cage 6. The imine metathesis of 6 and aromatic tris-amine 4 into CBC 5 was optimized to bias the equilibrium favouring 6. Addition of tribromoacetic acid (TBA) as a chemical fuel perturbs this equilibrium to result in the transient formation of CBC 5, with subsequent consumption of TBA via decarboxylation driving the system back to the starting state.

Light-Driven Proton Transfer for Cyclic and Temporal Switching of Enzymatic Nanoreactors.

Temporal activation of biological processes by visible light and subsequent return to an inactive state in the absence of light is an essential characteristic of photoreceptor cells. Inspired by these phenomena, light-responsive materials are very attractive due to the high spatiotemporal control of light irradiation, with light being able to precisely orchestrate processes repeatedly over many cycles. Herein, it is reported that light-driven proton transfer triggered by a merocyanine-based photoacid can be used to modulate the permeability of pH-responsive polymersomes through cyclic, temporally controlled protonation and deprotonation of the polymersome membrane. The membranes can undergo repeated light-driven swelling-contraction cycles without losing functional effectiveness. When applied to enzyme loaded-nanoreactors, this membrane responsiveness is used for the reversible control of enzymatic reactions. This combination of the merocyanine-based photoacid and pH-switchable nanoreactors results in rapidly responding and versatile supramolecular systems successfully used to switch enzymatic reactions ON and OFF on demand.

Organocatalytic Control over a Fuel-Driven Transient-Esterification Network*.

Signal transduction in living systems is the conversion of information into a chemical change, and is the principal process by which cells communicate. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. However, man-made catalytically controlled networks are rare. We incorporated catalysis into an artificial fuel-driven out-of-equilibrium CRN, where the forward (ester formation) and backward (ester hydrolysis) reactions are controlled by varying the ratio of two organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. This fuel-driven strategy was expanded to a responsive polymer system, where transient polymer conformation and aggregation are controlled through fuel and catalyst levels. Altogether, we show that organocatalysis can be used to control a man-made fuel-driven system and induce a change in a macromolecular superstructure, as in natural non-equilibrium systems.

Revising Complex Supramolecular Polymerization under Kinetic and Thermodynamic Control.

Pathway complexity, hierarchical organization, out of equilibrium, and metastable or kinetically trapped species are common terms widely used in recent, high-quality publications in the field of supramolecular polymers. Often, the terminologies used to describe the different self-assembly pathways, the species involved, as well as their relationship and relative stability are not trivial. Different terms and classifications are commonly found in the literature, however, in many cases, without clear definitions or guidelines on how to use them and how to determine them experimentally. The aim of this Minireview is to classify, differentiate, and correlate the existing concepts with the help of recent literature reports to provide the reader with a general insight into thermodynamic and kinetic aspects of complex supramolecular polymerization processes. A good comprehension of these terms and concepts should contribute to the development of new complex, functional materials.

ATP-Mediated Transient Behavior of Stomatocyte Nanosystems.

In nature, dynamic processes are ubiquitous and often characterized by adaptive, transient behavior. Herein, we present the development of a transient bowl-shaped nanoreactor system, or stomatocyte, the properties of which are mediated by molecular interactions. In a stepwise fashion, we couple motility to a dynamic process, which is maintained by transient events; namely, binding and unbinding of adenosine triphosphate (ATP). The surface of the nanosystem is decorated with polylysine (PLL), and regulation is achieved by addition of ATP. The dynamic interaction between PLL and ATP leads to an increase in the hydrophobicity of the PLL-ATP complex and subsequently to a collapse of the polymer; this causes a narrowing of the opening of the stomatocytes. The presence of the apyrase, which hydrolyzes ATP, leads to a decrease of the ATP concentration, decomplexation of PLL, and reopening of the stomatocyte. The competition between ATP input and consumption gives rise to a transient state that is controlled by the out-of-equilibrium process.

Access to Metastable Gel States Using Seeded Self-Assembly of Low-Molecular-Weight Gelators.

Here we report on how metastable supramolecular gels can be formed through seeded self-assembly of multicomponent gelators. Hydrazone-based gelators decorated with non-ionic and anionic groups are formed in situ from hydrazide and aldehyde building blocks, and lead through multiple self-sorting processes to the formation of heterogeneous gels approaching thermodynamic equilibrium. Interestingly, the addition of seeds composing of oligomers of gelators bypasses the self-sorting processes and accelerates the self-assembly along a kinetically favored pathway, resulting in homogeneous gels of which the network morphologies and gel stiffness are markedly different from the thermodynamically more stable gel products. Importantly, over time, these metastable homogeneous gel networks are capable of converting into the thermodynamically more stable state. This seeding-driven formation of out-of-equilibrium supramolecular structures is expected to serve as a simple approach towards functional materials with pathway-dependent properties.

Dissipative Catalysis with a Molecular Machine.

We report on catalysis by a fuel-induced transient state of a synthetic molecular machine. A [2]rotaxane molecular shuttle containing secondary ammonium/amine and thiourea stations is converted between catalytically inactive and active states by pulses of a chemical fuel (trichloroacetic acid), which is itself decomposed by the machine and/or the presence of additional base. The ON-state of the rotaxane catalyzes the reduction of a nitrostyrene by transfer hydrogenation. By varying the amount of fuel added, the lifetime of the rotaxane ON-state can be regulated and temporal control of catalysis achieved. The system can be pulsed with chemical fuel several times in succession, with each pulse activating catalysis for a time period determined by the amount of fuel added. Dissipative catalysis by synthetic molecular machines has implications for the future design of networks that feature communication and signaling between the components.

Seeded Polymerization through the Interplay of Folding and Aggregation of an Amino-Acid-based Diamide.

Amino acid based diamides are widely used as a substructure in supramolecular polymers and are also key components of polypeptides that help to understand protein folding. The interplay of folding and aggregation of a diamide was used to achieve seed-initiated supramolecular polymerization. For that purpose, a pyrene-substituted diamide was synthesized in which pyrene is used as a tracer to monitor the supramolecular polymerization. Thermodynamics and time-dependent studies revealed that the folding of the diamide moiety, via the formation of intramolecular hydrogen bonds, effectively prevents a spontaneous nucleation that leads to supramolecular polymerization. Under such out-of-equilibrium conditions, the addition of seeds successfully initiates the supramolecular polymerization. These results demonstrate the utility of such amino acid based diamides in programmable supramolecular polymerizations.

Pathway Complexity Versus Hierarchical Self-Assembly in N-Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization.

Studies were carried out on the hierarchical self-assembly versus pathway complexity of N-annulated perylenes 1-3, which differ only in the nature of the linking groups connecting the perylene core and the side alkoxy chains. Despite the structural similarity, compounds 1 and 2 exhibit noticeable differences in their self-assembly. Whereas 1 forms an off-pathway aggregate I that converts over time (or by addition of seeds) into the thermodynamic, on-pathway product, 2 undergoes a hierarchical process in which the kinetically trapped monomer species does not lead to a kinetically controlled supramolecular growth. Finally, compound 3, which lacks the amide groups, is unable to self-assemble under identical experimental conditions and highlights the key relevance of the amide groups and their position to govern the self-assembly pathways.

Out-of-Equilibrium Mechanical Disruption of ß-Amyloid-Like Fibers using Light-Driven Molecular Motors.

Artificial molecular motors have the potential to generate mechanical work on their environment by producing autonomous unidirectional motions when supplied with a source of energy. However, the harnessing of this mechanical work to subsequently activate various endoenergetic processes that can be useful in materials science remains elusive. Here, it is shown that by integrating a light-driven rotary motor through hydrogen bonds in a ß-amyloid-like structure forming supramolecular hydrogels, the mechanical work generated during the constant rotation of the molecular machine under UV irradiation is sufficient to disrupt the ß-amyloid fibers and to trigger a gel-to-sol transition at macroscopic scale. This melting of the gel under UV irradiation occurs 25 °C below the temperature needed to melt it by solely using thermal activation. In the dark, a reversible sol-gel transition is observed as the system fully recovers its original microstructure, thus illustrating the possible access to new kinds of motorized materials that can be controlled by advanced out-of-equilibrium thermodynamics.

Bioinspired Self-Resettable Hydrogel Actuators Powered by a Chemical Fuel.

The movements of soft living tissues, such as muscle, have sparked a strong interest in the design of hydrogel actuators; however, so far, typical manmade examples still lag behind their biological counterparts, which usually function under nonequilibrium conditions through the consumption of high-energy biomolecules and show highly autonomous behaviors. Here, we report on self-resettable hydrogel actuators that are powered by a chemical fuel and can spontaneously return to their original states over time once the fuels are depleted. Self-resettable actuation originates from a chemical fuel-mediated transient change in the hydrophilicity of the hydrogel networks. The actuation extent and duration can be programmed by the fuel levels, and the self-resettable actuation process is highly recyclable through refueling. Furthermore, various proof-of-concept autonomous soft robots are created, resembling the movements of soft-bodied creatures in nature. This work may serve as a starting point for the development of lifelike soft robots with autonomous behaviors.

Driven quantum many-body systems and out-of-equilibrium topology.

In this review we present some of the work done in India in the area of driven and out-of-equilibrium systems with topological phases. After presenting some well-known examples of topological systems in one and two dimensions, we discuss the effects of periodic driving in some of them. We discuss the unitary as well as the non-unitary dynamical preparation of topologically non-trivial states in one and two dimensional systems. We then discuss the effects of Majorana end modes on transport through a Kitaev chain and a junction of three Kitaev chains. Following this, transport through the surface states of a three-dimensional topological insulator has also been reviewed. The effects of hybridization between the top and bottom surfaces in such systems and the application of electromagnetic radiation on a strip-like region on the top surface are described. Two unusual topological systems are mentioned briefly, namely, a spin system on a kagome lattice and a Josephson junction of three superconducting wires. We have also included a pedagogical discussion on topology and topological invariants in the appendices, where the connection between topological properties and the intrinsic geometry of many-body quantum states is also elucidated.

Vision Statement: Interactive Materials-Drivers of Future Robotic Systems.

A robot senses its environment, processes the sensory information, acts in response to these inputs, and possibly communicates with the outside world. Robots generally achieve these tasks with electronics-based hardware or by receiving inputs from some external hardware. In contrast, simple microorganisms can autonomously perceive, act, and communicate via purely physicochemical processes in soft material systems. A key property of biological systems is that they are built from energy-consuming "active" units. Exciting developments in material science show that even very simple artificial active building blocks can show surprisingly rich emergent behaviors. Active nonequilibrium systems are therefore predicted to play an essential role in realizing interactive materials. A major challenge is to find robust ways to couple and integrate the energy-consuming building blocks to the mechanical structure of the material. However, success in this endeavor will lead to a new generation of sophisticated micro and soft-robotic systems that can operate autonomously.

Fluctuating Dynamics of Nanoscale Chemical Oscillations: Theory and Experiments.

Chemical oscillations are observed in a variety of reactive systems, including biological cells, for the functionality of which they play a central role. However, at such scales, molecular fluctuations are expected to endanger the regularity of these behaviors. The question of the mechanism by which robust oscillations can nevertheless emerge is still open. In this work, we report on the experimental investigation of nanoscale chemical oscillations observed during the NO2 + H2 reaction on platinum, using field electron microscopy. We show that the correlation time and the variance of the period of oscillations are connected by a universal constraint, as predicted theoretically for systems subjected to a phenomenon called phase diffusion. These results open the way to a better understanding, modeling, and control of nanoscale oscillators.