Quantum integrability and chaos in a periodic Toda lattice with balanced loss-gain.

We consider an equal-mass quantum Toda lattice with balanced loss-gain for two and three particles. The two-particle Toda lattice is integrable, and two integrals of motion that are in involution have been found. The bound-state energy and the corresponding eigenfunctions have been obtained numerically for a few low-lying states. The three-particle quantum Toda lattice with balanced loss-gain and velocity-mediated coupling admits mixed phases of integrability and chaos depending on the value of the loss-gain parameter. We have obtained analytic expressions for two integrals of motion that are in involution. Although an analytic expression for the third integral has not been found, the numerical investigation suggests integrability below a critical value of the loss-gain strength and chaos above this critical value. The level spacing distribution changes from the Wigner-Dyson to the Poisson distribution as the loss-gain parameter passes through this critical value and approaches zero. An identical behavior is seen in terms of the gap-ratio distribution of the energy levels. The existence of mixed phases of quantum integrability and chaos in the specified ranges of the loss-gain parameter has also been confirmed independently via the study of level repulsion and complexity in higher order excited states.

An embedded interface regulates the underwater actuation of solvent-responsive soft grippers.

In this work, we report the role of an embedded interface between two polymer thin films in determining the overall folding and actuation characteristics of a bilayer system applied for gripping submerged objects. Along with the material properties and geometry of the individual films involved, the strength of the embedded interface governs the folding behaviour of the bilayer when exposed to a solvent. The concentration gradient developed across the film thickness when exposed to the solvent results in the deformation of the film. The evolution of concentration through the film thickness as a function of time is closely related to the interface strength. It affects various aspects of the deformation, such as the direction of folding, curvature attained, and actuation rate. In this work, we have varied the strength of the interface between solvent responsive chitosan and hydrophobic Poly(methyl-methacrylate) (PMMA) by treating the substrate (chitosan) with varying concentrations of silane before coating. Experimentally, the folding characteristics of the solvent responsive bilayer films have been investigated for four different interfacial strengths. A coupled diffusion-deformation model for the film and a cohesive zone model for the interface is developed to provide insights into the underlying mechanism behind the observations made. Finally, the application of the bilayer as a gripper for submerged objects for two different types of interfaces is demonstrated. Interestingly, in this approach, the medium where the object is immersed acts as a trigger for folding the grippers.

Intrinsic-water desorption induced thermomechanical response of hydrogels.

We report an interplay between the desorption of intrinsic water and relaxation of polymer chains resulting in an unusual thermomechanical response of a hydrogel, wherein the elastic modulus increases in a certain temperature range followed by a sharp decrease with a further increase in temperature. We establish that, in a hydrogel, the desorption of disparate water types having distinct binding energy affects the consolidation and relaxation behaviour of the matrix, which in turn affects the mechanical properties at different temperature ranges. Using temperature-dependent dielectric relaxation spectroscopy and nanoindentation techniques, the chain dynamics and mechanical properties are investigated.

Engineering polymer film porosity for solvent triggered actuation.

We report a novel approach for the fabrication of porous polymer films and their self-folding behavior in response to water. In this approach, the poly(vinyl alcohol) (PVA) films of tunable porosity are prepared by direct casting of aqueous PVA solution into a nonsolvent, isopropyl alcohol (IPA). The method developed is simple, efficient and low-cost. The results presented provide a modular route to tune the distribution of pores across the film thickness by varying the volume of nonsolvent and the polymer solution. We show that asymmetric porous polymer films (which consist of pores across a certain thickness of the film in the plane perpendicular to its surface) as well as symmetric porous polymer films (which have pores across the entire film) can be fabricated by this versatile method. The percentage of pores in the polymer film calculated as , where tp is the thickness of the film across which the pores exist and ttotal is the total thickness of the film, can be tuned over a wide range. The emanated porous PVA films are found to show self-folding behaviour in response to water. Our results indicate that the pore architecture in the films significantly enhances the actuation speed. The self-folding originating due to the diffusion of water molecules across the film is observed to occur in a controlled and predictable manner for the films with 60% pores and above. A detailed study of the folding characteristics and actuation speed in relation to folding time is substantiated.

Controlled shape morphing of solvent free thermoresponsive soft actuators.

High performance thermoresponsive soft, controllable and reversible actuators are highly desirable for diverse applications. The practical implementation of the existing poly(N-isopropylacrylamide) (pNipam) based soft thermoresponsive actuators faces serious limitations due to their functional requirement of proximal bulk solvent medium. In this work, addressing this issue, we report the development of a bilayer based actuator composed of a solvent responsive biodegradable polymer and temperature responsive pNipam. The designed bilayer is capable of achieving reversible and irreversible actuation as needed when exposed to a physiological range of body temperature, without any solvent bath around. The solvent or water supplied by the pNipam layer at its lower critical solution temperature (LCST) builds a concentration gradient across the thickness of the polymer layer. The concentration gradient results in a strain gradient, causing an out-of-plane folding of the bilayer. The underlying coupled diffusion-deformation interaction during folding and unfolding is incorporated in the reported finite element model, capable of predicting actuation characteristics under different initial conditions. The combined experimental and modelling effort in this work highlights the possibility of engineering 2-dimensional films into complex 3-dimensional shapes, which could have potential applications in soft machines and robotics.

Solvent triggered irreversible shape morphism of biopolymer films.

We report the controlled reversible and irreversible folding behavior of a biopolymer film simply by tuning the solvent characteristics. Generally, solvent triggered folding of soft membranes or film is achieved by unfolding. Here, we show that this unfolding behavior can be suppressed/delayed or even completely eliminated by altering the intrinsic nature of the solvent. A reversible folding of biopolymer film is observed in response to water, whereas, an irreversible folding is observed in the presence of an aromatic alcohol (AA) solution of different molar concentrations. The folding and unfolding behavior originates from the coupled deformation-diffusion phenomena. Our study indicates that the presence of an AA influences the relaxation behavior of polymer chains, which in turn affects the release of stored strain energy during folding. Controlling the reversibility as well as the actuation time of the biopolymer film by tuning the solvent is explained in detail at the bulk scale by applying appropriate experimental techniques. The underlying mechanism for the observed phenomena is complemented by performing a simulation study for a single polymer chain at the molecular length scale. Due to the solvent-triggered hygromorphic response, biopolymer films exhibit huge potential as sensors, soft robots, drug delivery agents, morphing medical devices and in biomedical applications. We provide experimental evidence for the weight lifting capacity of permanently folded membranes, amounting to ∼200 times their own weight.

Folding behavior and molecular mechanism of cross-linked biopolymer film in response to water.

Water responsive biopolymers are gaining enormous attention in the different areas of research and applications related to self-folding. In this work, we report that cross-linking is an efficient means of modifying a single layer biopolymer film for a controlled and predictable pathway of folding. The initiation of the folding of a film is caused by the diffusion of water molecules along the film thickness. However, this folding is observed to take place in an unpredictable and random fashion with a pristine biopolymer film and a nano-particle reinforced film. The mechanical properties and the diffusion characteristics of the film are strongly interrelated and affect the overall folding behavior. The underlying mechanism behind this relation is appropriately substantiated by an in depth molecular dynamic study. The detailed characterization of the folding shape and material behavior is performed applying suitable experimental techniques. The potential application of the controlled folding of the cross-linked film as a sensor and as a soft crane is demonstrated in this report.

Efficient reduction of the scrolling of Descemet membrane endothelial keratoplasty grafts by engineering the medium.

The Descemet Membrane Endothelial Keratoplasty (DMEK) procedure for corneal transplantation is challenging due to the need to unscroll the donor graft within the recipient's eye. This process of unscrolling is complex, time-consuming, leads to a loss of endothelial cells and, most importantly, can negatively impact the graft's adhesion and integration with the host tissue after surgery. This problem is particularly evident when the graft is young. However, the physics behind this scrolling is not well understood, and therefore no sustainable solution is attained. Here, we propose that the concentration gradient of the medium used during transplant leads to a displacement gradient across the graft thickness, resulting in an out-of-plane folding or scrolling of the graft tissue. Using chitosan bilayer-based experimental models, it is experimentally demonstrated that this diffusion-coupled-deformation phenomenon can successfully explain why younger donor grafts tend to scroll tighter than older ones. Most importantly, we illustrate here through experiments that the medium can be engineered to reduce the scroll tightness and thus reduce the surgical inconveniences and improve post-transplant recovery. STATEMENT OF SIGNIFICANCE: This paper addresses a major issue that surgeons face while doing Descemet Membrane Endothelial Keratoplasty (DMEK) in unscrolling grafts during the graft insertion procedure. The currently used tapping method to unscroll the graft inside the patient's eye significantly reduces endothelial cell count, thus affecting its lifetime. Surprisingly, the physics behind graft scrolling is not well understood, so no sustainable solutions are proposed by the medical community. In this work, we present the underlying mechanism of DMEK graft scroll and illustrate experimentally the reason for scroll tightness through a chitosan bilayer based experiment model. Most importantly, we have successfully demonstrated that the preserving medium of the grafts can be engineered to reduce scroll tightness.

Engineering the Nonmorphing Point of Actuation for Controlled Drug Release by Hydrogel Bilayer across the pH Spectrum.

Hydrogel-based pH-responsive bilayer actuators exhibit bidirectional actuation due to the differences in the concentration gradient developed across the thickness, the volume expansion due to swelling, and the mechanical stiffness of the layers involved. At a pH value (point), where the sum of these factors generates moments of equal magnitudes, the moments cancel each other and result in no net actuation. This pH point is termed here as a "nonmorphing point". In this work, we present a bilayer of chitosan (CS) and carboxymethyl cellulose (CMC) cross-linked with citric acid (CA) with tunable nonmorphing points across the pH spectrum by modulating the concentration and cross-linking density of the layers involved. The standard CS/CMC bilayer films took about 40 s to completely fold (clockwise) in 0.1 M HCl and 78 s to completely fold (anticlockwise) in 0.1 M NaOH. Generally, pH-responsive actuators are designed for targeted drug delivery to a specific site inside the body as they show bidirectional (clockwise/anticlockwise) actuation around a single nonmorphing point. The same pH-responsive system cannot be applied for drug release at another site with a different functioning pH. Thus, having a pH-responsive system with multiple nonmorphing points is highly desirable. Drug release experiments were performed with FITC and EtBr as model drugs loaded in CS and CMC layers. Moreover, the clockwise/anticlockwise actuation of the bilayer around the nonmorphing point can facilitate or inhibit the release of a drug. The clockwise actuation resulted in 55% FITC release and inhibited EtBr release to 4%; anticlockwise actuation resulted in 50% EtBr release and inhibited FITC release to 5%. We demonstrated morphing induced drug release by hydrogel bilayer films with tunable nonmorphing points across the pH spectrum.

Coherent-interface-induced strain in large lattice-mismatched materials: A new approach for modeling Raman shift.

Strain engineering as one of the most powerful techniques for tuning optical and electronic properties of Ill-nitrides requires reliable methods for strain investigation. In this work, we reveal, that the linear model based on the experimental data limited to within a small range of biaxial strains (< 0.2%), which is widely used for the non-destructive Raman study of strain with nanometer-scale spatial resolution is not valid for the binary wurtzite-structure group-III nitrides GaN and AlN. Importantly, we found that the discrepancy between the experimental values of strain and those calculated via Raman spectroscopy increases as the strain in both GaN and AlN increases. Herein, a new model has been developed to describe the strain-induced Raman frequency shift in GaN and AlN for a wide range of biaxial strains (up to 2.5%). Finally, we proposed a new approach to correlate the Raman frequency shift and strain, which is based on the lattice coherency in the epitaxial layers of superlattice structures and can be used for a wide range of materials. Electronic Supplementary Material: Supplementary material (Table S1: Values of bulk phonon deformation potentials and elastic constants for GaN and AlN from each reference used in Table 1, Fig. S1: Lattice parameters of SL layers using Eq. (8), and Fig. S2: Raman mapping using Eq. (7)) is available in the online version of this article at 10.1007/s12274-021-3855-4.

Hierarchical Assembly of Atomically Precise Metal Clusters as a Luminescent Strain Sensor.

We demonstrate the formation of a versatile luminescent organo-inorganic layered hybrid material, composed of bovine serum albumin (BSA)-protected Au30 clusters and aminoclay sheets. X-ray diffraction revealed the intercalation of Au30@BSA in the layered superstructure of aminoclay sheets. Coulombic attraction of the clusters and the clay initiates the interaction, and the appropriate size of the clusters allowed them to intercalate within the lamellar aminoclay galleries. Electron microscopy measurements confirmed the hierarchical structure of the material and also showed the cluster-attached clay sheets. Zeta potential measurement and dynamic light scattering probed the gradual formation of the ordered aggregates in solution. The hybrid material could be stretched up to 300% without fracture. The emergence of a new peak in the luminescence spectrum was observed during the course of mechanical stretching. This peak increased in intensity gradually with the degree of elongation or strain of the material. A mechanochromic luminescence response was further demonstrated with a writing experiment on a luminescent mat of the material, made by electrospinning.

Quantum phase transition in a pseudo-Hermitian Dicke model.

We show that a Dicke-type non-Hermitian Hamiltonian admits entirely real spectra by mapping it to the "dressed Dicke model" through a similarity transformation. We find a positive-definite metric in the Hilbert space of the non-Hermitian Hamiltonian so that the time evolution is unitary and allows a consistent quantum description. We then show that this non-Hermitian Hamiltonian describing nondissipative quantum processes undergoes quantum phase transition. The exactly solvable limit of the non-Hermitian Hamiltonian has also been discussed.

Level statistics of a pseudo-Hermitian Dicke model.

A non-Hermitian operator that is related to its adjoint through a similarity transformation is defined as a pseudo-Hermitian operator. We study the level statistics of a pseudo-Hermitian Dicke Hamiltonian that undergoes quantum phase transition (QPT). We find that the level-spacing distribution of this Hamiltonian near the integrable limit is close to Poisson distribution, while it is Wigner distribution for the ranges of the parameters for which the Hamiltonian is nonintegrable. We show that the assertion in the context of the standard Dicke model that QPT is a precursor to a change in the level statistics is not valid in general.

Tailoring pore distribution in polymer films via evaporation induced phase separation.

By considering a mixture of poly(methyl methacrylate)-tetrahydrofuran-water (PMMA-THF-H2O), we report an experimental approach to tune the distribution of pores in polymer films formed via evaporation induced phase separation (EIPS). We show that the drying induced composition and microstructural changes that occur due to the evaporation of the solvent (THF) and the nonsolvent (H2O) delineate the ultimate polymer film morphology. The temporal evolution of the microstructure, the phase behavior and the change in the composition of the PMMA-THF-H2O mixture at air-solution (top surface) and solution-substrate (bottom surface) interfaces is monitored to provide insights into the origin of the pore distribution in the final polymer films. The effects of various parameters such as nonsolvent and polymer concentration in the casting solution, casting solution thickness, relative humidity and temperature on the final film morphology are investigated to correlate how the composition path (CP) change under various conditions ultimately dictates the film morphology. We show that depending on the change in the composition of the polymer solution (evolution of CP) and the water/PMMA ratio at the time of phase separation, the morphology of the final film formed varies as - (1) non porous i.e., dense film (2) a film with pores only at the bottom surface (3) an asymmetric film i.e., films with a top dense layer (non-porous) supported by porous sub-layers (4) a porous film with uniform pores distributed across the entire film thickness and (5) a film with pores only at the top surface. In addition, we show that the morphology of the PMMA film can also be tuned by varying the composition of low and high molecular weight PMMA in the casting solution. These porous PMMA structures, being biocompatible, are useful for applications in cell culture, drug delivery and wound dressing.

Comparative Role of Chain Scission and Solvation in the Biodegradation of Polylactic Acid (PLA).

The molecular mechanism behind the process of biodegradation and consequently the loss in mechanical properties of polylactic acid (PLA) requires detailed understanding for the successful designing of various technological devices. In this study, we examine the role of free water and chain scission in this degradation process and quantify the mechanical properties of pristine and nanoparticle-reinforced PLA as it degrades over time. The in situ mechanical response of the degrading polymer is determined experimentally using nano-dynamic mechanical analysis (nanoDMA). Water present in the polymer matrix contributes to hydrolysis and subsequent scission of polymer chains. Water in excess of hydrolysis, however, alters the load transfer mechanism within the polymer chains. Molecular mechanism study applied in this work provides detailed insights into the relative role of these two mechanisms, (i) chain scission and (ii) solvation, in the reduction of mechanical properties during degradation. Functional groups such as ester (-COO-) and terminal acid (-COOH) interact with water molecules leading to the formation of water bridges and solvation shells, respectively. These are found to hinder the load transfer between polymer chains. It is observed that, compared to scission, solvation plays a more active role in the reduction of mechanical properties of degrading PLA.

Influence of Microstructure on the Nanomechanical Properties of Polymorphic Phases of Poly(vinylidene fluoride).

Poly(vinylidine fluoride) (PVDF) is a semicrystalline polymer which is known to exist in several polymorphic phases, namely, α, ß, and γ. Each one of these polymorphic phases is characterized by unique features such as spherulite formation in the case of the α and γ phases and the presence of large piezoelectric and ferroelectric activity in the ß phase. Despite being widely used as thin coatings in sensors, lack of reports on nanomechanical properties suggests that investigation of mechanical properties of PVDF, let alone those of its polymorphic phases, seems to have evaded the sight of the research community. Herein, we report the nanomechanical properties of the α, ß, and γ phases of PVDF. The modulus and hardness values were evaluated from nanoindentation experiments; it was found that the electroactive ß phase is the softest among the three polymorphic phases. This result was further confirmed by scratch experiments. We have attempted to establish a correlation between the microstructure and nanomechanical properties of these phases. This work sheds light on the mechanisms responsible for the observed mechanical behavior and the role of tie molecules and amorphous content in providing flexibility to the polymer.

Insights on Water Dynamics in the Hygromorphic Phenomenon of Biopolymer Films.

Water-responsive biopolymer thin films with engineered matrix characteristics can accomplish desirable shape changing properties such as self-folding. Self-folding response of chitosan film is experimentally characterized by its total folding time and rate of folding. Here, atomistic simulation is employed to investigate the molecular mechanism responsible for modified self-folding behavior observed in nanoparticle reinforced chitosan films. The nanocomposite system is solvated with water content varying from 10% to 100% of total mass of the system. The free volume available for diffusion of water molecules is affected by the flexibility of glycosidic linkages present in chitosan chains. The increase in mobility of water molecules with increase in water content decides the rate of folding. A separate molecular system is modeled with confined region between nanoparticles densified with chitosan chains and water molecules. The thickness of confined region is determined from the critical distance of influence of nanoparticles on water molecules. The adsorption of water on nanoparticle surface and relaxation of chitosan chains are responsible for increased total folding time with nanoparticle concentration. This simulation study, complemented with experimental observations provides a useful insight into the designing of actuators and sensors based on the phenomenon of hygromorphism.

Calculated thickness dependent plasmonic properties of gold nanobars in the visible to near-infrared light regime.

Metallic, especially gold, nanostructures exhibit plasmonic behavior in the visible to near-infrared light range. In this study, we investigate optical enhancement and absorption of gold nanobars with different thicknesses for transverse and longitudinal polarizations using finite element method simulations. This study also reports on the discrepancy in the resonance wavelengths and optical enhancement of the sharp-corner and round-corner nanobars of constant length 100 nm and width 60 nm. The result shows that resonance amplitude and wavelength have strong dependences on the thickness of the nanostructure as well as the sharpness of the corners, which is significant since actual fabricated structure often have rounded corners. Primary resonance mode blue-shifts and broadens as the thickess increases due to decoupling of charge dipoles at the surface for both polarizations. The broadening effect is characterized by measuring the full width at half maximum of the spectra. We also present the surface charge distribution showing dipole mode oscillations at resonance frequency and multimode resonance indicating different oscillation directions of the surface charge based on the polarization direction of the field. Results of this work give insight for precisely tuning nanobar structures for sensing and other enhanced optical applications.

Molecular mechanisms in deformation of cross-linked hydrogel nanocomposite.

The self-folding behavior in response to external stimuli observed in hydrogels is potentially used in biomedical applications. However, the use of hydrogels is limited because of its reduced mechanical properties. These properties are enhanced when the hydrogels are cross-linked and reinforced with nanoparticles. In this work, molecular dynamics (MD) simulation is applied to perform uniaxial tension and pull out tests to understand the mechanism contributing towards the enhanced mechanical properties. Also, nanomechanical characterization is performed using quasi static nanoindentation experiments to determine the Young's modulus of hydrogels in the presence of nanoparticles. The stress-strain responses for chitosan (CS), chitosan reinforced with hydroxyapatite (HAP) and cross-linked chitosan are obtained from uniaxial tension test. It is observed that the Young's modulus and maximum stress increase as the HAP content increases and also with cross-linking process. Load displacement plot from pullout test is compared for uncross-linked and cross-linked chitosan chains on hydroxyapatite surface. MD simulation reveals that the variation in the dihedral conformation of chitosan chains and the evolution of internal structural variables are associated with mechanical properties. Additional results reveal that the formation of hydrogen bonds and electrostatic interactions is responsible for the above variations in different systems.

Nanomechanical characterization and molecular mechanism study of nanoparticle reinforced and cross-linked chitosan biopolymer.

Chitosan (CS) is a biomaterial that offers many sophisticated and innovative applications in the biomedical field owing to its excellent characteristics of biodegradability, biocompatibility and non-toxicity. However, very low mechanical properties of chitosan polymer impose restriction on its further development. Cross-linking and nanoparticle reinforcement are the two possible methods to improve the mechanical properties of chitosan films. In this research, these two methods are adopted individually by using tripolyphosphate as cross-linker and nano-hydroxyapatite as particle reinforcement. The nanomechanical characterizations under static loading conditions are performed on these modified chitosan films. It is observed that nanoparticle reinforcement provided necessary mechanical properties such as ductility and modulus. The mechanisms involved in improvement of mechanical properties due to particle reinforcement are studied by molecular dynamics (MD). Further, improvement in mechanical properties due to combination of particle reinforcement and cross-linking agent with chitosan is investigated. The stress relaxation behavior for all these types of films is characterized under dynamic loading conditions using dynamic mechanical analysis (nanoDMA) experiment. A viscoelastic solid like response is observed for all types of film with modulus relaxing by 3-6% of its initial value. A suitable generalized Maxwell model is fitted with the obtained viscoelastic response of these films. The response to nano-scratch behavior is also studied for particle reinforced composite films.