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.

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.

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.