Pijush Ghosh

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.

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 Youngs 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 Youngs 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.

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.

Surface dissimilarity affects critical distance of influence for confined water

Water at interfaces and under nano-confinement is part of many natural processes. The behavior of this water is greatly influenced by the nature of the surfaces it is in contact with and the confinement distance. The objective of this study is to understand the behaviour of confined water between dissimilar (X–Y) surfaces under varying confinement spacing. The surfaces considered were hydrophilic in nature and the combinations were considered based on crystal structure and surface energy. The critical distance of influence of mineral substrates on the water molecules was determined by applying time-averaged static properties such as interfacial layer density and orientation and dynamic properties such as diffusion. It was observed that dynamic properties provide a higher value of critical distance compared to static properties for dissimilar surface combination. The reason for this disparity is probed in terms of mineral–water and water–water interactions. The disproportion of strong and weak H-bonds was observed to be significant in determining the dynamic behaviour of interfacial layer. We applied hydrophilic surface combinations of tricalcium silicate (C3S) and dicalcium silicate (C2S) for our investigations.

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.

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, β, 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 β 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, β, and γ phases of PVDF. The modulus and hardness values were evaluated from nanoindentation experiments; it was found that the electroactive β 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.

Deformation Mechanism of Chitosan/Hydroxyapatite Nanocomposite: A Molecular Dynamics study

Biopolymers are new generation polymers which find applications in biomedical field, in food packaging, as edible films etc., due to its unique property of biodegradability and biocompatibility, which is a major concern in case of fossil derived polymers. The application of biopolymers gets limited due to its low mechanical properties. The mechanical properties of these biopolymers however can be enhanced by reinforcing with suitable fillers of nanometer size range, thereby forming nanocomposites. Chitosan (CS) is a polysaccharide which is one of the most extensively used biopolymer in drug delivery, bone tissue engineering etc. Chitosan/Hydroxyapatite (HAP) nanocomposite can be formed by dispersing HAP nanoparticles in chitosan matrix. The mechanical properties of nanocomposites are dependent on the interactions between nanoparticles and polymer matrix. It is thus essential to understand the mechanism between matrix and nanoparticles in order to tailor the mechanical properties for suitable applications. Molecular Dynamics (MD) is one of the possible tools to study the interactions at atomic level. It can also contribute significantly in the prediction of macro level properties. In this work, MD has been applied to study the underlying mechanisms at atomic length scale during the uniaxial deformation process of CS/HAP nanocomposites. The interaction between HAP and CS has been analyzed using radial distribution function, evolution of hydrogen bonding and electrostatic interactions during the deformation process. The initial results indicate an increase in the modulus of elasticity of CS/HAP nanocomposite when compared to pure chitosan for a given strain rate. It is observed that the primary interaction between nanoparticle and polymer matrix is in the form of an electrostatic attraction between the calcium present in HAP and the oxygen in chitosan chains.

Influence of Protein Structures on Mechanical Response

In biological nanocomposites such as bones, teeth and seashells, proteins play an important role in their mechanical response. Proteins in nacre, the inner layer of seashells have been shown to have exceptional mechanical properties. The secondary structures, β-sheets of protein when present close to each other in multiple numbers could take the shape of a planar β-sheath like structure or a β-barrel to form a domain. In natural proteins both these types of structures are commonly found. Effort has been made through this work to study the mechanical response of these β-planar sheath and β-barrel structures when subjected to external loads. Comparative study of the stress-deformation characteristics of these two types of structures has been made. The influence of shear force on the conformation of planar and barrel structure is investigated. Both these structures with almost similar number of amino acids have been extracted from one single spinach protein, Ferredoxin Reductase (1FNR). Steered molecular dynamics has been used to conduct these studies. The paper deals with the separation of the two domains from the main protein, simulation details and results comparing the responses.