Insights into nanomechanical behavior of B. mori silk fibroin-hydroxyapatite bio-nanocomposite using MD simulations: Role of varying hydroxyapatite content.

Nanocomposite material composed of Bombyx mori Silk Fibroin and hydroxyapatite (B. mori SF-HA) is a potential biomaterial for bone tissue engineering. Here, Bombyx mori Silk Fibroin (B. mori SF) is a flexible and tough organic, polymer phase, and hydroxyapatite (HA) is hard and stiff mineral phase. Knowledge about mechanical deformation behavior together with governing mechanisms, and the role of the two phases (SF and HA phase) and interfacial interactions between them, in B. mori SF-HA biomaterial, at fundamental level is an important factor to consider while developing the tissue grafts. Such nanometer scale behavior is often preferably investigated using molecular dynamics method. Present study aims at understanding the mechanical deformation behavior and associated physical mechanisms in B. mori SF-HA bio-nanocomposite, at nanoscale. For this purpose, computational atomistic models of B. mori SF-HA bio-nanocomposite are developed with varying HA content. Mechanical behavior analysis of these composite models under tensile loading were performed using Molecular Dynamics (MD) simulations. Elastic modulus and tensile strength values in the range of 7-20 GPa and 200-700 MPa, respectively, are obtained for B. mori SF-HA composite, in case of different HA contents, wherein, increased mechanical properties are observed with increase in HA content. Analyses of the deformation trajectories show that the deformation flow behavior in B. mori SF-HA bio-nanocomposites is mainly defined by the soft SF phase. However, energetics analyses show that, the HA phase and SF-HA interfacial interactions also play a considerable role in mechanical performance of B. mori SF-HA bio-nanocomposite. Additionally, interfacial shear strength values in B. mori SF-HA bio-nanocomposite, for different HA contents, have also been obtained. The observations made and insights gained in present work has contribution and impact in gaining an insight into the mechanistic interactions occurring at nanoscale between SF and HA phases in B. mori SF-HA bio-composite.

Molecular mechanics and failure mechanisms in B. mori Silk Fibroin-hydroxyapatite composite interfaces: Effect of crystal thickness and surface characteristics.

Bombyx mori Silk Fibroin-hydroxyapatite (B. mori SF-HA) bio-nanocomposite is a prospective biomaterial for tissue engineered graft for bone repair. Here, B. mori SF is primarily a soft and tough organic phase, and HA is a hard and stiff mineral phase. In biomaterial design, an understanding about the nanoscale mechanics of SF-HA interface, such as interfacial interaction and interface debonding mechanisms between the two phases is essential for obtaining required functionality. To investigate such nanoscale behavior, molecular dynamics method is a preferred approach. Present study focuses on understanding of the interface debonding mechanisms at SF-HA interface in B. mori SF-HA bio-nanocomposite at nanometer length scale. For this purpose, nanoscale atomistic models of SF-HA interface are also developed based on the HA crystal size and HA surface type (Ca2+ dominated and OH- dominated) in contact with SF. Mechanical behavior analysis of these SF-HA interface models under pull-out type test were performed using Molecular Dynamics (MD) simulations. Surface pull-off strength values in the range of 0.4-0.8 GPa were obtained for SF-HA interface models, for different HA crystal thicknesses, wherein, the pull-off strength values are found to increase with increase in HA thicknesses. Analyses show that deformation mechanisms in SF-HA interface deformation, is a combination of shear deformation in SF phase followed by disintegration of SF phase from HA block. Furthermore, higher rupture force values were obtained for SF-HA interface with Ca2+ dominated HA surface in contact with SF phase, indicating that SF protein has a higher affinity for Ca2+ dominated surface of HA phase. Current work contributes in developing an understanding of mechanistic interactions between organic and inorganic phases in B. mori SF-HA composite nanostructure.

Phenomenological models of Bombyx mori silk fibroin and their mechanical behavior using molecular dynamics simulations.

Bombyx mori silk fibroin (B. mori SF) is a promising biopolymer for use in biomedical applications such as tissue engineered grafts and as a load bearing biopolymer with biocompatible and bioresorbable properties. B. mori SF is a hierarchical bio- macro-molecule made up of amino acid (residue) chains consisting of a crystalline phase and an amorphous phase arranged in a specific order. Understanding about the mechanical behavior of B. mori SF at multiple length scales is of importance when developing tissue grafts, which requires a deeper understanding of the mechanics of its nanostructure. Four phenomenological models of B. mori SF nanostructures were developed, based on crystalline and amorphous phase connectivity. Tensile loading based mechanical behavior analysis of these models were performed using molecular dynamics (MD) simulations and compared with existing results from literature for selection of best performing model. Elastic modulus of ~7.4GPa and tensile strength of ~340 MPa were obtained for this model. Analysis of results reveals that deformation mechanisms in B. mori SF at nanoscale are a combination of tensile and shear deformations, wherein, the tensile deformation of amorphous region results into excessive extension of B. mori SF, whereas, shear deformation of crystalline region results into a high tensile strength. Overall, this work is instrumental in development of a right computational nanoscale model of SF nanostructure and provides deeper insights into the mechanistic interactions and mechanisms between amorphous and crystalline regions of B. mori SF, which would be useful for further studies of silk based biomaterials.