Session F36: Physics of Bioinspired Materials II

The Effect of Water Molecules on Mechanical Properties of Bamboo Microfibrils

Bamboo fibers have higher strength-to-weight ratios than steel and concrete. The unique properties of bamboo fibers come from their natural composite structures that comprise mainly cellulose nanofibrils in a matrix of intertwined hemicellulose and lignin called lignin-carbohydrate complex (LCC). Here, we have utilized atomistic simulations to investigate the mechanical properties and mechanisms of interactions between these materials, in the presence of water molecules. Our results suggest that hemicellulose exhibits better mechanical properties and lignin shows greater tendency to adhere to cellulose nanofibrils. Consequently, the role of hemicellulose found to be enhancing the mechanical properties and lignin found to be providing the strength of bamboo fibers. The abundance of Hbonds in hemicellulose chains is responsible for improving the mechanical behavior of LCC. The strong van der Waals forces between lignin molecules and cellulose nanofibrils is responsible for higher adhesion energy between LCC/cellulose nanofibrils. We also found out that the amorphous regions of cellulose nanofibrils is the weakest interface in bamboo Microfibrils. In presence of water, the elastic modulus of lignin increases at low water content (less than 10%) and decreases in higher water content   

Water-Floating Giant Nanosheets from Helical Peptide Pentamers.

One of the important challenges in the development of protein-mimetic materials is to understand the sequence specific assembly behavior and the dynamic folding change. Conventional strategies to construct two dimensional nanostructures from the peptides have been limited to beta-sheet forming sequences in use of basic building blocks because of their natural tendency to form sheet like aggregations. Here we identified a new peptide sequence, YFCFY that can form dimers by the disulfide bridge, fold into helix and assemble into macroscopic flat sheet at the air/water interface. Because of large driving force for two dimensional assembly and high elastic modulus of the resulting sheet, the peptide assembly induces the flattening of initially round water droplet. Additionally, we found that stabilization of helix by the dimerization is a key determinant for maintaining macroscopic flatness over a few tens centimeter even with a uniform thickness below 10 nm. Furthermore, the capability to transfer 2D film from water droplet to other substrates allows for the multiple stacking of 2D peptide nanostructure, suggesting possible applications in the biomimetic catalysts, biosensor and 2D related electronic devices.   

DNA-linked NanoParticle Lattices with Diamond Symmetry: Stability and Shape

The linking of nanoparticles (NP) by DNA has been proven to be an effective means to create NP lattices with specific order. Lattices with diamond symmetry are predicted to offer novel photonic properties, but self-assembly of such lattices has proven to be challenging due to the low packing fraction, sensitivity to bond orientation, and local heterogeneity. Recently, we reported an approach to create diamond NP lattices based on the association between anisotropic particles with well-defined tetravalent DNA binding topology and isotropically functionalized NP. Here, we use molecular dynamics simulations to evaluate the Gibbs free energy of these lattices, and thereby determine the stability of these lattices as a function of NP size. The lattice free energy has a minimum for NP size near 50 nm, and rapid increases for larger NP, destabilizing the lattice. We also predict the equilibrium shape for the cubic diamond crystallite using the Wulff construction method. Specifically, we predict the equilibrium shape using the surface energy for different crystallographic planes. We evaluate surface energy directly form molecular dynamics simulation, which we correlate with theoretical estimates from the expected number of broken DNA bonds along a facet.   

Multifunctional Memprocessor Device with DNA-Guided Nickel Ions Chain

Molecular metal ion wires are highly desirable for their potential applications in the field of molecular electronics. However, synthesis of a scaffold-free and long metal chain is exceptional challenging. DNA is a self-assembly wire that chelates metal ions with its base-pairs. By using DNA as template, an 830-nm equivalent conducting nickel ion chain was fabricated. This nickel ion chain device demonstrates the functionality of memristor (memory resistor), memcapacitor (memory capacitor), and redox-induced hysteresis effects. The memory state operation is attributed to the dynamic response of nickel-ion states caused by redox reaction. The redox state of Ni ions is controllable by external bias, making it a multi-state memory component for a possible “memcomputer”, namely a computer that uses memory to store and process information simultaneously [1]. Ref: [1] M. Di Ventra and Y.V. Pershin, Nature Physics, 9, 200 (2013).   

Elastic Properties of Lysozyme Confined in Nanoporous Polymer Films

Retaining the conformational structure and bioactivity of immobilized proteins is important for biosensor designs and drug delivery systems. It is known that confined media provide a protective environment to the encapsulated proteins and prevent diffusion of the denaturant. In this study, different types of proteins (streptavidin, lysozyme and fibrinogen) were chemically attached into the nanopores of poly(methyl methacrylate) thin films. Heterogeneous flat surfaces with varying cylinder pore sizes (10-50 nm) were used to confine proteins of different sizes and shapes. Stiffness of protein functionalized nanopores was measured in nanoindentation experiments. Our results showed that streptavidin behaved more stiffly when pore dimension changed from micron to nanosize. Further, it was found that lysozyme confined within nanopores showed higher specific bioactivity than proteins on flat surfaces. These results on surface elasticity and protein activity may help in understanding protein interactions with surfaces of different topologies and chemistry.   

\textbf{Bioinspired Non-iridescent Structural Color from Polymer Blend Thin Films}

Colors exhibited in biological species are either due to natural pigments, sub-micron structural variation or both. Structural colors thus exhibited can be iridescent (ID) or non-iridescent (NID) in nature. NID colors originate due to interference and coherent scattering of light with quasi-ordered micro- and nano- structures. Specifically, in Eastern Bluebird (Sialia sialis) these nanostructures develop as a result of phase separation of $\beta $-keratin from cytoplasm present in cells. We replicate these structures \textit{via} spinodal blend phase separation of PS-PMMA thin films. Colors of films vary from ultraviolet to blue. Scattering of UV-visible light from selectively leeched phase separated blends are studied in terms of varying domain spacing (200nm to 2$\mu $m) of film. We control these parameters by tuning annealing time and temperature. Angle-resolved spectroscopy studies suggest that the films are weakly iridescent and scattering from phase-separated films is more diffused when compared to well-mixed films. This study offers solutions to several color-based application in paints and coatings industry.   

\textbf{Colloidal-based additive manufacturing of bio-inspired composites}

Composite materials in nature exhibit heterogeneous architectures that are tuned to fulfill the functional demands of the surrounding environment. Examples range from the cellulose-based organic structure of plants to highly mineralized collagen-based skeletal parts like bone and teeth. Because they are often utilized to combine opposing properties such as strength and low-density or stiffness and wear resistance, the heterogeneous architecture of natural materials can potentially address several of the technical limitations of artificial homogeneous composites. However, current man-made manufacturing technologies do not allow for the level of composition and fiber orientation control found in natural heterogeneous systems. In this talk, I will present two additive manufacturing technologies recently developed in our group to build composites with exquisite architectures only rivaled by structures made by living organisms in nature. Since the proposed techniques utilize colloidal suspensions as feedstock, understanding the physics underlying the stability, assembly and rheology of the printing inks is key to predict and control the architecture of manufactured parts. Our results will show that additive manufacturing routes offer a new exciting pathway for the fabrication of biologically-inspired composite materials with unprecedented architectures and functionalities.   

Mesh Size Control of Friction

Soft, permeable sliding interfaces in aqueous environments are ubiquitous in nature but their ability to maintain high lubricity in a poor lubricant (water) has not been well understood. Hydrogels are excellent materials for fundamental soft matter and biotribology studies due to their high water content. While mesh size controls the material and transport properties of a hydrogel, its effects on friction were only recently explored. Polyacrylamide hydrogels slid in a Gemini (self-mated) interface produced low friction under low speeds, low pressures, macroscopic contact areas, and room temperature aqueous environments. The friction coefficients at these interfaces are lowest at low speeds and are speed-independent. This behavior is due to thermal fluctuations at the interface separating the surfaces, with water shearing in this region being the main source of dissipation. We found that mesh size had an inverse correlation with friction. We further investigated a transition from this behavior at higher speeds, and found that the transition speed correlated with the mesh size and relaxation time of the polymer network. Very soft and correspondingly large mesh size Gemini hydrogels show superlubricity under specific conditions with friction being less than 0.005.