ABSTRACT
Cellulose, a renewable structural biopolymer, is ubiquitous in nature and is the basic reinforcement component of the natural hierarchical structures of living plants, bacteria, and tunicates. However, a detailed picture of the crystalline cellulose surface at the molecular level is still unavailable. Here, using atomic force microscopy (AFM) and molecular dynamics (MD) simulations, we revealed the molecular details of the cellulose chain arrangements on the surfaces of individual cellulose nanocrystals (CNCs) in water. Furthermore, we visualized the three-dimensional (3D) local arrangement of water molecules near the CNC surface using 3D AFM. AFM experiments and MD simulations showed anisotropic water structuring, as determined by the surface topologies and exposed chemical moieties. These findings provide important insights into our understanding of the interfacial interactions between CNCs and water at the molecular level. This may allow the establishment of the structure-property relationship of CNCs extracted from various biomass sources.
ABSTRACT
Chitin is one of the most abundant and renewable natural biopolymers. It exists in the form of crystalline microfibrils and is the basic structural building block of many biological materials. Its surface crystalline structure is yet to be reported at the molecular level. Herein, atomic force microscopy (AFM) in combination with molecular dynamics simulations reveals the molecular-scale structural details of the chitin nanocrystal (chitin NC)-water interface. High-resolution AFM images reveal the molecular details of chitin chain arrangements at the surfaces of individual chitin NCs, showing highly ordered, stable crystalline structures almost free of structural defects or disorder. 3D-AFM measurements with submolecular spatial resolution demonstrate that chitin NC surfaces interact strongly with interfacial water molecules creating stable, well-ordered hydration layers. Inhomogeneous encapsulation of the underlying chitin substrate by these hydration layers reflects the chitin NCs' multifaceted surface character with different chain arrangements and molecular packing. These findings provide important insights into chitin NC structures at the molecular level, which is critical for developing the properties of chitin-based nanomaterials. Furthermore, these results will contribute to a better understanding of the chemical and enzymatic hydrolysis of chitin and other native polysaccharides, which is also essential for the enzymatic conversion of biomass.
Subject(s)
Nanoparticles , Water , Chitin , Microscopy, Atomic Force/methods , Polysaccharides , Water/chemistryABSTRACT
Mineral-water interfaces play an important role in many natural as well as technological fields. Fundamental properties of these interfaces are governed by the presence of the interfacial water and its specific structure at the surface. Calcite is particularly interesting as a dominant rock-forming mineral in the earth's crust. Here, we combine atomic force microscopy, sum-frequency generation spectroscopy, and molecular dynamics simulations to determine the position and orientation of the water molecules in the hydration layers of the calcite surface with high resolution. While atomic force microscopy provides detailed information about the position of the water molecules at the interface, sum-frequency generation spectroscopy can deduce the orientation of the water molecules. Comparison of the calcite-water interface to the interfaces of magnesite-water, magnesite-ethanol, and calcite-ethanol reveals a comprehensive picture with opposite water orientations in the first and second layer of the interface, which is corroborated by the molecular dynamics simulations.
ABSTRACT
The mechanical and optical properties generated due to the stacking of different atomically thin materials have made it possible to tune and engineer these materials for next-generation electronics. The understanding of the interlayer interactions in such stacked structures is of fundamental interest for structure and property correlation. Here, a combined approach of in situ Raman spectroscopy and mechanical straining along with molecular dynamics (MD) simulations has been used to probe one such interface, namely, the WS2/MoS2 heterostructure. Vertical heterostructures on poly(methyl methacrylate), when flexed, showed signs of decoupling at 1.2% strain. Theoretical calculations showed strain-induced stacking changes at 1.75% strain. The sliding characteristics of layers were also investigated using scanning probe microscopy based nanoscratch testing, and the results are further supported by MD simulations. The present study could be used to design future optoelectronic devices based on WS2/MoS2 heterostructures.
