Biodegradable nanocomposites of amyloid fibrils and graphene with shape-memory and enzyme-sensing properties.

Graphene has exceptional mechanical and electronic properties, but its hydrophobic nature is a disadvantage in biologically related applications. Amyloid fibrils are naturally occurring protein aggregates that are stable in solution or under highly hydrated conditions, have well-organized supramolecular structures and outstanding strength. Here, we show that graphene and amyloid fibrils can be combined to create a new class of biodegradable composite materials with adaptable properties. This new composite material is inexpensive, highly conductive and can be degraded by enzymes. Furthermore, it can reversibly change shape in response to variations in humidity, and can be used in the design of biosensors for quantifying the activity of enzymes. The properties of the composite can be fine-tuned by changing the graphene-to-amyloid ratio.

[1]  R. Ruoff,et al.  Chemical methods for the production of graphenes. , 2009, Nature nanotechnology.

[2]  Tal Dvir,et al.  Nanotechnological strategies for engineering complex tissues. , 2020, Nature nanotechnology.

[3]  Ji Won Suk,et al.  Graphene-based actuators. , 2010, Small.

[4]  Zhaoxia Jin,et al.  Fabrication, mechanical properties, and biocompatibility of graphene-reinforced chitosan composites. , 2010, Biomacromolecules.

[5]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[6]  S. Stankovich,et al.  Graphene-based composite materials , 2006, Nature.

[7]  Zhiqiang Wang,et al.  Environment-Friendly Method To Produce Graphene That Employs Vitamin C and Amino Acid , 2010 .

[8]  Michele Vendruscolo,et al.  Role of Intermolecular Forces in Defining Material Properties of Protein Nanofibrils , 2007, Science.

[9]  Markus J Buehler,et al.  Atomistic Simulation of Nanomechanical Properties of Alzheimer's Ab(1–40) Amyloid Fibrils under Compressive and Tensile Loading , 2022 .

[10]  Xinsheng Peng,et al.  General method for ultrathin free-standing films of nanofibrous composite materials. , 2007, Journal of the American Chemical Society.

[11]  Tae Hee Han,et al.  Peptide/Graphene Hybrid Assembly into Core/Shell Nanowires , 2010, Advanced materials.

[12]  A. K. Sood,et al.  Graphene: The New Two‐Dimensional Nanomaterial , 2009 .

[13]  R. Mezzenga,et al.  Single-step direct measurement of amyloid fibrils stiffness by peak force quantitative nanomechanical atomic force microscopy , 2011 .

[14]  J. Ahopelto,et al.  Interfacial engineering by proteins: exfoliation and functionalization of graphene by hydrophobins. , 2010, Angewandte Chemie.

[15]  Ehud Gazit,et al.  Amyloids: not only pathological agents but also ordered nanomaterials. , 2008, Angewandte Chemie.

[16]  R. Piner,et al.  Biocompatible, Robust Free‐Standing Paper Composed of a TWEEN/Graphene Composite , 2010, Advanced materials.

[17]  Chun Li,et al.  Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets. , 2008, Journal of the American Chemical Society.

[18]  Lucio Isa,et al.  Unravelling adsorption and alignment of amyloid fibrils at interfaces by probe particle tracking , 2011 .

[19]  Alexander Hexemer,et al.  Biomimetic self-templating supramolecular structures , 2011, Nature.

[20]  D. Small,et al.  β‐Amyloid fibril formation is promoted by step edges of highly oriented pyrolytic graphite , 2006, Biopolymers.

[21]  Jin-Mi Jung,et al.  Structure of heat-induced beta-lactoglobulin aggregates and their complexes with sodium-dodecyl sulfate. , 2008, Biomacromolecules.

[22]  Rudy J. Koopmans,et al.  Engineering aspects of self-organizing materials , 2009 .

[23]  R. Mezzenga,et al.  General self-assembly mechanism converting hydrolyzed globular proteins into giant multistranded amyloid ribbons. , 2011, Biomacromolecules.

[24]  R. Ruoff,et al.  Graphene and Graphene Oxide: Synthesis, Properties, and Applications , 2010, Advanced materials.

[25]  R. Mezzenga,et al.  Snapshots of fibrillation and aggregation kinetics in multistranded amyloid β-lactoglobulin fibrils , 2011 .

[26]  G. Wallace,et al.  Processable aqueous dispersions of graphene nanosheets. , 2008, Nature nanotechnology.

[27]  R. Mezzenga,et al.  Amyloid-mediated synthesis of giant, fluorescent, gold single crystals and their hybrid sandwiched composites driven by liquid crystalline interactions. , 2011, Journal of colloid and interface science.

[28]  Alexander K. Buell,et al.  Nanostructured films from hierarchical self-assembly of amyloidogenic proteins. , 2010, Nature nanotechnology.

[29]  J. Kysar,et al.  Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene , 2008, Science.

[30]  T. Zyung.  Synthesis, Properties, and Applications of Graphene , 2011 .

[31]  A. Patil,et al.  Aqueous Stabilization and Self‐Assembly of Graphene Sheets into Layered Bio‐Nanocomposites using DNA , 2009 .

[32]  Andreas Walther,et al.  Genetic engineering of biomimetic nanocomposites: diblock proteins, graphene, and nanofibrillated cellulose. , 2011, Angewandte Chemie.

[33]  S. Jarvis,et al.  Beneficial characteristics of mechanically functional amyloid fibrils evolutionarily preserved in natural adhesives , 2007 .

[34]  Christopher M Dobson,et al.  Characterization of the nanoscale properties of individual amyloid fibrils , 2006, Proceedings of the National Academy of Sciences.

[35]  S. Jarvis,et al.  Characterisation of Amyloid Nanostructures in the Natural Adhesive of Unicellular Subaerial Algae , 2009 .

[36]  I. Grigorieva,et al.  Unimpeded Permeation of Water Through Helium-Leak–Tight Graphene-Based Membranes , 2011, Science.

[37]  Giovanni Dietler,et al.  Understanding amyloid aggregation by statistical analysis of atomic force microscopy images. , 2010, Nature nanotechnology.

[38]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

[39]  R. Mezzenga,et al.  Liquid crystalline phase behavior of protein fibers in water: experiments versus theory. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[40]  O. Ikkala,et al.  Large-area, lightweight and thick biomimetic composites with superior material properties via fast, economic, and green pathways. , 2010, Nano letters.

[41]  P. Hilbers,et al.  The role of collagen in bone apatite formation in the presence of hydroxyapatite nucleation inhibitors. , 2010, Nature materials.

[42]  S. Gras.  Surface- and Solution-Based Assembly of Amyloid Fibrils for Biomedical and Nanotechnology Applications , 2009 .

[43]  Jin-Mi Jung,et al.  Interfacial activity and interfacial shear rheology of native β-lactoglobulin monomers and their heat-induced fibers. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[44]  Markus J Buehler,et al.  Nanomechanics of functional and pathological amyloid materials. , 2011, Nature nanotechnology.

[45]  Harjinder Singh,et al.  In vitro digestion of beta-lactoglobulin fibrils formed by heat treatment at low pH. , 2010, Journal of agricultural and food chemistry.