Amyloids: From molecular structure to mechanical properties

AbstractMany proteins of diverse sequence, structure and function self-assemble into morphologically similar fibrillar aggregates known as amyloids. Amyloids are remarkable polymers in several respects. First of all, amyloids can be formed from proteins with very different amino acid sequences; the common denominator is that the individual proteins constituting the amyloid fold predominantly into a β-sheet structure. Secondly, the formation of the fibril occurs through non-covalent interactions between primarily the β-sheets, causing the monomers to stack into fibrils. The fibrils are remarkably robust, considering that the monomers are bound non-covalently. Finally, a common characteristic of fibrils is their unbranched, straight, fiber-like structure arising from the intertwining of the multiple β-sheet filaments. These remarkably ordered and stable nanofibrils can be useful as building blocks for protein-based functional materials, but they are also implicated in severe neurodegenerative diseases. The overall aim of this article is to highlight recent efforts aimed at obtaining insights into amyloid proteins on different length scales. Starting from molecular information on amyloids, single fibril properties and mechanical properties of networks of fibrils are described. Specifically, we focus on the self-assembly of amyloid protein fibrils composed of peptides and denatured model proteins, as well as the influence of inhibitors of fibril formation. Additionally, we will demonstrate how the application of recently developed vibrational spectroscopic techniques has emerged as a powerful approach to gain spatially resolved information on the structure–function relation of amyloids. While spectroscopy provides information on local molecular conformations and protein secondary structure, information on the single fibril level has been developed by diverse microscopic techniques. The approaches to reveal basic mechanical properties of single fibrils like bending rigidity, shear modulus, ultimate tensile strength and fracture behavior are illustrated. Lastly, mechanics of networks of amyloid fibrils, typically forming viscoelastic gels are outlined, with a focus on (micro-) rheological properties. The resulting fundamental insights are essential for the rational design of novel edible and biodegradable protein-based polymers, but also to devise therapeutic strategies to combat amyloid assembly and accumulation during pathogenic disorders

In situ N-doped graphene and Mo nanoribbon formation from Mo2Ti2C3 MXene monolayers

Since the advent of monolayered 2D transition metal carbide and nitrides (MXenes) in 2011, the number of different monolayer systems and the study thereof have been on the rise. Mo2Ti2C3 is one of the least studied MXenes and new insights to this material are of value to the field. Here, the stability of Mo2Ti2C3 under electron irradiation is investigated. A transmission electron microscope (TEM) is used to study the structural and elemental changes in situ. It is found that Mo2Ti2C3 is reasonably stable for the first 2 min of irradiation. However, structural changes occur thereafter, which trigger increasingly rapid and significant rearrangement. This results in the formation of pores and two new nanomaterials, namely, N-doped graphene membranes and Mo nanoribbons. The study provides insight into the stability of Mo2Ti2C3 monolayers against electron irradiation, which will allow for reliable future study of the material using TEM. Furthermore, these findings will facilitate further research in the rapidly growing field of electron beam driven chemistry and engineering of nanomaterials.Web of Scienceart. no. 190711

Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation

Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, [double bond, length as m-dash]NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4

Compartmentalization of gold nanoparticle clusters in hollow silica spheres and their assembly induced by an external electric field

Assembly of plasmonic nanoparticle clusters having hotspots in a specific space is an effective way to efficiently utilize their plasmonic properties. In the assembly, however, bulk-like aggregates of the nanoparticles are readily formed by strong van der Waals forces, inducing a decrease of the properties. The present work proposes an advanced method to avoid aggregation of the clusters by encapsulating into a confined space of hollow silica interior. Hollow spheres incorporating gold nanoparticle clusters were synthesized by a surface-protected etching process. The observation of inner nanoparticles with liquid cell transmission electron microscopy experimentally proved that the nanoparticles moved as a cluster instead of as dispersed nanoparticles within the water-filled hollow compartment. The hollow spheres incorporating the nanoparticle clusters were assembled in the vicinity of electrodes by application of an external AC electric field, resulting in the enhancement of Raman intensities of probe molecules. The nanoparticle-cluster-containing hollow spheres were redispersed when the electric field was turned off, showing that the hollow silica spheres can act as a physical barrier to avoid the cluster aggregation. The Raman intensities were reversibly changed by switching the electric field on and off to control the assembled or dispersed states of the hollow spheres

Solution-Mediated Inversion of SnSe to Sb2Se3 Thin-Films

New facile and controllable approaches to fabricating metal chalcogenide thin films with adjustable properties can significantly expand the scope of these materials in numerous optoelectronic and photovoltaic devices. Most traditional and especially wet-chemical synthetic pathways suffer from a sluggish ability to regulate the composition and have difficulty achieving the high-quality structural properties of the sought-after metal chalcogenides, especially at large 2D length scales. In this effort, and for the first time, we illustrated the fast and complete inversion of continuous SnSe thin-films to Sb2Se3 using a scalable top-down ion-exchange approach. Processing in dense solution systems yielded the formation of Sb2Se3 films with favorable structural characteristics, while oxide phases, which are typically present in most Sb2Se3 films regardless of the synthetic protocols used, were eliminated. Density functional theory (DFT) calculations performed on intermediate phases show strong relaxations of the atomic lattice due to the presence of substitutional and vacancy defects, which likely enhances the mobility of cationic species during cation exchange. Our concept can be applied to customize the properties of other metal chalcogenides or manufacture layered structures

Multivalent Patchy Colloids for Quantitative 3D Self-Assembly Studies.

We report methods to synthesize sub-micron- and micron-sized patchy silica particles with fluorescently labeled hemispherical titania protrusions, as well as routes to efficiently characterize these particles and self-assemble these particles into non-close-packed structures. The synthesis methods expand upon earlier work in the literature, in which silica particles packed in a colloidal crystal were surface-patterned with a silane coupling agent. Here, hemispherical amorphous titania protrusions were successfully labeled with fluorescent dyes, allowing for imaging by confocal microscopy and super-resolution techniques. Confocal microscopy was exploited to experimentally determine the numbers of protrusions per particle over large numbers of particles for good statistical significance, and these distributions were compared to simulations predicting the number of patches as a function of core particle polydispersity and maximum separation between the particle surfaces. We self-assembled these patchy particles into open percolating gel networks by exploiting solvophobic attractions between the protrusions

Multivalent Patchy Colloids for Quantitative 3D Self-Assembly Studies.

We report methods to synthesize sub-micron- and micron-sized patchy silica particles with fluorescently labeled hemispherical titania protrusions, as well as routes to efficiently characterize these particles and self-assemble these particles into non-close-packed structures. The synthesis methods expand upon earlier work in the literature, in which silica particles packed in a colloidal crystal were surface-patterned with a silane coupling agent. Here, hemispherical amorphous titania protrusions were successfully labeled with fluorescent dyes, allowing for imaging by confocal microscopy and super-resolution techniques. Confocal microscopy was exploited to experimentally determine the numbers of protrusions per particle over large numbers of particles for good statistical significance, and these distributions were compared to simulations predicting the number of patches as a function of core particle polydispersity and maximum separation between the particle surfaces. We self-assembled these patchy particles into open percolating gel networks by exploiting solvophobic attractions between the protrusions

Interplay between spherical confinement and particle shape on the self-assembly of rounded cubes.

Self-assembly of nanoparticles (NPs) inside drying emulsion droplets provides a general strategy for hierarchical structuring of matter at different length scales. The local orientation of neighboring crystalline NPs can be crucial to optimize for instance the optical and electronic properties of the self-assembled superstructures. By integrating experiments and computer simulations, we demonstrate that the orientational correlations of cubic NPs inside drying emulsion droplets are significantly determined by their flat faces. We analyze the rich interplay of positional and orientational order as the particle shape changes from a sharp cube to a rounded cube. Sharp cubes strongly align to form simple-cubic superstructures whereas rounded cubes assemble into icosahedral clusters with additionally strong local orientational correlations. This demonstrates that the interplay between packing, confinement and shape can be utilized to develop new materials with novel properties

Spontaneous Hetero-attachment of Single-Component Colloidal Precursors for the Synthesis of Asymmetric Au-Ag2X (X = S, Se) Heterodimers

Finding simple, easily controlled, and flexible synthetic routes for the preparation of ternary and hybrid nanostructured semiconductors is always highly desirable, especially to fulfill the requirements for mass production to enable application to many fields such as optoelectronics, thermoelectricity, and catalysis. Moreover, understanding the underlying reaction mechanisms is equally important, offering a starting point for its extrapolation from one system to another. In this work, we developed a new and more straightforward colloidal synthetic way to form hybrid Au-Ag2X (X = S, Se) nanoparticles under mild conditions through the reaction of Au and Ag2X nanostructured precursors in solution. At the solid-solid interface between metallic domains and the binary chalcogenide domains, a small fraction of a ternary AuAg3X2phase was observed to have grown as a consequence of a solid-state electrochemical reaction, as confirmed by computational studies. Thus, the formation of stable ternary phases drives the selective hetero-attachment of Au and Ag2X nanoparticles in solution, consolidates the interface between their domains, and stabilizes the whole hybrid Au-Ag2X systems

Twisting DNA by salt

The structure and properties of DNA depend on the environment, in particular the ion atmosphere. Here, we investigate how DNA twist -one of the central properties of DNA- changes with concentration and identity of the surrounding ions. To resolve how cations influence the twist, we combine single-molecule magnetic tweezer experiments and extensive all-atom molecular dynamics simulations. Two interconnected trends are observed for monovalent alkali and divalent alkaline earth cations. First, DNA twist increases monotonously with increasing concentration for all ions investigated. Second, for a given salt concentration, DNA twist strongly depends on cation identity. At 100 mM concentration, DNA twist increases as Na+ + + 2+ + ≈ Cs+ 2+ 2+ 2+. Our molecular dynamics simulations reveal that preferential binding of the cations to the DNA backbone or the nucleobases has opposing effects on DNA twist and provides the microscopic explanation of the observed ion specificity. However, the simulations also reveal shortcomings of existing force field parameters for Cs+ and Sr2+. The comprehensive view gained from our combined approach provides a foundation for understanding and predicting cation-induced structural changes both in nature and in DNA nanotechnology