Correlation between protein secondary structure and mechanical performance for the ultra-tough dragline silk of Darwin's bark spider

The spider major ampullate (MA) silk exhibits high tensile strength and extensibility and is typically a blend of MaSp1 and MaSp2 proteins with the latter comprising glycine–proline–glycine–glycine-X repeating motifs that promote extensibility and supercontraction. The MA silk from Darwin''s bark spider (Caerostris darwini) is estimated to be two to three times tougher than the MA silk from other spider species. Previous research suggests that a unique MaSp4 protein incorporates proline into a novel glycine–proline–glycine–proline motif and may explain C. darwini MA silk''s extraordinary toughness. However, no direct correlation has been made between the silk''s molecular structure and its mechanical properties for C. darwini. Here, we correlate the relative protein secondary structure composition of MA silk from C. darwini and four other spider species with mechanical properties before and after supercontraction to understand the effect of the additional MaSp4 protein. Our results demonstrate that C. darwini MA silk possesses a unique protein composition with a lower ratio of helices (31%) and β-sheets (20%) than other species. Before supercontraction, toughness, modulus and tensile strength correlate with percentages of β-sheets, unordered or random coiled regions and β-turns. However, after supercontraction, only modulus and strain at break correlate with percentages of β-sheets and β-turns. Our study highlights that additional information including crystal size and crystal and chain orientation is necessary to build a complete structure–property correlation model.     

Post-secretion processing influences spider silk performance

Phenotypic variation facilitates adaptations to novel environments. Silk is an example of a highly variable biomaterial. The two-spidroin (MaSp) model suggests that spider major ampullate (MA) silk is composed of two proteins—MaSp1 predominately contains alanine and glycine and forms strength enhancing β-sheet crystals, while MaSp2 contains proline and forms elastic spirals. Nonetheless, mechanical properties can vary in spider silks without congruent amino acid compositional changes. We predicted that post-secretion processing causes variation in the mechanical performance of wild MA silk independent of protein composition or spinning speed across 10 species of spider. We used supercontraction to remove post-secretion effects and compared the mechanics of silk in this ‘ground state’ with wild native silks. Native silk mechanics varied less among species compared with ‘ground state’ silks. Variability in the mechanics of ‘ground state’ silks was associated with proline composition. However, variability in native silks did not. We attribute interspecific similarities in the mechanical properties of native silks, regardless of amino acid compositions, to glandular processes altering molecular alignment of the proteins prior to extrusion. Such post-secretion processing may enable MA silk to maintain functionality across environments, facilitating its function as a component of an insect-catching web.     

Comparative Study of Strain‐Dependent Structural Changes of Silkworm Silks: Insight into the Structural Origin of Strain‐Stiffening

Structure–property relationships of silk is an intriguing topic for silk‐based biomaterials research since these features are related to biomimicking the processing in natural silk fiber formation which results in excellent mechanical properties. Strain‐stiffening is common for spider silks and nonmulberry silkworm silks. However, the structural origin of strain‐stiffening remains unclear. In this paper, the strain‐dependent structural change of Antheraea pernyi silkworm silk is studied by X‐ray fiber diffraction and Fourier transform infrared spectroscopy under stretching. Based on a combination of mechanical and structural analysis, the molecular origins of strain‐stiffening in A. pernyi silk were determined. The relatively high content of the β‐sheets within the amorphous domains in A. pernyi silk is responsible for strain‐stiffening, where “molecular spindles” enhance the extensibility and toughness of the fiber.     

Impact of different silkworm dietary supplements on its silk performance

This study aims to evaluate the effect of silkworm larva (Bombyx mori) diet supplementation with two amino acids (threonine and valine) on the cocoon production and on the structural and mechanical properties of the silk produced. Negligible morphological differences were observed in the silk fiber threads from silkworm larvae supplemented with the tested amino acids. Higher production (yield) of silk was obtained using threonine in the diet of the silkworm. The treatments with threonine have increased the limit of proportionality, tensile strength, toughness, and maximum deformation of the thread of silk fibers. No significant increment in these properties was observed due to the increase in the threonine content. The treatments with valine led to lower increase in tensile strength and toughness. The real density of the silk has decreased with the use of supplements. The present study contributes to engineering of advanced silk materials, which should be attractive candidates for multipurpose applications.     

Theoretical and computational hierarchical nanomechanics of protein materials: Deformation and fracture

Proteins constitute the building blocks of biological materials such as tendon, bone, skin, spider silk or cells. An important trait of these materials is that they display highly characteristic hierarchical structures, across multiple scales, from nano to macro. Protein materials are intriguing examples of materials that balance multiple tasks, representing some of the most sustainable material solutions that integrate structure and function. Here we review progress in understanding the deformation and fracture mechanisms of hierarchical protein materials by using a materials science approach to develop structure-process-property relations, an effort defined as materiomics. Deformation processes begin with an erratic motion of individual atoms around flaws or defects that quickly evolve into formation of macroscopic fractures as chemical bonds rupture rapidly, eventually compromising the integrity of the structure or the biological system leading to failure. The combination of large-scale atomistic simulation, multi-scale modeling methods, theoretical analyses combined with experimental validation provides a powerful approach in studying deformation and failure phenomena in protein materials. Here we review studies focused on the molecular origin of deformation and fracture processes of three types of protein materials. The review includes studies of collagen - Nature’s super-glue; beta-sheet rich protein structures as found in spider silk - a natural fiber that can reach the strength of a steel cable; as well as intermediate filaments - a class of alpha-helix based structural proteins responsible for the mechanical integrity of eukaryotic cells. The article concludes with a discussion of the significance of universally found structural patterns such as the staggered collagen fibril architecture or the alpha-helical protein motif.     

Comparing the rheology of native spider and silkworm spinning dope

Silk production has evolved to be energetically efficient and functionally optimized, yielding a material that can outperform most industrial fibres, particularly in toughness. Spider silk has hitherto defied all attempts at reproduction, despite advances in our understanding of the molecular mechanisms behind its superb mechanical properties. Spun fibres, natural and man-made, rely on the extrusion process to facilitate molecular orientation and bonding. Hence a full understanding of the flow characteristics of native spinning feedstock (dope) will be essential to translate natural spinning to artificial silk production. Here we show remarkable similarity between the rheologies for native spider-dragline and silkworm-cocoon silk, despite their independent evolution and substantial differences in protein structure. Surprisingly, both dopes behave like typical polymer melts. This observation opens the door to using polymer theory to clarify our general understanding of natural silks, despite the many specializations found in different animal species.     

Nanoconfinement of spider silk fibrils begets superior strength, extensibility, and toughness

Silk is an exceptionally strong, extensible, and tough material made from simple protein building blocks. The molecular structure of dragline spider silk repeat units consists of semiamorphous and nanocrystalline β-sheet protein domains. Here we show by a series of computational experiments how the nanoscale properties of silk repeat units are scaled up to create macroscopic silk fibers with outstanding mechanical properties despite the presence of cavities, tears, and cracks. We demonstrate that the geometric confinement of silk fibrils to diameters of 50 ± 30 nm is critical to facilitate a powerful mechanism by which hundreds of thousands of protein domains synergistically resist deformation and failure to provide enhanced strength, extensibility, and toughness at the macroscale, closely matching experimentally measured mechanical properties. Through this mechanism silk fibers exploit the full potential of the nanoscale building blocks, regardless of the details of microscopic loading conditions and despite the presence of large defects. Experimental results confirm that silk fibers are composed of silk fibril bundles with diameters in the range of 20-150 nm, in agreement with our predicted length scale. Our study reveals a general mechanism to map nanoscale properties to the macroscale and provides a potent design strategy toward novel fiber and bulk nanomaterials through hierarchical structures.     

An experimental confirmation of thermal transitions in native and regenerated spider silks

Biological structures such as spider silks are formed by proteins. The physical properties of such proteins are determined by environmental conditions such as temperature and humidity. In this paper, we confirm the thermal transitions that take place in spider silks using differential scanning calorimetry and study how the interaction of spider silk proteins with water affects the onset temperatures for these thermal processes. Native fibres and regenerated films of dragline silk and egg sac silk from Argiope argentata spiders were used to study thermal transitions of protein based structures. For the first time, differential scanning calorimetry (DSC) tests were carried out with spider silk samples of relatively large mass (10 mg). Previous attempts of DSC tests applied to spider silk samples failed to detect thermal transitions in a conclusive way. The tests reported here, however, show thermal transitions on both natural and regenerated samples that are in agreement with results from dynamic mechanical analysis (DMA) tests reported in the literature. The water content on spider silks seems to lower the temperatures at which such thermal transitions take place. The results also confirm that the amorphous regions of native and regenerated spider silk and silk worm silk give rise to similar thermal transitions.     

层状复合陶瓷强韧化机制及其优化设计因素

层状复合是一种新型的陶瓷复合构型, 具有提高断裂韧性和强度的优异特性, 对优化陶瓷的显微结构和机械性能十分有效本文从层状复合界面结构出发, 综合评述了层状复合陶瓷的强韧化机制, 讨论基体单层强度、厚度, 界面的厚度和粘接强度等因素对断裂韧性等性能的影响, 探讨层状复合陶瓷的优化设计思路     

Effect of water and ice on strength and fracture toughness of intermittently bonded boron-epoxy composites

The effects of water and ice on the strength and fracture toughness of boron-epoxy composites with polyurethane intermittent bonding have been investigated. Neither simple soaking in water nor soaking followed by freezing and thawing have marked effects on the strength of the fully-coated composites, but they have disastrous effects on the uncoated composites. Toughness is affected only marginally, with some small reductions in the fully-coated samples, and with essentially no effect on the uncoated composites. An analysis is presented which explains adequately the experimental strength and toughness results obtained, and which is based on an argument that water absorption reduces the interfacial shear strength only of the uncoated areas and not those regions coated by the polyurethane varnish. The results indicate that the advantages of appropriate intermittent bonding (i.e. high strength combined with high toughness) are retained in wet conditions so that such composites may be favourably used in such adverse environmental conditions.     

Strong,Conductive, Foldable Graphene Sheets by Sequential Ionic and π Bridging

The goal of this work is to develop an inexpensive low‐temperature process that provides polymer‐free, high‐strength, high‐toughness, electrically conducting sheets of reduced graphene oxide (rGO). To develop this process, we have evaluated the mechanical and electrical properties resulting from the application of an ionic bonding agent (Cr³⁺), a π–π bonding agent comprising pyrene end groups, and their combinations for enhancing the performance of rGO sheets. When only one bonding agent was used, the π–π bonding agent is much more effective than the ionic bonding agent for improving both the mechanical and electrical properties of rGO sheets. However, the successive application of ionic bonding and π–π bonding agents maximizes tensile strength, toughness, long‐term electrical stability in various corrosive solutions, and resistance to mechanical abuse and ultrasonic dissolution. Using a combination of ionic bonding and π–π bonding agents, high tensile strength (821 MPa), high toughness (20 MJ m^?3), and electrical conductivity (416 S cm^?1) were obtained, as well as remarkable retention of mechanical and electrical properties during ultrasonication and mechanical cycling by both sheet stretch and sheet folding, suggesting high potential for applications in aerospace and flexible electronics.     

Tuning the mechanical properties of glass fiber-reinforced bismaleimide–triazine resin composites by constructing a flexible bridge at the interface

Abstract

We demonstrate a new method that can simultaneously improve the strength and toughness of the glass fiber-reinforced bismaleimide–triazine (BT) resin composites by using polyethylene glycol (PEG) to construct a flexible bridge at the interface. The mechanical properties, including the elongation, ultimate tensile stress, Young’s modulus, toughness and dynamical mechanical properties were studied as a function of the length of PEG molecular chain. It was found that the PEG molecule acts as a bridge to link BT resin and glass fiber through covalent and non-covalent bondings, respectively, resulting in improved interfacial bonding. The incorporation of PEG produces an increase in elongation, ultimate tensile stress and toughness. The Young’s modulus and T_g were slightly reduced when the length of the PEG molecular chain was high. The elongation of the PEG-modified glass fiber-reinforced composites containing 5 wt% PEG-8000 increased by 67.1%, the ultimate tensile stress by 17.9% and the toughness by 78.2% compared to the unmodified one. This approach provides an efficient way to develop substrate material with improved strength and toughness for integrated circuit packaging applications.     

Material Mechanical Properties Necessary for the Structural Intervention of Concrete Structures

Structural intervention involves the restoration and/or upgrading of the mechanical performances of structures. In addition to concrete and steel, which are typical materials for concrete structures, various fiber-reinforced polymers (FRPs), cementitious materials with fibers, polymers, and adhesives are often applied for structural intervention. In order to predict structural performance, it is necessary to develop a generic method that is applicable to not only to steel, but also to other materials. Such a generic model could provide information on the mechanical properties required to improve the structural performance. External bonding, which is a typical scheme for structural intervention, is not applied for new structures. It is necessary to clarify material properties and structural details in order to achieve better bonding strength at the interface between the substrate concrete and an externally bonded material. This paper presents the mechanical properties of substrate concrete and relevant intervention material for the following purposes: ① to achieve better shear strength and ultimate deformation of a member after structural intervention; and ② to achieve better debonding strength for external bonding. This paper concludes that some of the mechanical properties and structural details for intervention materials that are necessary for improvement in mechanical performance in structures with structural intervention are new, and differ from those of structures without intervention. For example, high strength and stiffness are important properties for materials in structures without structural intervention, whereas high fracturing strain and low stiffness are important properties for structural intervention materials.     

Multiscale Experimental Mechanics of Hierarchical Carbon‐Based Materials

Investigation of the mechanics of natural materials, such as spider silk, abalone shells, and bone, has provided great insight into the design of materials that can simultaneously achieve high specific strength and toughness. Research has shown that their emergent mechanical properties are owed in part to their specific self‐organization in hierarchical molecular structures, from nanoscale to macroscale, as well as their mixing and bonding. To apply these findings to manmade materials, researchers have devoted significant efforts in developing a fundamental understanding of multiscale mechanics of materials and its application to the design of novel materials with superior mechanical performance. These efforts included the utilization of some of the most promising carbon‐based nanomaterials, such as carbon nanotubes, carbon nanofibers, and graphene, together with a variety of matrix materials. At the core of these efforts lies the need to characterize material mechanical behavior across multiple length scales starting from nanoscale characterization of constituents and their interactions to emerging micro‐ and macroscale properties. In this report, progress made in experimental tools and methods currently used for material characterization across multiple length scales is reviewed, as well as a discussion of how they have impacted our current understanding of the mechanics of hierarchical carbon‐based materials. In addition, insight is provided into strategies for bridging experiments across length scales, which are essential in establishing a multiscale characterization approach. While the focus of this progress report is in experimental methods, their concerted use with theoretical‐computational approaches towards the establishment of a robust material by design methodology is also discussed, which can pave the way for the development of novel materials possessing unprecedented mechanical properties.     

高强度钢材钢结构研究进展综述

高强度钢材钢结构在结构受力性能、建筑使用功能以及社会经济效益等方面具有显著优势,近几年开始在国内外多个建筑和桥梁结构中取得了成功应用。该文全面综述了国内外学者针对高强度钢材钢结构在材料和构件层面受力性能方面取得的研究成果,包括材料的静力拉伸力学性能和韧性、断裂以及疲劳性能,构件的受压稳定和抗震性能,以及连接节点的力学性能等内容,为此类新型钢结构进一步的研究工作及设计方法制定提供参考,同时促进其在我国钢结构工程的应用。     

Geometric confinement governs the rupture strength of H-bond assemblies at a critical length scale

The ultrastructure of protein materials such as spider silk, muscle tissue, or amyloid fibers consists primarily of beta-sheets structures, composed of hierarchical assemblies of H-bonds. Despite the weakness of H-bond interactions, which have intermolecular bonds 100 to 1000 times weaker than those in ceramics or metals, these materials combine exceptional strength, robustness, and resilience. We discover that the rupture strength of H-bond assemblies is governed by geometric confinement effects, suggesting that clusters of at most 3-4 H-bonds break concurrently, even under uniform shear loading of a much larger number of H-bonds. This universally valid result leads to an intrinsic strength limitation that suggests that shorter strands with less H-bonds achieve the highest shear strength at a critical length scale. The hypothesis is confirmed by direct large-scale full-atomistic MD simulation studies of beta-sheet structures in explicit solvent. Our finding explains how the intrinsic strength limitation of H-bonds can be overcome by the formation of a nanocomposite structure of H-bond clusters, thereby enabling the formation of larger and much stronger beta-sheet structures. Our results explain recent experimental proteomics data, suggesting a correlation between the shear strength and the prevalence of beta-strand lengths in biology.     

Hierarchical Structure of Silk Materials Versus Mechanical Performance and Mesoscopic Engineering Principles

A comprehensive review on the five levels of hierarchical structures of silk materials and the correlation with macroscopic properties/performance of the silk materials, that is, the toughness, strain‐stiffening, etc., is presented. It follows that the crystalline binding force turns out to be very important in the stabilization of silk materials, while the β‐crystallite networks or nanofibrils and the interactions among helical nanofibrils are two of the most essential structural elements, which to a large extent determine the macroscopic performance of various forms of silk materials. In this context, the characteristic structural factors such as the orientation, size, and density of β‐crystallites are very crucial. It is revealed that the formation of these structural elements is mainly controlled by the intermolecular nucleation of β‐crystallites. Consequently, the rational design and reconstruction of silk materials can be implemented by controlling the molecular nucleation via applying sheering force and seeding (i.e., with carbon nanotubes). In general, the knowledge of the correlation between hierarchical structures and performance provides an understanding of the structural reasons behind the fascinating behaviors of silk materials.     

Modifications of spider silk sequences in an attempt to control the mechanical properties of the synthetic fibers

Bacteria were genetically engineered to produce two spider silk protein variants composed of basic repeat units combining a flagelliform elastic motif ([GPGGX]₄) and a major ampullate silk strength motif ([linker/poly-alanine]. The secondary structures of the pure recombinant proteins in solution were determined by circular dichroism. The data presented suggest that the nature of the 5th and 10th amino acid (X) in the [GPGGX]₂ elastic motif and temperature have an impact on the amount of β-sheet structures present in the proteins. More specifically, increasing temperatures seem to be positively correlated with β-sheet formation for both proteins and this state is irreversible or reversible when both X (5th and 10th) in the elastic motif are hydrophilic or hydrophobic respectively. Moreover, each pure silk-like protein was able to spontaneously self-assemble into films from aqueous solutions. Two kinds of synthetic fibers were made by pulling fibers from these preassembled films as well as spinning fibers from each protein resolubilized in HFIP. The mechanical data show that the pulled fibers are far tougher than the spun fibers suggesting a better fiber organization. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Multilayer DLC coatings via alternating bias during magnetron sputtering

To combat the high residual stress problem in monolayer diamond-like carbon coatings, this paper fabricated multilayer diamond-like carbon coatings with alternate soft and hard layers via alternating bias during magnetron sputtering. The surface, cross sectional morphology, bonding structures and mechanical properties are investigated. The atomic force microscopy images indicate low bias results in rougher surface with large graphite clusters and voids suggesting low coating density. The multilayered coatings demonstrate relatively smooth surface stemming from higher bias. The cross sectional images from field emission scanning electron microscopy indicate coating thickness decreases as substrate bias increases and confirm that higher bias results in denser coating. Delamination is observed in monolayer coatings due to high residual stress. The trend of sp³/sp² fraction estimated by X-ray photoelectron spectroscopy is consistent with that of I_D/I_G ratios from Raman spectra, indicating the change of bonding structure with change of substrate bias. Hardness of multilayer diamond-like carbon coating is comparable to the coatings deposited at low constant bias but the adhesion strength and toughness are significantly improved. Alternately biased sputtering deposition provides an alternative when combination of hardness, toughness and adhesion strength is needed in an all diamond-like carbon coating.     

On the strength of β-sheet crystallites of Bombyx mori silk fibroin

Silk fibroin, a natural multi-domain protein, has attracted great attention due to its superior mechanical properties such as ultra-high strength and stretchability, biocompatibility, as well as its versatile biodegradability and processability. It is mainly composed of β-sheet crystallites and amorphous domains. Although its strength is well known to be controlled by the dissociation of protein chains from β-sheet crystallites, the way that water as the solvent affects its strength and the reason that its theoretically predicted strength is several times higher than experimental measurement remain unclear. We perform all-atom molecular dynamics simulations on a β-sheet crystallite of Bombyx mori silk. We find that water solvent reduces the number and strength of hydrogen bonds between β-chains, and thus greatly weakens the strength of silk fibroin. By dissociating protein chains at different locations from the crystallite, we also find that the pulling strength for the interior chains is several times higher than that for the surface/corner chains, with the former being consistent with the theoretically predicted value, while the latter on par with the experimental value. It is shown that the weakest rupture strength controls the failure strength of silk fibre. Hence, this work sheds light on the role of water in the strength of silk fibroin and also provides clues on the origin of the strength difference between theory and experiment.