Development of mechanically-consistent coarse-grained molecular dynamics model: case study of mechanics of spider silk.

Understanding mechanics of spider silk holds immense importance due to its potential to drive innovation in the development of materials with exceptional mechanical characteristics suited for a wide range of applications. Coarse-grained (CG) molecular simulations plays a particularly valuable role in this endeavor, allowing for the efficient investigation of spider silk's mechanical properties. Our research is centered on the examination of spider silk, which comprises major ampullate silk protein (MaSp1). To achieve this, we developed a CG molecular dynamics model. Our investigation began with a focus on MaSp1 chains subjected to uniaxial tensile load, with comparisons made between the CG model results and all-atom simulations. Subsequently, we extended our simulations to encompass more extensive systems, including fully-ordered MaSp1 bundles undergoing uniaxial static stretching. Through comparison with existing literature, we assess how well the CG model reproduces the mechanical properties of spider silk in highly ordered structures. Furthermore, we explored a scenario where MaSp1 bundles were randomly positioned and stretched, providing valuable insights into silk behavior when the initial structure lacks order. Another simulation involved random positioning, but with some degree of orientation in the loading direction, allowing for a closer examination of the initial structure's influence.

Multiscale static and dynamic mechanical study of the Turritella terebra and Turritellinella tricarinata seashells.

Marine shells are designed by nature to ensure mechanical protection from predators and shelter for molluscs living inside them. A large amount of work has been done to study the multiscale mechanical properties of their complex microstructure and to draw inspiration for the design of impact-resistant biomimetic materials. Less is known regarding the dynamic behaviour related to their structure at multiple scales. Here, we present a combined experimental and numerical study of the shells of two different species of gastropod sea snail belonging to the Turritellidae family, featuring a peculiar helicoconic shape with hierarchical spiral elements. The proposed procedure involves the use of micro-computed tomography scans for the accurate determination of geometry, atomic force microscopy and nanoindentation to evaluate local mechanical properties, surface morphology and heterogeneity, as well as resonant ultrasound spectroscopy coupled with finite element analysis simulations to determine global modal behaviour. Results indicate that the specific features of the considered shells, in particular their helicoconic and hierarchical structure, can also be linked to their vibration attenuation behaviour. Moreover, the proposed investigation method can be extended to the study of other natural systems, to determine their structure-related dynamic properties, ultimately aiding the design of bioinspired metamaterials and of structures with advanced vibration control.

Topographically guided hierarchical mineralization.

Material platforms based on interaction between organic and inorganic phases offer enormous potential to develop materials that can recreate the structural and functional properties of biological systems. However, the capability of organic-mediated mineralizing strategies to guide mineralization with spatial control remains a major limitation. Here, we report on the integration of a protein-based mineralizing matrix with surface topographies to grow spatially guided mineralized structures. We reveal how well-defined geometrical spaces defined within the organic matrix by the surface topographies can trigger subtle changes in single nanocrystal co-alignment, which are then translated to drastic changes in mineralization at the microscale and macroscale. Furthermore, through systematic modifications of the surface topographies, we demonstrate the possibility of selectively guiding the growth of hierarchically mineralized structures. We foresee that the capacity to direct the anisotropic growth of such structures would have important implications in the design of biomineralizing synthetic materials to repair or regenerate hard tissues.

Correction: Thermoelectric properties of CZTS thin films: effect of Cu-Zn disorder.

Correction for 'Thermoelectric properties of CZTS thin films: effect of Cu-Zn disorder' by E. Isotta et al., Phys. Chem. Chem. Phys., 2021, DOI: 10.1039/d1cp01327k.

Thermoelectric properties of CZTS thin films: effect of Cu-Zn disorder.

Cu-Zn disorder is known to deeply affect kesterite (Cu2ZnSnS4, CZTS) due to the low temperature order-disorder phase transition, leading to a random occupation of the two cations in the shared crystallographic planes. This defect complex has been extensively studied in the thin film photovoltaic sector, with considerable efforts in developing methods to quantify disorder. In this study, a preliminary investigation of thermoelectric properties in temperature for thin film CZTS is presented. It is found that Cu-Zn disorder enhances both electrical conductivity and Seebeck coefficient. This can positively affect the thermoelectric performance, showing a mechanism of potential interest for a broad class of quaternary chalcogenides. The order-disorder transition is clearly visible in the electronic properties. This feature is repeatable, with samples from different preparations and groups showing consistent results, qualitatively suggesting electronic measurements as possible methods to quantify disorder. Furthermore, the reversibility of the transition allows the electronic properties to be tuned via specific thermal treatments, pointing to interesting applications in tunable electronics.

Air-encapsulating elastic mechanism of submerged Taraxacum blowballs.

In this article, we report the observation of an air-encapsulating elastic mechanism of Dandelion spherical seed heads, namely blowballs, when submerged underwater. This peculiarity seems to be fortuitous since Taraxacum is living outside water; nevertheless, it could become beneficial for a better survival under critical conditions, e.g. of temporary flooding. The scaling of the volume of the air entrapped suggests its fractal nature with a dimension of 2.782 and a fractal air volume fraction of 4.82 × 10-2 m0.218, resulting in nominal air volume fractions in the range of 14-23%. This aspect is essential for the optimal design of bioinspired materials made up of Dandelion-like components. The miniaturization of such components leads to an increase in the efficiency of the air encapsulation up to the threshold (efficiency = 1) achieved for an optimal critical size. Thus, the optimal design is accomplished using small elements, with the optimal size, rather than using larger elements in a lower number. The described phenomenon, interesting per se, also brings bioinspired insights toward new related technological solutions for underwater air-trapping and air-bubbles transportation, e.g. the body surface of a man could allow an apnea (air consumption of 5-10 l/min) of about 10 min if it is covered by a material made up of a periodic repetition of Dandelion components of diameter ≅ 18 µm and having a total thickness of about 3-6 cm.

Reduction of fibrillar strain-rate sensitivity in steroid-induced osteoporosis linked to changes in mineralized fibrillar nanostructure.

As bone is used in a dynamic mechanical environment, understanding the structural origins of its time-dependent mechanical behaviour - and the alterations in metabolic bone disease - is of interest. However, at the scale of the mineralized fibrillar matrix (nanometre-level), the nature of the strain-rate dependent mechanics is incompletely understood. Here, we investigate the fibrillar- and mineral-deformation behaviour in a murine model of Cushing's syndrome, used to understand steroid induced osteoporosis, using synchrotron small- and wide-angle scattering/diffraction combined with in situ tensile testing at three strain rates ranging from 10-4 to 10-1 s-1. We find that the effective fibril- and mineral-modulus and fibrillar-reorientation show no significant increase with strain-rate in osteoporotic bone, but increase significantly in normal (wild-type) bone. By applying a fibril-lamellar two-level structural model of bone matrix deformation to fit the results, we obtain indications that altered collagen-mineral interactions at the nanoscale - along with altered fibrillar orientation distributions - may be the underlying reason for this altered strain-rate sensitivity. Our results suggest that an altered strain-rate sensitivity of the bone matrix in osteoporosis may be one of the contributing factors to reduced mechanical competence in such metabolic bone disorders, and that increasing this sensitivity may improve biomechanical performance.

Proof of concept of a frequency-preserving and time-invariant metamaterial-based nonlinear acoustic diode.

Acoustic filters and metamaterials have become essential components for elastic wave control in applications ranging from ultrasonics to noise abatement. Other devices have been designed in this field, emulating their electromagnetic counterparts. One such case is an acoustic diode or rectifier, which enables one-way wave transmission by breaking the wave equation-related reciprocity. Its achievement, however, has proved to be rather problematic, and current realizations display a number of shortcomings in terms of simplicity and versatility. Here, we present the design, fabrication and characterization of a device able to work as an acoustic diode, a switch and a transistor-like apparatus, exploiting symmetry-breaking nonlinear effects like harmonic generation and wave mixing, and the filtering capabilities of metamaterials. This device presents several advantages compared with previous acoustic diode realizations, including versatility, time invariance, frequency preserving characteristics and switchability. We numerically evaluate its efficiency and demonstrate its feasibility in a preliminary experimental realization. This work may provide new opportunities for the practical realization of structural components with one-way wave propagation properties.

Cleaning interfaces in layered materials heterostructures.

Heterostructures formed by stacking layered materials require atomically clean interfaces. However, contaminants are usually trapped between the layers, aggregating into randomly located blisters, incompatible with scalable fabrication processes. Here we report a process to remove blisters from fully formed heterostructures. Our method is over an order of magnitude faster than those previously reported and allows multiple interfaces to be cleaned simultaneously. We fabricate blister-free regions of graphene encapsulated in hexagonal boron nitride with an area ~ 5000 µm2, achieving mobilities up to 180,000 cm2 V-1 s-1 at room temperature, and 1.8 × 106 cm2 V-1 s-1 at 9 K. We also assemble heterostructures using graphene intentionally exposed to polymers and solvents. After cleaning, these samples reach similar mobilities. This demonstrates that exposure of graphene to process-related contaminants is compatible with the realization of high mobility samples, paving the way to the development of wafer-scale processes for the integration of layered materials in (opto)electronic devices.

Bone matrix development in steroid-induced osteoporosis is associated with a consistently reduced fibrillar stiffness linked to altered bone mineral quality.

Glucocorticoid-induced osteoporosis (GIOP) is a major secondary form of osteoporosis, with the fracture risk significantly elevated - at similar levels of bone mineral density - in patients taking glucocorticoids compared with non-users. The adverse bone structural changes at multiple hierarchical levels in GIOP, and their mechanistic consequences leading to reduced load-bearing capacity, are not clearly understood. Here we combine experimental X-ray nanoscale mechanical imaging with analytical modelling of the bone matrix mechanics to determine mechanisms causing bone material quality deterioration during development of GIOP. In situ synchrotron small-angle X-ray diffraction combined with tensile testing was used to measure nanoscale deformation mechanisms in a murine model of GIOP, due to a corticotrophin-releasing hormone promoter mutation, at multiple ages (8-, 12-, 24- and 36 weeks), complemented by quantitative micro-computed tomography and backscattered electron imaging to determine mineral concentrations. We develop a two-level hierarchical model of the bone matrix (mineralized fibril and lamella) to predict fibrillar mechanical response as a function of architectural parameters of the mineralized matrix. The fibrillar elastic modulus of GIOP-bone is lower than healthy bone throughout development, and nearly constant in time, in contrast to the progressively increasing stiffness in healthy bone. The lower mineral platelet aspect ratio value for GIOP compared to healthy bone in the multiscale model can explain the fibrillar deformation. Consistent with this result, independent measurement of mineral platelet lengths from wide-angle X-ray diffraction finds a shorter mineral platelet length in GIOP. Our results show how lowered mineralization combined with altered mineral nanostructure in GIOP leads to lowered mechanical competence. SIGNIFICANCE STATEMENT: Increased fragility in musculoskeletal disorders like osteoporosis are believed to arise due to alterations in bone structure at multiple length-scales from the organ down to the supramolecular-level, where collagen molecules and elongated mineral nanoparticles form stiff fibrils. However, the nature of these molecular-level alterations are not known. Here we used X-ray scattering to determine both how bone fibrils deform in secondary osteoporosis, as well as how the fibril orientation and mineral nanoparticle structure changes. We found that osteoporotic fibrils become less stiff both because the mineral nanoparticles became shorter and less efficient at transferring load from collagen, and because the fibrils are more randomly oriented. These results will help in the design of new composite musculoskeletal implants for bone repair.

Towards in situ determination of 3D strain and reorientation in the interpenetrating nanofibre networks of cuticle.

Determining the in situ 3D nano- and microscale strain and reorientation fields in hierarchical nanocomposite materials is technically very challenging. Such a determination is important to understand the mechanisms enabling their functional optimization. An example of functional specialization to high dynamic mechanical resistance is the crustacean stomatopod cuticle. Here we develop a new 3D X-ray nanostrain reconstruction method combining analytical modelling of the diffraction signal, fibre-composite theory and in situ deformation, to determine the hitherto unknown nano- and microscale deformation mechanisms in stomatopod tergite cuticle. Stomatopod cuticle at the nanoscale consists of mineralized chitin fibres and calcified protein matrix, which form (at the microscale) plywood (Bouligand) layers with interpenetrating pore-canal fibres. We uncover anisotropic deformation patterns inside Bouligand lamellae, accompanied by load-induced fibre reorientation and pore-canal fibre compression. Lamination theory was used to decouple in-plane fibre reorientation from diffraction intensity changes induced by 3D lamellae tilting. Our method enables separation of deformation dynamics at multiple hierarchical levels, a critical consideration in the cooperative mechanics characteristic of biological and bioinspired materials. The nanostrain reconstruction technique is general, depending only on molecular-level fibre symmetry and can be applied to the in situ dynamics of advanced nanostructured materials with 3D hierarchical design.

Serpentine locomotion through elastic energy release.

A model for serpentine locomotion is derived from a novel perspective based on concepts from configurational mechanics. The motion is realized through the release of the elastic energy of a deformable rod, sliding inside a frictionless channel, which represents a snake moving against lateral restraints. A new formulation is presented, correcting previous results and including situations never analysed so far, as in the cases when the serpent's body lies only partially inside the restraining channel or when the body has a muscle relaxation localized in a small zone. Micromechanical considerations show that propulsion is the result of reactions tangential to the frictionless constraint and acting on the snake's body, a counter-intuitive feature in mechanics. It is also experimentally demonstrated that the propulsive force driving serpentine motion can be directly measured on a designed apparatus in which flexible bars sweep a frictionless channel. Experiments fully confirm the theoretical modelling, so that the presented results open the way to exploration of effects, such as variability in the bending stiffness or channel geometry or friction, on the propulsive force of snake models made up of elastic rods.

Proof of Concept for an Ultrasensitive Technique to Detect and Localize Sources of Elastic Nonlinearity Using Phononic Crystals.

The appearance of nonlinear effects in elastic wave propagation is one of the most reliable and sensitive indicators of the onset of material damage. However, these effects are usually very small and can be detected only using cumbersome digital signal processing techniques. Here, we propose and experimentally validate an alternative approach, using the filtering and focusing properties of phononic crystals to naturally select and reflect the higher harmonics generated by nonlinear effects, enabling the realization of time-reversal procedures for nonlinear elastic source detection. The proposed device demonstrates its potential as an efficient, compact, portable, passive apparatus for nonlinear elastic wave sensing and damage detection.

Homogeneity of ball milled ceramic powders: Effect of jar shape and milling conditions.

This paper contains data and supporting information of and complementary to the research article entitled "Effect of jar shape on high-energy planetary ball milling efficiency: simulations and experiments" (Broseghini et al.,) [1]. Calcium fluoride (CaF2) was ground using two jars of different shape (cylindrical and half-moon) installed on a planetary ball-mill, exploring different operating conditions (jar-to-plate angular velocity ratio and milling time). Scanning Electron Microscopy (SEM) images and X-Ray Powder Diffraction data (XRPD) were collected to assess the effect of milling conditions on the end-product crystallite size. Due to the inhomogeneity of the end product, the Whole Powder Pattern Model (WPPM, (Scardi, 2008) [2]) analysis of XRPD data required the hypothesis of a bimodal distribution of sizes - respectively ground (fine fraction) and less-to-not ground (coarse fraction) - confirmed by SEM images and suggested by the previous literature (Abdellatief et al., 2013) [3,4]. Predominance of fine fraction clearly indicates optimal milling conditions.

Micromechanical model for protein materials: From macromolecules to macroscopic fibers.

We propose a model for the mechanical behavior of protein materials. Based on a limited number of experimental macromolecular parameters (persistence and contour length) we obtain the macroscopic behavior of keratin fibers (human, cow, and rabbit hair), taking into account the damage and residual stretches effects that are fundamental in many functions of life. We also show the capability of our approach to describe the main dissipation and permanent strain effects observed in the more complex spider silk fibers. The comparison between our results and the data obtained experimentally from cyclic tests demonstrates that our model is robust and is able to reproduce with a remarkable accuracy the experimental behavior of all protein materials we tested.

Microorganism Nutrition Processes as a General Route for the Preparation of Bionic Nanocomposites Based on Intractable Polymers.

In this paper the fermentation process activated by living microorganisms of the baker's yeast is proposed as a facile assembly method of hybrid nanoparticles at liquid interface. Water dispersion of commercial baker's yeast extract used for bread production, graphene nanoplatelets (GNPs), and carbon nanotubes (CNTs) were added to oil/water interface; when the yeast is activated by adding sugar, the byproduct carbon dioxide bubbles migrate from the water phase to the oil/water interface generating a floating nanostructured film at liquid interface where it is trapped. Starting from this simple method, we propose a general approach for the stabilization of intractable poly(etheretherketone) polymeric particles with GNPs and CNTs at immiscible liquid interface. This process allowed the formation of sintered porous composites with improved mechanical properties. The porous structure of the composites gave rise to a low thermal conductivity making them good candidates for thermal insulating applications. Liquid absorption by these porous composites has been also reported. We believe that this new approach may have applications in the large scale fabrication of nanomaterials and is particularly suited for the preparation of nanocomposites starting from polymers that are intractable by solvent casting.

Graphene-Based Bionic Composites with Multifunctional and Repairing Properties.

In this work, a novel bionic composite inspired by the concept of yeast fermentation has been proposed. It was observed that the addition of graphene nanoplatelets during the fermentation of extract of Saccharomyces cerevisiae fungi allows coupling of the graphene sheets to the yeast cell wall. This process resulted in the formation of a composite film with improved mechanical and electrical properties along with the capability of converting the light stimulus in the electrical signal. The mechanical properties of the prepared composites, namely, the fracture strength and Young's modulus, were studied via numerical simulations and are related to the properties of the constituent phases via rules of mixture. Finally, it was observed that graphene nanoplatelets, added to the nutrient broth, were able to reassemble onto the stressed cell surface and repair the surface cracking, partially restoring the pristine electrical and mechanical properties. The method reported here may find potential application in the development of self-healable bioelectronic devices and microorganism-based strain and chemical biosensors.

A frequency-based hypothesis for mechanically targeting and selectively attacking cancer cells.

Experimental studies recently performed on single cancer and healthy cells have demonstrated that the former are about 70% softer than the latter, regardless of the cell lines and the measurement technique used for determining the mechanical properties. At least in principle, the difference in cell stiffness might thus be exploited to create mechanical-based targeting strategies for discriminating neoplastic transformations within human cell populations and for designing innovative complementary tools to cell-specific molecular tumour markers, leading to possible applications in the diagnosis and treatment of cancer diseases. With the aim of characterizing and gaining insight into the overall frequency response of single-cell systems to mechanical stimuli (typically low-intensity therapeutic ultrasound), a generalized viscoelastic paradigm, combining classical and spring-pot-based models, is introduced for modelling this problem by neglecting the cascade of mechanobiological events involving the cell nucleus, cytoskeleton, elastic membrane and cytosol. Theoretical results show that differences in stiffness, experimentally observed ex vivo and in vitro, allow healthy and cancer cells to be discriminated, by highlighting frequencies (from tens to hundreds of kilohertz) associated with resonance-like phenomena­prevailing on thermal fluctuations­that could be helpful in targeting and selectively attacking tumour cells.

Octopus-like suction cups: from natural to artificial solutions.

Octopus suckers are able to attach to all nonporous surfaces and generate a very strong attachment force. The well-known attachment features of this animal result from the softness of the sucker tissues and the surface morphology of the portion of the sucker that is in contact with objects or substrates. Unlike artificial suction cups, octopus suckers are characterized by a series of radial grooves that increase the area subjected to pressure reduction during attachment. In this study, we constructed artificial suction cups with different surface geometries and tested their attachment performances using a pull-off setup. First, smooth suction cups were obtained for casting; then, sucker surfaces were engraved with a laser cutter. As expected, for all the tested cases, the engraving treatment enhanced the attachment performance of the elastomeric suction cups compared with that of the smooth versions. Moreover, the results indicated that the surface geometry with the best attachment performance was the geometry most similar to octopus sucker morphology. The results obtained in this work can be utilized to design artificial suction cups with higher wet attachment performance.