Hierarchically-structured metalloprotein composite coatings biofabricated from co-existing condensed liquid phases

Complex hierarchical structure governs emergent properties in biopolymeric materials; yet, the material processing involved remains poorly understood. Here, we investigated the multi-scale structure and composition of the mussel byssus cuticle before, during and after formation to gain insight into the processing of this hard, yet extensible metal cross-linked protein composite. Our findings reveal that the granular substructure crucial to the cuticle’s function as a wear-resistant coating of an extensible polymer fiber is pre-organized in condensed liquid phase secretory vesicles. These are phase-separated into DOPA-rich proto-granules enveloped in a sulfur-rich proto-matrix which fuses during secretion, forming the sub-structure of the cuticle. Metal ions are added subsequently in a site-specific way, with iron contained in the sulfur-rich matrix and vanadium coordinated by DOPA-catechol in the granule. We posit that this hierarchical structure self-organizes via phase separation of specific amphiphilic proteins within secretory vesicles, resulting in a meso-scale structuring that governs cuticle function

The spider cuticle : a remarkable material toolbox for functional diversity

Engineered systems are typically based on a large variety of materials differing in composition and processing to provide the desired functionality. Nature, however, has evolved materials that are used for a wide range of functional challenges with minimal compositional changes. The exoskeletal cuticle of spiders, as well as of other arthropods such as insects and crustaceans, is based on a combination of chitin, protein, water and small amounts of organic cross-linkers or minerals. Spiders use it to obtain mechanical support structures and lever systems for locomotion, protection from adverse environmental influences, tools for piercing, cutting and interlocking, auxiliary structures for the transmission and filtering of sensory information, structural colours, transparent lenses for light manipulation and more. This paper illustrates the ‘design space’ of a single type of composite with varying internal architecture and its remarkable capability to serve a diversity of functions. This article is part of the theme issue ‘Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 1)’

Effects of moisture and cellulose fibril angle on the tensile properties of native single Norway spruce wood fibres

Isolated single wood fibres with cellulose fibril angles from 10 to 43° were tested in microtensile tests under controlled temperature and relative humidity of 5, 50, 75, 90% and in the wet state. This systematic study provides experimental stiffness and strength data, calculated on cell wall cross sections. It has been shown that stiffness reduction with increasing moisture content is more pronounced in fibres with large cellulose fibril angles. Interestingly, stiffness reduction in fibres with low cellulose fibril angles has been observed for the fully hydrated state only. The experimental dataset was fed into a model to determine moisture dependent stiffness of the hemicellulose-lignin-matrix and the stresses acting on the fibrils and the matrix

Analysis of the Flow Distribution in the Back Supporting Structure Manifolds of the HCPB Breeding Blanket for the EU DEMO Fusion Reactor

The European Union Demonstration Fusion Power Reactor (EU DEMO) is facing its preconceptual design phase. In this phase, the research and development activities make extensive use of computational tools, to, e.g., verify the design calculations or to perform parametric analyses aimed at optimization. The design of the breeding blanket (BB), which will be a first-of-a-kind component in EU DEMO, is supported from the thermal-hydraulic point of view by local three-dimensional (3-D) computational fluid dynamics (CFD) analyses, mainly aimed at verifying the heat removal capabilities of the system, and by analyses at the system level using one-dimensional (1-D) codes. This work presents the development and application of a detailed 1-D model of the coolant manifolds for the helium-cooled pebble bed BB concept for EU DEMO. This model, implemented in the GEneral Tokamak THErmal-hydraulic Model (GETTHEM), allows fast analyses to be performed at the global level but still maintain a good level of detail concerning the coolant distribution. The first results obtained with the model prove that 3-D CFD analyses of the manifolds may provide misleading results due to nonrepresentative boundary conditions (BCs), which must be used to avoid having a domain that is too complex. The application of a global model, which is indeed characterized exploiting local analyses, can in turn provide better BCs to the detailed 3-D CFD analyses

Osmotic pressure modulates single cell cycle dynamics inducing reversible growth arrest and reactivation of human metastatic cells

Biophysical cues such as osmotic pressure modulate proliferation and growth arrest of bacteria, yeast cells and seeds. In tissues, osmotic regulation takes place through blood and lymphatic capillaries and, at a single cell level, water and osmoregulation play a critical role. However, the effect of osmotic pressure on single cell cycle dynamics remains poorly understood. Here, we investigate the effect of osmotic pressure on single cell cycle dynamics, nuclear growth, proliferation, migration and protein expression, by quantitative time-lapse imaging of single cells genetically modified with fluorescent ubiquitination-based cell cycle indicator 2 (FUCCI2). Single cell data reveals that under hyperosmotic stress, distinct cell subpopulations emerge with impaired nuclear growth, delayed or growth arrested cell cycle and reduced migration. This state is reversible for mild hyperosmotic stress, where cells return to regular cell cycle dynamics, proliferation and migration. Thus, osmotic pressure can modulate the reversible growth arrest and reactivation of human metastatic cells

High resolution chemical stratigraphies of atmospheric depositions from a 4 m depth snow pit at dome C (East Antarctica)

In this work, we present chemical stratigraphies of two sampling lines collected within a 4 m depth snow pit dug in Dome C during the Antarctic summer Campaign 2017/2018, 12 years after the last reported snow pit. The first sampling line was analyzed for nine anionic and cationic species using Ion Chromatography (IC); the second sampling line was analyzed for seven major elements in an innovative way with Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) after sample pre-concentration, allowing the study of deposition processes of new markers especially related to crustal source. This coupled analysis, besides confirming previous studies, allowed us to investigate the depositions of the last decades at Dome C, enriching the number of the detected chemical markers, and yielding these two techniques complementary for the study of different markers in this kind of matrix. As a result of the dating, the snow layers analyzed covered the last 50 years of snow depositions. The assessment of the accumulation rate, estimated about 9 cm yr−1, was accomplished only for the period 1992–2016, as the eruption of 1992 constituted the only tie-point found in nssSO42− depth profile. Na, the reliable sea salt marker, together with Mg and Sr, mainly arose from marine sources, whereas Ca, Al and Fe originated from crustal inputs. Post-depositional processes occurred on Cl− as well as on NO3− and methanesulfonic acid (MSA); compared to the latter, Cl− had a more gradual decrease, reporting a threshold at 2.5 m for the post-depositional process completion. For NO3− and MSA, instead, the threshold was shallower, at about 1 m depth, with a loss of 87% for NO3− and of 50% for MSA

Three-dimensional structural interrelations between cells, extracellular matrix and mineral in normally mineralizing Aavian leg tendon

The spatial-temporal relationship between cells, extracellular matrices, and mineral deposits is fundamental for an improved understanding of mineralization mechanisms in vertebrate tissues. By utilizing focused ion beam-scanning electron microscopy with serial surface imaging, normally mineralizing avian tendons have been studied with nanometer resolution in three dimensions with volumes exceeding tens of micrometers in range. These parameters are necessary to yield sufficiently fine ultrastructural details while providing a comprehensive overview of the interrelationships between the tissue structural constituents. Investigation reveals a complex lacuno-canalicular network in highly mineralized tendon regions, where ∼100 nm diameter canaliculi emanating from cell (tenocyte) lacunae surround extracellular collagen fibril bundles. Canaliculi are linked to smaller channels of ∼40 nm diameter, occupying spaces between fibrils. Close to the tendon mineralization front, calcium-rich deposits appear between the fibrils and, with time, mineral propagates along and within them. These close associations between tenocytes, tenocyte lacunae, canaliculi, small channels, collagen, and mineral suggest a concept for the mineralization process, where ions and/or mineral precursors may be transported through spaces between fibrils before they crystallize along the surface of and within the fibrils