1,721,149 research outputs found

    Coral biomineralization: A focus on intra-skeletal organic matrix and calcification

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    In the recent years several papers and some reviews have dealt with characterization, localization and influence on the precipitation of calcium carbonate, of the organic matrix from scleractinian corals. In fact, it has been well established that coral calcification is a biological controlled process orchestrated in space and time by the organism also trough the secretion of organic matrix molecules because it has been well established that coral calcification is a biological controlled process, and thus is orchestrated in space and time by the organism also through the secretion of organic matrix molecules. In this review is presented a scientific path on the biomineralization of corals having as focusing point the intra-skeletal organic matrix, the molecules that are associated with mineral (aragonite). The review starts with a an overview on coral tissue, skeleton and tissue skeleton interface, describes the intra-skeletal organic matrix putting attention mainly on the proteins associated to aragonite and finally describes the in vivo and in vitro calcium carbonate precipitation experiments carried out aimed to evaluate the role of the organic matrix. The last paragraph reports studies on the role of the organic matrix in controlling calcification when corals are subject ocean acidification effects. The readers are expected to find a source of inspiration for new studies on the biomineralization of corals that are organic matrix addressed and merge diverse scientific disciplines

    Influence of proteins on mechanical properties of a natural chitin-protein composite

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    In many biogenic materials, chitin chains are assembled in fibrils that are wrapped by a protein fold. In them, the mechanical properties are supposed to be related to intra- and inter- interactions among chitin and proteins. This hypothesis has been poorly investigated. Here, this research theme is studied using the pen of Loligo vulgaris as a model material of chitin-protein composites. Chemical treatments were used to change the interactions involving only the proteic phase, through unfolding and/or degradation processes. Successively, structural and mechanical parameters were examined using spectroscopy, microscopy, X-ray diffractometry, and tensile tests. The data analysis showed that chemical treatments did not modify the structure of the chitin matrix. This allowed to derive from the mechanical test analysis the following conclusions: (i) the maximum stress (σmax) relies on the presence of the disulfide bonds; (ii) the Young's modulus (E) relies on the overall correct folding of the proteins; (iii) the whole removal of proteins induces a decrease of E (> 90%) and σmax (> 80%), and an increase in the maximum elongation. These observations indicate that in the chitin matrix the proteins act as a strengthener, which efficacy is controlled by the presence of disulfide bridges. This reinforcement links the chitin fibrils avoiding them to slide one on the other and maximizing their resistance and stiffness. In conclusion, this knowledge can explain the physio-chemical properties of other biogenic polymeric composites and inspire the design of new materials. STATEMENT OF SIGNIFICANCE: To date, no study has addressed on how proteins influence chitin-composite material's mechanical properties. Here we show that the Young's modulus and the maximum stress mainly rely on protein disulfide bonds, the inter-proteins ones and those controlling the folding of chitin-binding domains. The removal of protein matrix induce a reduction of Young's modulus and maximum stress, leaving the chitin matrix structurally unaltered. The measure of the maximum elongation shows that the chitin fibrils slide on each other only after removing the protein matrix. In conclusion, this research shows that the proteins act as a stiff matrix reinforced by di-sulfide bridges that link crystalline chitin fibrils avoiding them to slide one on the other

    Crystallization of Calcium Carbonate in Alginate and Xanthan Hydrogels

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    Calcium carbonate polymorphs were crystallized in alginate and xanthan hydrogels in which a degree of entanglement was altered by the polysaccharide concentration. Both hydrogels contain functional groups (COOH and OH) attached at diverse proportions on saccharide units. In all systems, the precipitation process was initiated simultaneously with gelation, by the fast mixing of the calcium and carbonate solutions, which contain the polysaccharide molecules at respective concentrations. The initial supersaturation was adjusted to be relatively high in order to ensure the conditions suitable for nucleation of all CaCO3 polymorphs and amorphous phase(s). In the model systems (no polysaccharide), a mixture of calcite, vaterite and amorphous calcium carbonate initially precipitated, but after short time only calcite remained. In the presence of xanthan hydrogels, precipitation of either, calcite single crystals, porous polyhedral aggregates, or calcite/vaterite mixtures were observed after five days of ageing, because of different degrees of gel entanglement. At the highest xanthan concentrations applied, the vaterite content was significantly higher. In the alginate hydrogels, calcite microcrystalline aggregates, rosette-like and/or stuck-like monocrystals and vaterite/calcite mixtures precipitated as well. Time resolved crystallization experiments performed in alginate hydrogels indicated the initial formation of a mixture of calcite, vaterite and amorphous calcium carbonate, which transformed to calcite after 24 h of ageing

    Aggregation Pathways of Native-Like Ubiquitin Promoted by Single-Point Mutation, Metal Ion Concentration, and Dielectric Constant of the Medium

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    Ubiquitin-positive protein aggregates are biomarkers of neurodegeneration, but the molecular mechanism responsible for their formation and accumulation is still unclear. Possible aggregation pathways of human ubiquitin (hUb) promoted by both intrinsic and extrinsic factors, are here investigated. By a computational analysis, two different hUb dimers are indicated as possible precursors of amyloid-like structures, but their formation is disfavored by an electrostatic repulsion involving Glu16 and other carboxylate residues present at the dimer interface. Experimental data on the E16V mutant of hUb shows that this single-point mutation, although not affecting the overall protein conformation, promotes protein aggregation. It is sufficient to shift the same mutation by only two residues (E18V) to regain the behavior of wild-type hUb. The neutralization of Glu16 negative charge by a metal ion and a decrease of the dielectric constant of the medium by addition of trifluoroethanol (TFE), also promote hUb aggregation. The outcomes of this research have important implications for the prediction of physiological parameters that favor aggregate formation

    β-Chitin samples with similar microfibril arrangement change mechanical properties varying the degree of acetylation

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    Chitin is widespread in nature and is increasingly used in synthetic process for the production of new biomaterials. Chitin degree of acetylation, crystalline structure and microfibril arrangement differentiate chemical, physical and mechanical properties. Nevertheless, no information are available on the relationship between the mechanical properties and the degree of acetylation (DA) in chitin samples in which the microfibril arrangement does not change. Here, samples of β-chitin with decreasing DA, up to chitosan, were prepared using the squid pen of Loligo vulgaris. These samples were characterized by CP-MAS NMR spectroscopy, scanning electron microscopy, thermal analyses, synchrotron X-ray fiber diffraction and tensile tests. The results showed a similar microfibril arrangement decreasing the DA, except for the chitosan sample. The mechanical properties showed an increase of the maximum strain and a reduction of the maximum stress and Young's modulus, decreasing the DA. These changes, not linear with the DA, were related to structural changes at molecular structure level. The knowledge deriving from this study is of interest both for the understanding of the mechanical properties of chitinous biological samples, but also for the design and synthesis of new biomacromolecular materials
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