Vegetable hierarchical structures as template for bone regeneration: New bio-ceramization process for the development of a bone scaffold applied to an experimental sheep model.

Long bone defects still represent a major clinical challenge in orthopedics, with the inherent loss of function considerably impairing the quality of life of the affected patients. Thus, the purpose of this study was to assess the safety and potential of bone regeneration offered by a load-bearing scaffold characterized by unique hierarchical architecture and high strength, with active surface facilitating new bone penetration and osseointegration in critical size bone defects. The results of this study showed the potential of bio-ceramization processes applied to vegetable hierarchical structures for the production of new wood-derived bone scaffolds, further improved by surface functionalization, with good biological and mechanical properties leading to successful treatment of critical size bone defects in the sheep model. Future studies are needed to evaluate if these scaffolds prototypes, as either biomaterial alone or in combination with augmentation strategies, may represent an optimal solution to enhance bone regeneration in humans.

Porous Graphene-like Carbon from Fast Catalytic Decomposition of Biomass for Energy Storage Applications.

A novel carbon material made of porous graphene-like nanosheets was synthesized from biomass resources by a simple catalytic graphitization process using nickel as a catalyst for applications in electrodes for energy storage devices. A recycled fiberboard precursor was impregnated with saturated nickel nitrate followed by high-temperature pyrolysis. The highly exothermic combustion of in situ formed nitrocellulose produces the expansion of the cellulose fibers and the reorganization of the carbon structure into a three-dimensional (3D) porous assembly of thin carbon nanosheets. After acid washing, nickel particles are fully removed, leaving nanosized holes in the wrinkled graphene-like sheets. These nanoholes confer the resulting carbon material with ≈75% capacitance retention, when applied as a supercapacitor electrode in aqueous media at a specific current of 100 A·g-1 compared to the capacitance reached at 20 mA·g-1, and ≈35% capacity retention, when applied as a negative electrode for lithium-ion battery cells at a specific current of 3720 mA·g-1 compared to the specific capacity at 37.2 mA·g-1. These findings suggest a novel way for synthesizing 3D nanocarbon networks from a cellulosic precursor requiring low temperatures and being amenable to large-scale production while using a sustainable starting precursor such as recycled fiberwood.

Iron-Catalyzed Graphitic Carbon Materials from Biomass Resources as Anodes for Lithium-Ion Batteries.

Graphitized carbon materials from biomass resources were successfully synthesized with an iron catalyst, and their electrochemical performance as anode materials for lithium-ion batteries (LIBs) was investigated. Peak pyrolysis temperatures between 850 and 2000 °C were covered to study the effect of crystallinity and microstructural parameters on the anodic behavior, with a focus on the first-cycle Coulombic efficiency, reversible specific capacity, and rate performance. In terms of capacity, results at the highest temperatures are comparable to those of commercially used synthetic graphite derived from a petroleum coke precursor at higher temperatures, and up to twice as much as that of uncatalyzed biomass-derived carbons. The opportunity to graphitize low-cost biomass resources at moderate temperatures through this one-step environmentally friendly process, and the positive effects on the specific capacity, make it interesting to develop more sustainable graphite-based anodes for LIBs.

Performance of biomorphic Silicon Carbide as particulate filter in diesel boilers.

Biomorphic Silicon Carbide (bioSiC) is a novel porous ceramic material with excellent mechanical and thermal properties. Previous studies have demonstrated that it may be a good candidate for its use as particle filter media of exhaust gases at medium or high temperature. In order to determine the filtration efficiency of biomorphic Silicon Carbide, and its adequacy as substrate for diesel particulate filters, different bioSiC-samples have been tested in the flue gases of a diesel boiler. For this purpose, an experimental facility to extract a fraction of the boiler exhaust flow and filter it under controlled conditions has been designed and built. Several filter samples with different microstructures, obtained from different precursors, have been tested in this bench. The experimental campaign was focused on the measurement of the number and size of particles before and after placing the samples. Results show that the initial efficiency of filters made from natural precursors is severely determined by the cutting direction and associated microstructure. In biomorphic Silicon Carbide derived from radially cut wood, the initial efficiency of the filter is higher than 95%. Nevertheless, when the cut of the wood is axial, the efficiency depends on the pore size and the permeability, reaching in some cases values in the range 70-90%. In this case, the presence of macropores in some of the samples reduces their efficiency as particle traps. In continuous operation, the accumulation of particles within the porous media leads to the formation of a soot cake, which improves the efficiency except in the case when extra-large pores exist. For all the samples, after a few operation cycles, capture efficiency was higher than 95%. These experimental results show the potential for developing filters for diesel boilers based on biomorphic Silicon Carbide.

Manganese Dioxide Supported on Porous Biomorphic Carbons as Hybrid Materials for Energy Storage Devices.

A facile and low-cost method has been employed to fabricate MnO2/C hybrid materials for use as binder-free electrodes for supercapacitor applications. Biocarbon monoliths were obtained through pyrolysis of beech wood, replicating the microstructure of the cellulosic precursor, and serve as 3D porous and conductive scaffolds for the direct growth of MnO2 nanosheets by a solution method. Evaluation of the experimental results indicates that a homogeneous and uniform composite material made of a carbon matrix exhibiting ordered hierarchical porosity and MnO2 nanosheets with a layered nanocrystalline structure is obtained. The tuning of the MnO2 content and crystallite size via the concentration of KMnO4 used as impregnation solution allows to obtain composites that exhibit enhanced electrochemical behavior, achieving a capacitance of 592 F g-1 in electrodes containing 3 wt % MnO2 with an excellent cyclic stability. The electrode materials were characterized before and after electrochemical testing.

Electrochemical Energy Storage Applications of CVD Grown Niobium Oxide Thin Films.

We report here on the controlled synthesis, characterization, and electrochemical properties of different polymorphs of niobium pentoxide grown by CVD of new single-source precursors. Nb2O5 films deposited at different temperatures showed systematic phase evolution from low-temperature tetragonal (TT-Nb2O5, T-Nb2O5) to high temperature monoclinic modifications (H-Nb2O5). Optimization of the precursor flux and substrate temperature enabled phase-selective growth of Nb2O5 nanorods and films on conductive mesoporous biomorphic carbon matrices (BioC). Nb2O5 thin films deposited on monolithic BioC scaffolds produced composite materials integrating the high surface area and conductivity of the carbonaceous matrix with the intrinsically high capacitance of nanostructured niobium oxide. Heterojunctions in Nb2O5/BioC composites were found to be beneficial in electrochemical capacitance. Electrochemical characterization of Nb2O5/BioC composites showed that small amounts of Nb2O5 (as low as 5%) in conjunction with BioCarbon resulted in a 7-fold increase in the electrode capacitance, from 15 to 104 F g(-1), while imparting good cycling stability, making these materials ideally suited for electrochemical energy storage applications.

Biological strategy for the fabrication of highly ordered aragonite helices: the microstructure of the cavolinioidean gastropods.

The Cavolinioidea are planktonic gastropods which construct their shells with the so-called aragonitic helical fibrous microstructure, consisting of a highly ordered arrangement of helically coiled interlocking continuous crystalline aragonite fibres. Our study reveals that, despite the high and continuous degree of interlocking between fibres, every fibre has a differentiated organic-rich thin external band, which is never invaded by neighbouring fibres. In this way, fibres avoid extinction. These intra-fibre organic-rich bands appear on the growth surface of the shell as minuscule elevations, which have to be secreted differentially by the outer mantle cells. We propose that, as the shell thickens during mineralization, fibre secretion proceeds by a mechanism of contact recognition and displacement of the tips along circular trajectories by the cells of the outer mantle surface. Given the sizes of the tips, this mechanism has to operate at the subcellular level. Accordingly, the fabrication of the helical microstructure is under strict biological control. This mechanism of fibre-by-fibre fabrication by the mantle cells is unlike that any other shell microstructure.

New bio-ceramization processes applied to vegetable hierarchical structures for bone regeneration: an experimental model in sheep.

Bone loss is still a major problem in orthopedics. The purpose of this experimental study is to evaluate the safety and regenerative potential of a new scaffold based on a bio-ceramization process for bone regeneration in long diaphyseal defects in a sheep model. The scaffold was obtained by transformation of wood pieces into porous biomorphic silicon carbide (BioSiC®). The process enabled the maintenance of the original wood microstructure, thus exhibiting hierarchically organized porosity and high mechanical strength. To improve cell adhesion and osseointegration, the external surface of the hollow cylinder was made more bioactive by electrodeposition of a uniform layer of collagen fibers that were mineralized with biomimetic hydroxyapatite, whereas the internal part was filled with a bio-hybrid HA/collagen composite. The final scaffold was then implanted in the metatarsus of 15 crossbred (Merinos-Sarda) adult sheep, divided into 3 groups: scaffold alone, scaffold with platelet-rich plasma (PRP) augmentation, and scaffold with bone marrow stromal cells (BMSCs) added during implantation. Radiological analysis was performed at 4, 8, 12 weeks, and 4 months, when animals were sacrificed for the final radiological, histological, and histomorphometric evaluation. In all tested treatments, these analyses highlighted the presence of newly formed bone at the bone scaffolds' interface. Although a lack of substantial effect of PRP was demonstrated, the scaffold+BMSC augmentation showed the highest value of bone-to-implant contact and new bone growth inside the scaffold. The findings of this study suggest the potential of bio-ceramization processes applied to vegetable hierarchical structures for the production of wood-derived bone scaffolds, and document a suitable augmentation procedure in enhancing bone regeneration, particularly when combined with BMSCs.

Crystallographic reorganization of the calcitic prismatic layer of oysters.

The calcitic columnar prisms of pteriomorphian bivalves have the crystallographic c-axis oriented perpendicular to the shell surface and the a-axes rotated without any preferential orientation. In oysters, SEM, XRD and EBSD analyses show that individual prisms initially have their a-axes randomly oriented but are able to progressively orient them parallel to those of their neighbors. This ability is apparently confined to groups, such as oysters and scallops, in which prisms are internally constituted by smaller lath-like crystal units. We have developed a competition model - not between prisms, but between the lath-like secondary units of prisms - which is based on differences in the inclination of laths relative to the shell growth surface. Units having a growth component which coincides with the growth direction protrude faster from the growth surface and out-compete those which are not favorably oriented, which reduces the overall dispersion of the a-axes of the prismatic lamella. The extent of re-alignment increases with the relative inclination of the growth surface and the length attained by the prisms. Oysters are the only group in which these two characters are pronounced enough to provide a measurable re-alignment. The proposed competition model is unprecedented in biomaterials and reveals how important crystal growth processes are in microstructure organization.

Nacre and false nacre (foliated aragonite) in extant monoplacophorans (=Tryblidiida: Mollusca).

Extant monoplacophorans (Tryblidiida, Mollusca) have traditionally been reported as having an internal nacreous layer, thus representing the ancestral molluscan condition. The examination of this layer in three species of Neopilinidae (Rokopella euglypta, Veleropilina zografi, and Micropilina arntzi) reveals that only V. zografi secretes an internal layer of true nacre, which occupies only part of the internal shell surface. The rest of the internal surface of V. zografi and the whole internal surfaces of the other two species examined are covered by a material consisting of lath-like, instead of brick-like, crystals, which are arranged into lamellae. In all cases examined, the crystallographic c-axis in this lamellar material is perpendicular to the surface of laths and the a-axis is parallel to their long dimension. The differences between taxa relate to the frequency of twins, which is much higher in Micropilina. In general, the material is well ordered, particularly towards the margin, where lamellae pile up at a small step size, which is most likely due to processes of crystal competition. Given its morphological resemblance to the foliated calcite of bivalves, we propose the name foliated aragonite for this previously undescribed biomaterial secreted by monoplacophorans. We conclude that the foliated aragonite probably lacks preformed interlamellar membranes and is therefore not a variant of nacre. A review of the existing literature reveals that previous reports of nacre in the group were instead of the aragonitic foliated layer and that our report of nacre in V. zografi is the first undisputed evidence of nacre in monoplacophorans. From the evolutionary viewpoint, the foliated aragonite could easily have been derived from nacre. Assuming that nacre represents the ancestral condition, as in other molluscan classes, it has been replaced by foliated aragonite along the tryblidiidan lineage, although the fossil record does not presently provide evidence as to when this replacement took place.