Long-Term Culture of Stem Cells on Phosphate-Based Glass Microspheres: Synergistic Role of Chemical Formulation and 3D Architecture.

Phosphate-based glasses (PBGs) are biomaterials that degrade under physiological conditions and can be modified to release various ions depending on end applications. This study utilized slow-degrading (P45:45P2O5-16CaO-24MgO-11Na2O-4Fe2O3, mol %) and comparatively faster degrading (P40:40P2O5-16CaO-24MgO-20Na2O, mol %) PBG microspheres with or without porosity, to evaluate the combined effect of chemical formulation and geometry on human mesenchymal stem cells (MSCs), a clinically relevant cell source for orthopedic applications. Scanning electron microscopy showed 2, 46, and 29% of P45 bulk (P45-B), P40 bulk (P40-B), and P40 porous (P40-P) microspheres, respectively, that had cracks or peeling off surfaces after 42 days of incubation in culture medium. Cytotoxicity assessment showed that glass debris released into the culture medium may interact with cells and affect their survival. Direct-contact cell experiments up to 42 days showed that P45-B microspheres did not sustain viable long-term cell cultures and did not facilitate extracellular matrix formation. On the other hand, P40-B microspheres enhanced alkaline phosphatase activity, calcium deposition, and collagen and osteocalcin production in MSCs. Introduction of porosity in P40 glass further enhanced these parameters and proliferation at later time points. The small pore windows (<5 µm wide) and interconnection (<10 µm wide) may have allowed limited cell penetration into the porous structures. P40-B and P40-P have potential for bone repair and reinforcement therapy based on their chemical formulation and porous geometry.

Three dimensional nanoscale analysis reveals aperiodic mesopores in a covalent organic framework and conjugated microporous polymer.

The integrated analytical approach developed in this study offers a powerful methodology for the structural characterisation of complex molecular nanomaterials. Structures of a covalent organic framework based on boronate esters (COF-5) and a conjugated microporous polymer (Aza-CMP) have been investigated by a combination of several electron microscopy techniques elucidating the three-dimensional topology of the complex polycrystalline (COF) and non-crystalline (CMP) materials. Unexpected, aperiodic mesoporous channels of 20-50 nm in diameter were found to be penetrating the COF and CMP particles, which cannot be detected by X-ray diffraction techniques. The mesopores appear to be stable under a range of different conditions and accessible to gas molecules, exhibiting a particular bonding capability with CO2 in the case of the CMP. The mesoporosity is unrelated to the intrinsic chemical structures of the COF or CMP but rather it reflects the mechanisms of polymer particle formation in a polycondensation reaction. The mesopores may be templated by clusters of solvent molecules during the COF or CMP synthesis, leaving cavities within the polymer particles. The unexpected mesoporosity discovered in COF and CMP materials begs for re-assessment of the nature of framework materials and may open new opportunities for applications of these molecular materials in gas sorption or catalysis.

Interactions at the Silica-Peptide Interface: Influence of the Extent of Functionalization on the Conformational Ensemble.

In this contribution, the effect of silica particle size (28 and 210 nm) and surface chemistry (i.e., hydroxyl, methyl, or amino groups) on peptide binding response is studied with a specific emphasis on the effect of the extent of functionalization on binding. Exhaustive characterization of the silica surfaces was crucial for knowledge of the chemistry and topography of the solid surface under study and, thus, to understand their impact on adsorption and the conformational ensemble of the peptides. The extent of surface functionalization was shown to be particle-size dependent, a higher level of 3-aminopropyl functionality being obtained for smaller particles, whereas a higher degree of methyl group functionality was found for the larger particles. We demonstrated that peptide interactions at the aqueous interface were not only influenced by the surface chemistry but also by the extent of functionalization where a "switch" of peptide adsorption behavior was observed, whereas the changes in the conformational ensemble revealed by circular dichroism were independent of the extent of functionalization. In addition to electrostatic interactions and hydrogen bonding driving interaction at the silica-peptide interface, the data obtained suggested that stronger interactions such as hydrophobic and/or covalent interactions may moderate the interaction. The insights gained from this peptide-mineral study give a more comprehensive view of mechanisms concerning mineral-peptide interactions which may allow for the design and synthesis of novel (nano)materials with properties tailored for specific applications.

Super-Hydrophobic/Icephobic Coatings Based on Silica Nanoparticles Modified by Self-Assembled Monolayers.

A super-hydrophobic surface has been obtained from nanocomposite materials based on silica nanoparticles and self-assembled monolayers of 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) using spin coating and chemical vapor deposition methods. Scanning electron microscope images reveal the porous structure of the silica nanoparticles, which can trap small-scale air pockets. An average water contact angle of 163° and bouncing off of incoming water droplets suggest that a super-hydrophobic surface has been obtained based on the silica nanoparticles and POTS coating. The monitored water droplet icing test results show that icing is significantly delayed by silica-based nano-coatings compared with bare substrates and commercial icephobic products. Ice adhesion test results show that the ice adhesion strength is reduced remarkably by silica-based nano-coatings. The bouncing phenomenon of water droplets, the icing delay performance and the lower ice adhesion strength suggest that the super-hydrophobic coatings based on a combination of silica and POTS also show icephobicity. An erosion test rig based on pressurized pneumatic water impinging impact was used to evaluate the durability of the super-hydrophobic/icephobic coatings. The results show that durable coatings have been obtained, although improvement will be needed in future work aiming for applications in aerospace.

Peptide-directed crystal growth modification in the formation of ZnO.

Biomolecule-mediated synthesis is fascinating in terms of the level of control and the intricate hierarchical structures of the materials that can be produced. In this study we compare the behavior of a phage display identified peptide, EAHVMHKVAPRP (EM-12) with that of a mutant peptide EAHVCHKVAPRP (EC-12), having additional complexation capability, on the formation of ZnO from solution. The synthesis conditions (Zn(CH3COO)2-NH3 hydrothermal method at 50 °C) were chosen to generate rod-shaped ZnO via layered basic zinc salts (LBZs) as intermediates. Both peptides affected the crystal formation process by moderating the amount of Zn2+ ions in solution (EC12 having a greater effect than EM12) but only EC12 was shown to interact with the solid phase(s) formed during the reaction. Depending on the peptide concentration used, EM-12 was shown to delay and/or suppress ZnO formation. In contrast, additions of EC-12, although leading to the retention of higher levels of Zn2+ ions in solution did not similarly delay the transformation of the intermediate phases to ZnO but were found to dramatically modify the morphology of ZnO crystallites with mushroom shaped crystals being formed. From the results of detailed materials characterization and changes in the morphology observed, the interactions between the peptide(s) and solution and solid state species present during the process of ZnO crystal formation in the presence of EM-12 and EC-12 are proposed.

Enhanced conductivity of reduced graphene oxide decorated with aluminium oxide nanoparticles by oxygen annealing.

A process involving the filtration of graphene oxide (GO) dispersion through an alumina membrane, followed by oxygen annealing to synthesize alumina nanoparticles exclusively at the edges of holes or vacancies in the reduced graphene oxide (rGO) plane, is used to prepare paper-like composites with a 21% enhanced electrical conductivity. Moreover, the rGO/alumina nanocomposites have a smaller band gap and hydrophilic properties.

Growth and characterization of iron oxide nanorods/nanobelts prepared by a simple iron-water reaction.

Single-crystalline hexagonal alpha-Fe(2)O(3) nanorods/nanobelts have been created by a simple iron-water reaction in the low-temperature range of 350-450 degrees C. Scanning electron microscopy examination shows that the needle-like products, radiating from and perpendicular to the original large iron particle surfaces, are up to a few micrometers in length with an average diameter from 20 nm (tip) to 100 nm (base). X-ray photoelectron spectroscopy and FTIR spectroscopy reveal that the outermost surface of the nanorods consists of Fe(2)O(3) without organic impurity contaminants, which could possibly result from other methods, such as hydrothermal growth. Nanobelt-like structures are believed to result from a combination of increased reaction temperature and time. The initial formation and subsequent growth of alpha-Fe(2)O(3) nanorods may be explained by the iron metal corrosion mechanism.

Shock-absorbing and failure mechanisms of WS2 and MoS2 nanoparticles with fullerene-like structures under shock wave pressure.

The excellent shock-absorbing performance of WS2 and MoS2 nanoparticles with inorganic fullerene-like structures (IFs) under very high shock wave pressures of 25 GPa is described. The combined techniques of X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, thermal analysis, and transmission electron microscopy have been used to evaluate the diverse, intriguing features of shock recovered IFs, of interest for their tribological applications, thereby allowing improved understanding of their antishock behavior and structure-property relationships. Two possible failure mechanisms are proposed and discussed. The supershock-absorbing ability of the IF-WS2 enables them to survive pressures up to 25 GPa accompanied with concurrent temperatures of up to 1000 degrees C without any significant structural degradation or phase change making them probably the strongest cage molecules now known.

Chromium remediation or release? Effect of iron(II) sulfate addition on chromium(VI) leaching from columns of chromite ore processing residue.

Chromite ore processing residue (COPR), derived from the so-called high lime processing of chromite ore, contains high levels of Cr(III) and Cr(VI) and has a pH between 11 and 12. Ferrous sulfate, which is used for remediation of Cr(VI) contamination in wastewater and soils via reduction to Cr(III) and subsequent precipitation of iron(III)/chromium(III) hydroxide, has also been proposed for remediation of Cr(VI) in COPR. Instead, however, addition of FeSO4 to the infiltrating solution in column experiments with COPR greatly increased leaching of Cr(VI). Leached Cr(VI) increased from 3.8 to 12.3 mmol kg(-1) COPR in 25 pore volumes with 20 mM FeSO4, reaching solution concentrations as high as 1.6 mM. Fe(II) was ineffective in reducing Cr(VI) to Cr(III) because it precipitated when it entered the column due to the high pH of COPR, while Cr(VI) in solution was transported away with the infiltrating solution. The large increase in leaching of Cr(VI) upon infiltration of sulfate, either as FeSO4 or Na2SO4, was caused by anion exchange of sulfate for chromate in the layered double hydroxide mineral hydrocalumite, a process for which scanning electron microscopy with energy-dispersive X-ray microanalysis provided direct evidence.