Conversion of rice husks into carbonaceous materials with porous structures via hydrothermal process.

Carbonaceous materials hydrothermally produced using waste biomass have small specific surface areas (SSA) and poor porosity properties. In this study, we prepare a novel carbonaceous material with excellent porosity properties by suppressing the formation of a secondary char phase (spheres) and promoting biomass hydrolysis by controlling the hydrothermal conditions. Rice husk powders, as the starting material, are hydrothermally treated using acidic solvents of different types and concentrations at 180 °C. The surfaces of the samples hydrothermally prepared using the acidic solvents have no spheres. In the case of 0.1-0.2 mol L-1 hydrochloric acid (HA), the amorphous carbonaceous materials contain numerous mesopores and exhibit a larger SSA (approximately 100 m2 g-1) than those prepared using acetic acid and distilled water. An increase in the hydrothermal temperature reduces the porosity properties of the materials. Finally, the high-porosity amorphous carbonaceous material showed excellent trimethylamine adsorption ability.

Preparation of Hydrogarnet/Poly(Lactic Acid) Composite Adsorbents for Humic Substance Removal.

Humic substances are constituents of organic matter that require removal from water environments because of their adverse ecological and sanitation effects. A mixture of hydrogarnet and poly(lactic acid) dissolved in chloroform was electrospun to prepare a composite as a adsorbent for humic substance removal. Here, humic acid was used as the model substance for evaluating the adsorbent's water remediation efficiency. Despite the hydrogarnet particles being embedded in its poly(lactic acid) fibers, the composites demonstrated a higher humic acid removal ability than the pure poly(lactic acid) sample prepared using an electrospinning process. Pores were introduced to the fiber surfaces of the composite by controlling the relative humidity during electrospinning, thus enhancing their humic acid removal ability (4.6 ± 2.4 mg/g), compared to the composite consisting of the fibers without pores (1.2 ± 0.9 mg/g).

Diffusion of protons and sodium ions in silicophosphate glasses: insight based on first-principles molecular dynamic simulations.

We propose a microscopic diffusion mechanism of protons and Na+ ions in phosphate glasses using first-principles molecular dynamic simulations. Protons hop and are chemisorbed onto non-bridging oxygen (NBO) of nearby PO4 tetrahedra through hydrogen bonds. The subsequent behavior depends on the morphology of the PO4 tetrahedra (QnP values). When a proton is adsorbed onto the NBO of a Q3P unit, it is desorbed on a short time scale of within 10 fs and re-adsorbed onto the NBO that was previously adsorbed. However, when a proton is adsorbed onto the NBO of a Q2P unit, another proton coordinated before adsorption is desorbed in a chain, resulting in the diffusion of protons. When a Na+ ion is present in the vicinity, the adsorption of a proton onto a Q2P unit leads to a decrease in the electrostatic interaction between Na+ and O- ions and induces the diffusion of Na+ ions. We conclude that the difference in the morphology of PO4 tetrahedra greatly affects the diffusion of protons and Na+ ions.

First-Principles Density Functional Theory Calculations for Formic Acid Adsorption onto Hydro-Garnet Compounds.

Efficient and large-scale removal of humic acid (HA) from aqueous environments is required since HA causes human health and esthetic issues. Hydro-garnet compounds, Ca3Al2(SiO4)3-x (OH)4x , have recently been suggested as HA adsorbents not only due to their superior adsorption behaviors but also because they are ubiquitous element-derived compounds. In this study, the adsorption behavior of formic acid to hydro-garnets was investigated by means of first-principles density functional theory (DFT) computations. Formic acid was chosen owing to its reasonable computational cost and inclusion of carboxylic acid as HA. Comparisons of adsorption energies for formic acid among various compounds (including platinum and kaolinite) indicate that hydro-garnet compounds are promising due to their lower (more stable) adsorption energies. Also, the optimization of composition x enables selective adsorption of formic acid against solvent water molecules. Relationships between surface electronic/atomistic structures and adsorption properties are discussed.

Water wettability dependence on surface structure of a snail shell.

There are many reports on the special wettability of hierarchical surface structures in nature. Snail shells with three types of roughness of 10, 100, and 500 µm have a unique wetting behavior. In the present study, we investigate the influence of the surface structure on the water wettability using snail shells with different surface roughness. The wettability of a water droplet on the samples was evaluated. The three types of roughness on the surface structure of snail shell had higher water droplet spreading properties than the two types of roughness 500 µm and, 10 or 100 µm. Surface structures of snail shells with different surface roughness were simulated using epoxy resins to clarify the mechanism for the dynamics wetting behavior. The contact angle with a hydrophobic nature, of the epoxy resin with the three types of roughness decreased with increasing time, indicating a hydrophilic nature. The base diameter of the epoxy resins with the three types of roughness increased with increasing time. This was larger than that for a flat epoxy resin with hydrophilicity. Other epoxy resins with shell texture containing 100 and 500 or 10 and 500 µm roughness showed almost no change in the contact angle and diameter of the droplet base. The three types of roughness on the sample surface contributed to development of the water droplet spreading. The 10 µm roughness of the sample surface influenced the dynamic contact angles.

Heat transfer properties of Morpho butterfly wings and the dependence of these properties on the wing surface structure.

The heat transfer properties of a material strongly rely on its surface structure. The wings of the Morpho butterfly have a unique surface structure with features of order and disorder. In this work, the surface temperature and radiative heat flux of Morpho butterfly wings with structural colour when a ceramic heater attached to the opposite surface of the wings was heated to 250 °C were evaluated in terms of their heat transfer properties. Morpho menelaus butterfly (MM) wings and Cithaerias (CE) wings with no periodic structure on their surface, were used as samples. The MM wings had higher surface temperature and radiative heat flux than the CE wings, which is the first report of heat transfer properties of the wings. The surface structure of the MM wings was changed by heat treatment in order to investigate the effect of the surface structural change on their heat transfer properties. The treatment changed the colour of the wings to red and brown, distorting the periodic structure. The radiative heat flux increased due to the change in the structure on their surface. XPS spectra revealed that the treatment leads to a slight change in the chemical structure of the wings. The spectral analyses results showed there was no obvious change in the mid-infrared absorbance. The heat radiative properties of the MM wings were strongly influenced by the surface structural changes due to the heat treatment.

Tuning of ion-release capability from bio-ceramic-polymer composites for enhancing cellular activity.

In our previous study, we investigated the synergetic effects of inorganic ions, such as silicate, Mg2+ and Ca2+ ions on the osteoblast-like cell behaviour. Mg2+ ions play an important role in cell adhesion. In the present study, we designed a new composite that releases a high concentration of Mg2+ ions during the early stage of the bone-forming process, and silicate and Ca2+ ions continuously throughout this process. Here, 40SiO2-40MgO-20Na2O glass (G) with high solubility and vaterite-based calcium carbonate (V) were selected as the source of silicate and Mg2+ and Ca2+ ions, respectively. These particles were mixed with poly(lactic-co-glycolic acid) (PLGA) using a kneading method at 110°C to prepare the composite (G-V/PLGA, G/V/PLGA = 4/56/40 (in weight ratio)). Most of the Mg2+ ions were released within 3 days of immersion at an important stage for cell adhesion, and silicate and Ca2+ ions were released continuously at rates of 70-80 and 180 ppm d-1, respectively, throughout the experiment (until day 7). Mouse-derived osteoblast-like MC3T3-E1 proliferated more vigorously on G-V/PLGA in comparison with V-containing PLGA without G particles; it is possible to control the ion-release behaviour by incorporating a small amount of glass particles.

Enhancing Wettability of Radio Frequency Magnetron-Sputtered Glass Films by Exploiting Structural Defects.

Silica-based films were prepared by radio-frequency magnetron sputtering to investigate the influence of the chemical compositions of the target glass on the structure and wettability of the sputtered films. The sputtered films were more hydrophilic than the untreated glasses. Oxygen defects formed in the silica units of the sputtered films and resulted in the formation of hydroxyl groups, regardless of the chemical composition of the glass. The three-phase contact lines were distorted by chemical heterogeneities on the surfaces of the sputtered films.

Wettability and dynamics of water droplet on a snail shell.

HYPOTHESIS: There are many natural surfaces with special wettabilities. Snail shells have unique rough structures, which indicates a specific wettability. In this study, the surface of a snail shell was simulated using epoxy resins, and water droplet dynamics on original and simulated snail shells were investigated to understand its special wettability. EXPERIMENTS: The shell of the Euhadra sandai species of snails was used. The surface structure of the snail shell was simulated using epoxy resins. The surface of this EP resin was treated with UV-O3 for different periods of time. Wettabilities and dynamics of water droplet on the samples were characterized. FINDINGS: The surface of the snail shell with a water contact angle of approximately 85° caused the droplet to spread, which is the first report of water droplet dynamics on the shell surface. The behavior of a water droplet on the shell transformed from the Cassie state into the Wenzel state. Changes in the contact angle and diameter of the droplet base on the snail shell were larger than those on the epoxy resins. The surface roughness and chemical heterogeneity of the snail shell led to distortion of the three-phase contact line and enhancement of the spreading of the water droplet.

Correction to: 'Adsorption behaviour of hydrogarnet for humic acid'.

[This corrects the article DOI: 10.1098/rsos.172023.].

Adsorption behaviour of hydrogarnet for humic acid.

Discharge of humic acid (HA) in aqueous environments is a key health and aesthetic issue. The present work investigates the use of hydrogarnet as a novel adsorbent for HA. Hydrogarnet was hydrothermally synthesized with different solvents to control the chemical composition. Hydrogarnet with three types of chemical compositions had better adsorption properties for HA than hydrogarnet with a single chemical composition. Controlling the chemical composition of hydrogarnet increased the number of hydroxyl groups and the overall binding energy of the system, leading to changes in the zeta potential. The enhancement of these adsorption properties is related to the increased numbers of hydroxyl groups on the surface and their diverse binding energies.

Structural changes in calcium silicate hydrate gel and resulting improvement in phosphate species removal properties after mechanochemical treatment.

The discharge of phosphate species into aqueous environments is a key issue for eutrophication prevention. In this study, we investigate a mechanochemical treatment of calcium silicate hydrate (C-S-H) gel with different organic solvents with the aim of changing its structure and improving its phosphate species removal properties. The treatment leads to a collapse of the gel structure, resulting in the formation of defective structures in the silicate anion chains. The C-S-H gel sample milled with acetone exhibits better phosphate species recovery characteristics than does the unmilled C-S-H gel sample or the C-S-H gel sample milled with 1-propanol. Ultraviolet irradiation during phosphate recovery using the C-S-H gel sample milled with acetone further enhances the recovery properties.

Structural effects of phosphate groups on apatite formation in a copolymer modified with Ca2+ in a simulated body fluid.

Organic-inorganic composites are novel bone substitutes that can ameliorate the mismatch of Young's moduli between natural bone and implanted ceramics. Phosphate groups contribute to the formation of apatite in a simulated body fluid (SBF) and the adhesion of osteoblast-like cells. Therefore, modification of a polymer with these functional groups is expected to enhance the ability of the organic-inorganic composite to bond with bone. Two phosphate groups have been used, phosphonic acid (-C-PO3H2) and phosphoric acid (-O-PO3H2). However, the effects of structural differences between these phosphate groups have not been clarified. In this study, the apatite formation of copolymers modified with Ca2+ and either -C-PO3H2 or -O-PO3H2 was examined. The mechanism of apatite formation is discussed based on analytical and computational approaches. The copolymers containing -O-PO3H2, but not those containing -C-PO3H2, formed apatite in the SBF, although both released similar amounts of Ca2+ into the SBF. Adsorption of HPO4 2- from -O-PO3H2 in the SBF following Ca2+ adsorption was confirmed by zeta-potential measurement and X-ray photoelectron spectroscopy. The measurement of the complex formation constant revealed that the -O-PO3 2-Ca2+ complex was thermodynamically unstable enough to convert into CaHPO4, which was not the case with -C-PO3 2-Ca2+. The formation of CaHPO4-based clusters was found to be a key factor for apatite nucleation. In conclusion, this study revealed that modification with -O-PO3H2 was more effective for enhancing apatite formation compared with -C-PO3H2.

Experimental and Theoretical Investigation of the Structural Role of Titanium Oxide in CaO-P2O5-TiO2 Invert Glass.

Understanding the structural role of TiO2 in calcium phosphate invert glasses is key for developing a new glass design for biomedical applications. Experimental and computational analysis methods were used to investigate the impact of TiO2 substitution in these glasses. Spectroscopic analyses indicated that titanium oxide exists as both TiO4 and TiO6 units, leading to the formation of Ti-O-P bonds, in spite of depolymerization of the phosphate chains. Classical molecular dynamics showed that the presence of TiO2 influences the phosphate units and CaO polyhedral structures. The formation of the Ti-O-P bonds caused an increase in the network connectivity of the invert glasses, leading to the improvement of the glass forming ability and wettability. The addition of TiO2 to calcium phosphate invert glasses led to the introduction of bioactivity.

Improving the biocompatibility of tobermorite by incorporating calcium phosphate clusters.

BACKGROUND: In our earlier work, tobermorite containing calcium phosphate (CP) clusters (CP-Tob) was hydrothermally prepared in the CaO-SiO2-P2O5-H2O system for biomedical applications. OBJECTIVE: CP-Tob was used to investigate the influence of CP cluster incorporation on its biocompatibility. METHODS: Tobermorite samples with and without CP clusters were hydrothermally prepared at 180°C for 40 h. The biocompatibility, structure, and density of states of the tobermorite samples were investigated by experimental and first principles methods. RESULTS: The amounts of lysozyme and bovine serum albumin adsorbed on CP-Tob were higher than those on tobermorite without CP clusters. Cluster incorporation caused a decrease in the solubility, resulting in the enhancement of the cell compatibility. The calculated results indicated that incorporating clusters, which interact with the silicate units of tobermorite, led to a change of the density of states of tobermorite. CONCLUSIONS: Incorporation of CP clusters in tobermorite led to improvement of the biocompatibility evaluated by biological and computational analyses.

Development of Magnesium and Siloxane-Containing Vaterite and Its Composite Materials for Bone Regeneration.

Development of novel biomaterials with Mg(2+), Ca(2+), and silicate ions releasability for bone regeneration is now in progress. Several inorganic ions have been reported to stimulate bone-forming cells. We featured Ca(2+), silicate, and especially, Mg(2+) ions as growth factors for osteoblasts. Various biomaterials, such as ceramic powders and organic-inorganic composites, that release the ions, have been developed and investigated for their cytocompatibilities in our previous work. Through the investigation, providing the three ions was found to be effective to activate osteogenic cells. Magnesium and siloxane--containing vaterite was prepared by a carbonation process as an inorganic particle that can has the ability to simultaneously release Ca(2+), silicate, and Mg(2+) ions to biodegradable polymers. Poly (l-lactic acid) (PLLA)- and bioactive PLLA-based composites containing vaterite coatings were discussed regarding their degradability and cytocompatibility using a metallic Mg substrate as Mg(2+) ion source. PLLA/SiV composite film, which has a releasability of silicate ions besides Ca(2+) ion, was coated on a pure Mg substrate to be compared with the PLLA/V coating. The degradability and releasability of inorganic ions were morphologically and quantitatively monitored in a cell culture medium. The bonding strength between the coatings and Mg substrates was one of the key factors to control Mg(2+) ion release from the substrates. The cell culture tests were conducted using mouse osteoblast-like cells (MC3T3-E1 cells); cellular morphology, proliferation, and differentiation on the materials were evaluated. The PLLA/V and PLLA/SiV coatings on Mg substrates were found to enhance the proliferation, especially the PLLA/SiV coating possessed a higher ability to induce the osteogenic differentiation of the cells.

Cytocompatibility of Siloxane-Containing Vaterite/Poly(l-lactic acid) Composite Coatings on Metallic Magnesium.

Poly(l-lactic acid)-based films which include 60 wt % of vaterite (V) or siloxane-containing vaterite (SiV) were coated on a pure magnesium substrate, denoted by PLLA/V or PLLA/SiV, respectively, to suppress early corrosion and improve its cytocompatibility. Both coating films adhered to the Mg substrate with 2.3-2.8 MPa of tensile bonding strength. Soaking test for 7 days in α-modified minimum essential medium revealed that the morphological instability of the PLLA/V film caused a higher amount of Mg2+ ion to be released from the coating sample. On the other hand, in the case of the coating with the PLLA/SiV film, no morphological change even after the soaking test was observed, owing to the suppression of the degradation rate. In cell culture tests, the proliferation of mouse osteoblast-like cell (MC3T3-E1) was significantly enhanced by both coatings, in comparison with the uncoated magnesium substrate. The cell morphology revealed that a few less-spread cells were observed on the PLLA/V film, while more elongated cells were done on the PLLA/SiV film. The cells on the PLLA/SiV film exhibited an extremely higher alkaline phosphatase activity after 21 days of incubation than that on the PLLA/V one. The PLLA/SiV film suppressed the early corrosion and enhanced cytocompatibility on metallic magnesium.

Siloxane-poly(lactic acid)-vaterite composites with 3D cotton-like structure.

Trace amounts of ionic calcium and silicon species have been reported to stimulate the proliferation, differentiation, and mineralization of bone-forming cells. Composite materials comprising siloxane-doped calcium carbonate (vaterite) particles and poly(L-lactic acid) have been developed [siloxane-poly(lactic acid)-vaterite hybrid-composite, SiPVH] so far; they were designed such that calcium and silicate ions are gradually released from SiPVH and they show the chronic effects of ions on cellular activities. In the present work, SiPVH with a 3D cotton-like structure was prepared by electrospinning to obtain the major advantages of excellent bioactivity and ease of handling for bone filling surgery. The diameter of the fibrous skeletons that form structure of the cotton-like SiPVH was controlled to ~10 µm to achieve cellular migration into the spaces between fibers. The resulting cotton-like SiPVH showed good flexibility. The fiber surface was coated rapidly with numerous particles of several hundred nanometers in size by alternate soaking in CaCl(2) and Na(2)HPO(4). The treated cotton-like material, which released calcium and silicate ions gradually, showed good cellular migration behavior into the 3D structure in cell culture tests using murine osteoblast-like MC3T3-E1 cells.

Utilization of calcite and waste glass for preparing construction materials with a low environmental load.

In this study, porous calcite materials are hydrothermally treated at 200 °C using powder compacts consisting of calcite and glasses composed of silica-rich soda-lime. After treatment, the glasses are converted into calcium aluminosilicate hydrates, such as zeolite phases, which increase their strength. The porosity and morphology of new deposits of hydrothermally solidified materials depend up on the chemical composition of glass. The use of calcite and glass in the hydrothermal treatment plays an important role in the solidification of calcite without thermal decomposition.

Hydrothermal preparation of diatomaceous earth combined with calcium silicate hydrate gels.

A novel composite for the removal of color in waste water was prepared by subjecting slurries consisting diatomaceous earth and slaked lime to a hydrothermal reaction at 180 °C. Subsequently, calcium silicate hydrate gels covered the surface of diatomaceous earth due to the reaction between the amorphous silica of diatomaceous earth and slaked lime. The formation of calcium silicate hydrate gels led to an increase in the specific surface area. The composites showed higher methylene blue adsorption capacity compared with diatomaceous earth. The improved adsorption capacity of the composites depended on the amount of the calcium silicate hydrate gels and their silicate anion chain-lengths.