A copper-containing analog of the biomineral whitlockite: dissolution-precipitation synthesis, structural and biological properties.

In the present work, copper whitlockite (Cu-WH, Ca18Cu2(HPO4)2(PO4)12) was successfully synthesized and comprehensively characterized, founding the base knowledge for its future studies in medicine, particularly for bone regeneration. This material is a copper-containing analog of the well-known biomineral magnesium whitlockite (Mg-WH, Ca18Mg2(HPO4)2(PO4)12). The synthesis of powders was performed by a dissolution-precipitation method in an aqueous medium under hydrothermal conditions. Phase conversion from brushite (CaHPO4·2H2O) to Cu-WH took place in an acidic medium in the presence of Cu2+ ions. Optimization of the synthesis conditions in terms of medium pH, temperature, time, Ca/Cu molar ratio and concentration of starting materials was performed. The crystal structure of the synthesized products was confirmed by XRD, FTIR and Raman spectroscopy, 1H and 31P solid-state NMR, and EPR. Morphological features and elemental distribution of the synthesized powders were studied by means of SEM/EDX analysis. The ion release in SBF solution was estimated using ICP-OES. Cytotoxicity experiments were performed with MC3T3-E1 cells. The study on thermal stability revealed that the synthesized material is thermally unstable and gradually decomposes upon annealing to Cu-substituted ß-Ca3(PO4)2 and Ca2P2O7.

Porous Lithium Disilicate Glass-Ceramics Prepared by Cold Sintering Process Associated with Post-Annealing Technique.

Using melt-derived LD glass powders and 5-20 M NaOH solutions, porous lithium disilicate (Li2Si2O5, LD) glass-ceramics were prepared by the cold sintering process (CSP) associated with the post-annealing technique. In this novel technique, H2O vapor originating from condensation reactions between residual Si-OH groups in cold-sintered LD glasses played the role of a foaming agent. With the increasing concentration of NaOH solutions, many more residual Si-OH groups appeared, and then rising trends in number as well as size were found for spherical pores formed in the resultant porous LD glass-ceramics. Correspondingly, the total porosities and average pore sizes varied from 25.6 ± 1.3% to 48.6 ± 1.9% and from 1.89 ± 0.68 µm to 13.40 ± 10.27 µm, respectively. Meanwhile, both the volume fractions and average aspect ratios of precipitated LD crystals within their pore walls presented progressively increasing tendencies, ranging from 55.75% to 76.85% and from 4.18 to 6.53, respectively. Young's modulus and the hardness of pore walls for resultant porous LD glass-ceramics presented remarkable enhancement from 56.9 ± 2.5 GPa to 79.1 ± 2.1 GPa and from 4.6 ± 0.9 GPa to 8.1 ± 0.8 GPa, whereas their biaxial flexural strengths dropped from 152.0 ± 6.8 MPa to 77.4 ± 5.4 MPa. Using H2O vapor as a foaming agent, this work reveals that CSP associated with the post-annealing technique is a feasible and eco-friendly methodology by which to prepare porous glass-ceramics.

Development of bioinspired damage-tolerant calcium phosphate bulk materials.

Improving the damage tolerance and reliability of ceramic artificial bone materials, such as sintered bodies of hydroxyapatite (HAp), that remain in vivo for long periods of time is of utmost importance. However, the intrinsic brittleness and low damage tolerance of ceramics make this challenging. This paper reports the synthesis of highly damage tolerant calcium phosphate-based materials with a bioinspired design for novel artificial bones. The heat treatment of isophthalate ion-containing octacalcium phosphate compacts in a nitrogen atmosphere at 1000°C for 24 h produced an HAp/ß-tricalcium phosphate/pyrolytic carbon composite with a brick-and-mortar structure (similar to that of the nacreous layer). This composite exhibited excellent damage tolerance, with no brittle fracture upon nailing, likely attributable to the specific mechanical properties derived from its unique microstructure. Its maximum bending stress, maximum bending strain, Young's modulus, and Vickers hardness were 11.7 MPa, 2.8 × 10‒2, 5.3 GPa, and 11.7 kgf/mm2, respectively. The material exhibited a lower Young's modulus and higher fracture strain than that of HAp-sintered bodies and sintered-body samples prepared from pure octacalcium phosphate compacts. Additionally, the apatite-forming ability of the obtained material was confirmed in vitro, using a simulated body fluid. The proposed bioinspired material design could enable the fabrication of highly damage tolerant artificial bones that remain in vivo for long durations of time.

Porphyrin covalent organic nanodisks synthesized using acid-assisted exfoliation for improved bactericidal efficacy.

Porphyrin covalent organic nanodisks (CONs) were synthesized by exfoliating covalent organic frameworks (COFs) in acidic aqueous solutions at pH 4. The synthesized CONs showed remarkable bactericidal activity against Escherichia coli owing to enhanced generation of singlet oxygen upon visible light irradiation.

A facile bottom-up method for synthesis of peroxo-potassium titanate nanoribbons and visible light photocatalytic activity derived from a peroxo-titanium bond.

Low-dimensional titanate nanostructures are gaining attention as a promising material for various photocatalytic applications. However, these conventional titanium oxide-based materials cannot utilize visible light because of their wide bandgap, and their synthesis generally requires high-alkali (10 mol L-1) and high-temperature (160-200 °C) conditions. Here, we report facile bottom-up synthesis for the visible light-activated peroxo-titanate nanoribbon (PTNR). The use of the peroxo-titanium complex ion containing the potassium ion as a precursor can induce the formation of a layered potassium titanate structure (K2-x H x Ti2O5) based on the self-organization reaction between titanium complex ions and potassium ions under mild synthetic conditions (0.29-4.39 mol L-1 KOH, 100 °C). Furthermore, the requirement of potassium ions in the formation of layered potassium titanate was stoichiometrically examined. The layered titanate crystals could be grown anisotropically, which depended on the radius of the cation used. Our results newly revealed that the larger radius of the interlayer cation promotes anisotropic crystal growth. As a result, in the case of the potassium base, a nanoribbon structure with a higher aspect ratio and larger specific surface area than those of lithium and sodium bases was formed. The formed peroxo-titanium functional groups significantly reduced the bandgap of titanate to 2.64 eV. In a photocatalytic decolorization test, the PTNR showed excellent photocatalytic performance based on the large surface area and enhanced light absorption in the visible light range while still performing well under UV light. These findings show not only that the proposed synthetic process has a low environmental impact but also that it contributes to the development of highly functionalized materials for photochemical applications.

Enhanced Photocatalytic Activity of Porphyrin Nanodisks Prepared by Exfoliation of Metalloporphyrin-Based Covalent Organic Frameworks.

Organic polymers derived from covalent organic frameworks (COFs) have various applications, including photocatalysis. The synthesis of organic polymer materials from COFs to obtain higher activity for photocatalysis by changing the unit molecule has been investigated. The choice of the unit molecule is important to characterize the photochemical properties. Among various such unit molecules, porphyrins have attracted much attention as organic chromophores commonly used in photocatalytic reactions with COFs. Although COFs with various organic chromophores have been synthesized and attempts have been made to improve their photocatalytic activity, enhancing the photocatalytic activity by adjusting the layer thickness through exfoliation of COFs has yet to be fully studied. In the present study, the exfoliation of metalloporphyrin-based COFs with pyridine as the axial ligand and adjustment of the layer thickness were found to enhance the photocatalytic activity. Hydrogen generation and 3,3',5,5'-tetramethylbenzidine oxidation reactions were investigated as representative photocatalytic reactions, with the photocatalytic activity up to 7 times that of the original free-base porphyrin COFs. These results indicate that the different thicknesses synthesized by exfoliating COFs increased the photocatalytic effect of polymers.

Mechanism investigation of the enhanced oxygen storage performance of YBaCo4O7+δ synthesized by a glycine-complex decomposition method.

A YBaCo4O7 oxygen storage material has been synthesized by the glycine-complex decomposition method at a low temperature of 800 °C and its crystal structure and reaction kinetics were investigated. This sample showed the highest storage/release speed among all the reported YBaCo4O7+δ materials.

Synthesis of Octacalcium Phosphate Containing Glutarate Ions with a High Incorporation Fraction.

Octacalcium phosphate (OCP) has received considerable attention in the field of ceramic biomaterials as an advanced functional material. It exhibits a layered structure composed of apatitic and hydrated layers and can incorporate various dicarboxylate ions into the hydrated layer. Saturated dicarboxylic acids (HOOC(CH2)nCOOH) with an odd number of methylene groups (-CH2-) exhibit lower incorporation fractions than those with an even number of methylene groups, possibly owing to a compositional dependence on the synthetic method. In this study, calcium carbonate, phosphoric acid, and various amounts of glutaric acid were used to produce glutarate-ion-incorporated OCP by a wet chemical method, which is different from the conventional synthetic strategy. While utilising 1-20 mmol of glutaric acid during synthesis did not produce the desired product, using 25 mmol of glutaric acid resulted in the formation of single-phase glutarate-ion-incorporated OCP with a Ca/P molar ratio of 1.57 and a 90% incorporation fraction of glutarate ions. This glutarate-ion-incorporation fraction is significantly higher than that reported in the previous studies (35%). Thus, the synthetic procedure proposed herein was able to produce single-phase OCP containing glutarate ions with a high incorporation fraction. Our findings can contribute to development of novel functional ceramic biomaterials in the future.

Bottom-up method for synthesis of layered lithium titanate nanoplates using ion precursor.

A facile bottom-up method for the synthesis of lithium titanate nanoplates using a peroxo titanium complex ion precursor is reported. Instead of employing complicated treatment with high alkali concentration, the self-organization reaction between lithium and titanium ions in the prepared ion precursor can enable the formation of layered lithium titanate crystals (Li2-xHxTi2O5, where x = 0.1 and 1.52 for as-synthesise and acid-treated samples, respectively) under low alkaline conditions. We demonstrate that layered lithium titanate crystals can be grown anisotropically into individual nanoplates. Our work presents an easy and useful platform for the production of titanate materials with various morphologies based on the interaction with ionic species.

Sr2+ sorption property of seaweed-like sodium titanate mats: effects of crystallographic properties.

Layered sodium titanate is a typical ion-exchanger for water purification aimed at removing cationic heavy metals and radionuclides. The material design of an ion-exchanger is effective for cation removal. For that purpose, understanding the basic impacts of crystallographic properties such as crystal size, morphology, and phase is critical for developing highly functional nanoscale ion-exchangers. In this study, we investigate the principal relationship between the crystallographic properties of seaweed-like sodium titanate mats (SSTs), which consist of a dititanate (H x Na2-x Ti2O5) phase of nanofibers synthesised by the alkaline hydrothermal method and their Sr2+ sorption mechanism. A trititanate (H x Na2-x Ti3O7) phase, which has a micro-sized fibre morphology, was also synthesised using the same method by adjusting the NaOH concentration. The SST demonstrates a high ion-exchange selectivity of Sr2+ against H+ and a high maximum sorption capacity (2 mmol g-1), which was four times higher than that of the trititanate phase (0.49 mmol g-1). In contrast, the trititanate phase, which is the comparison target, had a low Sr2+ ion-exchange selectivity and precipitated SrCO3. We conclude that these differences in Sr2+ sorption mechanisms were derived from not only the unique morphology but also the crystal structure of sodium titanates. Although almost all of the Na+ in dititanate with lamellar structure was consumed by the ion-exchange reaction, some Na+ remained in the trititanate because there are two sites in the zigzag layered structure. These findings on the crystallographic properties of SST for Sr2+ sorption may contribute to the functionalisation of a nanoscale ion-exchanger.

Incorporation of tetracarboxylate ions into octacalcium phosphate for the development of next-generation biofriendly materials.

Octacalcium phosphate (OCP; Ca8(HPO4)2(PO4)4 ∙ 5H2O) is a precursor of hydroxyapatite found in human bones and teeth, and is among the inorganic substances critical for hard tissue formation and regeneration in the human body. OCP has a layered structure and can incorporate carboxylate ions into its interlayers. However, studies involving the incorporation of tetracarboxylic and multivalent (pentavalent and above) carboxylic acids into OCP have not yet been reported. In this study, we investigate the incorporation of pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), a type of tetracarboxylic acid, into OCP. We established that pyromellitate ions could be incorporated into OCP by a wet chemical method using an acetate buffer solution containing pyromellitic acid. The derived OCP showed a brilliant blue emission under UV light owing to the incorporated pyromellitate ions. Incorporation of a carboxylic acid into OCP imparted new functions, which could enable the development of novel functional materials for biomedical applications.

Enhancing Visible Light Absorption of Yellow-Colored Peroxo-Titanate Nanotubes Prepared Using Peroxo Titanium Complex Ions.

Visible light-activated yellow titanate nanotubes (TNTs) modified by peroxo groups were directly synthesized via a facile chemical reaction route using peroxo titanium complex ions as a precursor. Obtained peroxo-modified TNTs (PTNTs) possessed a cylindrical-shaped tubular morphology with an outer diameter of approximately 10 nm. The peroxo titanium functional group (Ti-O-O) was formed between the interlayers of the lepidocrocite-type titanate crystal that was the base structure of TNTs, with the interlayer distance estimated at approximately 10.02 Å. The formation of the peroxo functional groups reduced the electron density adjacent to the titanium atom, raising the valence band to 1.35 eV and forming a band gap of 2.50 eV, which is lower than that of TNTs (3.19 eV). In addition, the peroxo titanium functional group had a negative potential, which increased the chemical adsorption performances with positively charged rhodamine B molecules in water. Meanwhile, the photocatalytic investigation indicated that the PTNTs have enhanced the photocatalytic performance for RhB decolorization under visible light irradiating in comparison with TNTs. These findings show not only the improvement in the photocatalytic performance but also the potential of processing design by selecting the precursor with arbitrary characteristics.

Effects of Annealing Temperature on the Crystal Structure, Morphology, and Optical Properties of Peroxo-Titanate Nanotubes Prepared by Peroxo-Titanium Complex Ion.

This study addresses the effects of annealing temperatures (up to 500 °C) on the crystal structure, morphology, and optical properties of peroxo groups (-O-O-) containing titanate nanotubes (PTNTs). PTNTs, which possess a unique tubular morphology of layered-compound-like hydrogen titanate structure (approximately 10 nm in diameter), were synthesized using peroxo-titanium (Ti-O-O) complex ions as a precursor under very mild conditions-temperature of 100 °C and alkali concentration of 1.5 M-in the precursor solution. The nanotubular structure was dismantled by annealing and a nanoplate-like structure within the range of 20-50 nm in width and 100-300 nm in length was formed at 500 °C via a nanosheet structure by decreasing the specific surface area. Hydrogen titanate-based structures of the as-synthesized PTNTs transformed directly into anatase-type TiO2 at a temperature above 360 °C due to dehydration and phase transition. The final product, anatase-based titania nanoplate, was partially hydrogen titanate crystal in nature, in which hydroxyl (-OH) bonds exist in their interlayers. Therefore, the use of Ti-O-O complex ions contributes to the improved thermal stability of hydrogen titanate nanotubes. These results show a simple and environmentally friendly method that is useful for the synthesis of functional nanomaterials for applications in various fields.

Crystallization Behavior of the Low-Temperature Mineralization Sintering Process for Glass Nanoparticles.

Bioactive glasses are promising materials for various applications, such as bone grafts and implants. The development of sintering techniques for bioactive glasses is one of the most important ways to expand the application to biomaterials. In this paper, we demonstrate the low-temperature mineralization sintering process (LMSP) of glass nanoparticles and their crystallization behavior. LMSP is a novel process employed to densify glass nanoparticles at an extremely low temperature of 120 °C. For this new approach, the hydrothermal condition, mineralization, and the nanosize effect are integrated into LMSP. To induce mineralization in LMSP, bioactive glass nanoparticles (BGNPs, 55SiO2-40CaO-5P2O5, mol%), prepared by the sol-gel process, were mixed with a small amount of simulated body fluid (SBF) solution. As a result, 93% dense BGNPs were realized under a temperature of 120 °C and a uniaxial pressure of 300 MPa. Due to the effect of mineralization, crystalline hydroxyapatite (HAp) was clearly formed at the boundaries of BGNPs, filling particles and interstitials. As a result, the relative density was remarkably close to that of the BGNPs conventionally sintered at 1050 °C. Additionally, the Vickers hardness value of LMSP samples varied from 2.10 ± 0.12 GPa to 4.28 ± 0.11 GPa, and was higher than that of the BGNPs conventionally sintered at 850 °C (2.02 ± 0.11 GPa). These results suggest that, in addition to LMSP being an efficient densification method for obtaining bulk bioactive glasses at a significantly lower temperature level, this process has great potential for tissue engineering applications, such as scaffolds and implants.

Sorption capacity of seaweed-like sodium titanate mats for Co2+ removal.

The development of new technologies for securing and recycling water resources are in high demand. A key focus of these technologies is the development of various ion exchangers or adsorbents that are used for the purification of aqueous solutions. Layered sodium titanate is one of the cation exchangers utilised in the removal of heavy metals and radionuclides from wastewater. To enhance the removal efficiency, the precise design of the crystal morphology, structure, and chemical composition is important. Herein, we synthesised a unique seaweed-like sodium titanate mat (SST) using a template-free alkaline hydrothermal process. The Co2+ sorption capacity of SST was investigated by batch testing with cobalt(ii) nitrate. SST, which was synthesised from titanium sulphate in a 10 M NaOH solution at 200 °C, had a seaweed-like structure composed of randomly distributed nanofibres of layered sodium titanate that is approximately 9 nm in diameter. The crystal shape changed from roundish crystals to fibrous crystals as the hydrothermal reaction period increased. The Co2+ sorption isotherm of SST was fitted with the Langmuir isotherm model and the maximum sorption density was 1.85 mmol g-1. The selectivity of the Co2+ sorption on SST was high in comparison to that of Ca2+ and Mg2+. Herein, the Co2+ sorption mechanisms of SST were studied in comparison with commercially available sodium titanate. Results show that controlling the crystal morphology, structure, and Na concentration of the layered titanate that can be ion-exchanged determines the cation sorption properties of sodium titanate.

Thermoelectric Array Sensors with Selective Combustion Catalysts for Breath Gas Monitoring.

Inflammable breath gases such as H2 and CH4 are used as bio markers for monitoring the condition of the colon. However, their typical concentrations of below 100 ppm pose sensitivity and selectivity challenges to current gas sensing systems without the use of chromatography. We fabricated a compact, gas-selective thermoelectric array sensor (TAS) that uses micro-machined sensor devices with three different combustion catalysts to detect gases such as H2, CO, and CH4 in breath. Using Pt/Pt-W thin-film micro-heater meanders, Pd/Al2O3, Pt,Pd,Au/Co3O4, and Pt/Al2O3 catalysts were heated to 320, 200, and 125 °C, respectively, and the gas sensing performances of the TAS for each gas and for a model breath gas mixture of 100 ppm H2, 25 ppm CO, 50 ppm CH4, and 199 ppm CO2 in air were investigated. Owing to its high catalyst temperature, the Pd/Al2O3 catalyst burned all three gases, while the Pt,Pd,Au/Co3O4 burned CO and H2 and the Pt/Al2O3 burned H2 selectively. To calibrate the gas concentration of the mixture gas without the use of a gas separation tool, linear discriminant analysis was applied to measure the sensing performance of TAS. To enhance the gas selectivity against H2, a double catalyst structure was integrated into the TAS sensor.

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3.

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3-30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2.

Interfacial shear strength of bioactive-coated carbon fiber reinforced polyetheretherketone after in vivo implantation.

Despite the excellent osseointegration of carbon-fiber-reinforced polyetheretherketone (CFR/PEEK) with a surface hydroxyapatite (HA) coating, the bone-implant interfacial shear strength of HA-coated CFR/PEEK after osseointegration is unclear. We examined the interfacial shear strength of HA-coated CFR/PEEK implants after in vivo implantation in a rabbit femur-implant pull-out test model. HA coating was performed by a newly developed method. Uncoated CFR/PEEK, HA-coated blasted titanium alloy, and uncoated blasted titanium alloy were used as control implants. The implants were inserted into drilled femoral cortex, and pull-out tests were conducted after 6 and 12 weeks of implantation to determine maximum interfacial shear strength. The HA-coated CFR/PEEK (15.7 ± 4.5 MPa) and HA-coated titanium alloy (14.1 ± 6.0 MPa) exhibited significantly larger interfacial shear strengths than the uncoated CFR/PEEK (7.7 ± 1.8 MPa) and the uncoated titanium alloy (7.8 ± 2.1 MPa) at 6 weeks. At 12 weeks, only the uncoated CFR/PEEK (8.3 ± 3.0 MPa) exhibited a significantly smaller interfacial shear strength, as compared to the HA-coated CFR/PEEK (17.4 ± 3.6 MPa), HA-coated titanium alloy (14.2 ± 4.8 MPa), and uncoated titanium alloy (15.0 ± 2.6 MPa). Surface analysis of the removed implants revealed detachment of the HA layer in both the HA-coated CFR/PEEK and titanium alloy implants. The proposed novel HA coating method of CFR/PEEK significantly increased interfacial shear strength between bone and CFR/PEEK. The achieved interfacial shear strength of the HA-coated CFR/PEEK implant is of the same level as that of grit-blasted titanium alloy with HA.