Graphitic Hollow Nanocarbon as a Promising Conducting Agent for Solid-State Lithium Batteries.

All-solid-state batteries (ASSBs) have lately received enormous attention for electric vehicle applications because of their exceptional stability by engaging all-solidified cell components. However, there are many formidable hurdles such as low ionic conductivity, interface instability, and difficulty in the manufacturing process, for its practical use. Recently, carbon, one of the representative conducting agents, turns out to largely participate in side reactions with the solid electrolyte, which finally leads to the formation of insulating side products at the interface. Although the battery community mentioned that parasitic reactions are presumably attributed to carbon itself or the generation of electronic conducting paths lowering the kinetic barrier for reactions, the underlying origin for such reactions as well as appropriate solutions have not been provided yet. In this study, for the first time, it is verified that the functional group on carbon is an origin for causing negative effects on interfacial stability and a graphitized hollow nanocarbon as a promising solution for improving-electrochemical performance is introduced. This work offers an invaluable lesson that a relatively minor part, such as a conducting agent, in ASSBs sometimes gives more positive impact on improving electrochemical performance than huge efforts for resolving other parts.

Dentin sealing and antibacterial effects of silver-doped bioactive glass/mesoporous silica nanocomposite: an in vitro study.

OBJECTIVES: To synthesize a silver-doped bioactive glass/mesoporous silica nanoparticle (Ag-BGN@MSN), as well as to investigate its effects on dentinal tubule occlusion, microtensile bond strength (MTBS), and antibacterial activity. MATERIALS AND METHODS: Ag-BGN@MSN was synthesized using a modified "quick alkali-mediated sol-gel" method. Demineralized tooth disc models were made and divided into four groups; the following treatments were then applied: group 1-no treatment, group 2-bioglass, group 3-MSN, group 4-Ag-BGN@MSN. Next, four discs were selected from each group and soaked into 6 wt% citric acid to test acid-resistant stability. Dentinal tubule occlusion, as well as the occlusion ratio, was observed using field-emission scanning electron microscopy. The MTBS was also measured to evaluate the desensitizing effect of the treatments. Cytotoxicity was examined using the MTT assay. Antibacterial activity was detected against Lactobacillus casei, and ion dissolution was evaluated using inductively coupled plasma optical emission spectrometry. RESULTS: Ag-BGN@MSN effectively occluded the dentinal tubule and formed a membrane-like layer. After the acid challenge, Ag-BGN@MSN had the highest rate of dentinal tubule occlusion. There were no significant differences in MTBS among the four groups (P > 0.05). All concentrations of Ag-BGN@MSN used had a relative cell viability above 72%. CONCLUSIONS: Ag-BGN@MSN was successfully fabricated using a modified sol-gel method. The Ag-BGN@MSN biocomposite effectively occluded dentinal with acid-resistant stability, did not decrease bond strength in self-etch adhesive system, had low cytotoxicity, and antibacterial effect. CLININAL RELEVANCE: Dentinal tubule sealing induced by Ag-BGN@MSN biocomposite with antibacterial effect is likely to increase long-term stability in DH.

Effect of different sizes of bioactive glass-coated mesoporous silica nanoparticles on dentinal tubule occlusion and mineralization.

OBJECTIVES: To synthesize two different sizes of bioactive glass-coated mesoporous silica nanoparticles (BGN@MSNs) and to investigate their effects on dentinal tubule occlusion and remineralization. MATERIALS AND METHODS: Two different sizes of mesoporous silica nanoparticles (MSNs) were synthesized using the Stöber method (368A, 1840A) and coated with bioactive glass nanoparticles (BGNs) using a modified quick alkali-mediated sol-gel method (368B, 1840B). Sensitive tooth disc models were prepared and divided into six groups and the following treatments were applied: group 1-no treatment, group 2-bioglass, group 3-368A, group 4-368B, group 5-1840A, and group 6-1840B. Then, five discs were selected from each group and soaked in 6 wt% citric acid to test acid resistance. Dentinal tubule occlusion and occlusion ratio were observed using field-emission scanning electron microscopy. In vitro mineralization tests using simulated body fluid solution were performed to evaluate the remineralization effect of the treatment. RESULTS: All samples effectively occluded the dentinal tubule and formed a membrane-like layer. After acid treatment, 1840B (group 6) exhibited the highest rate of dentinal tubule occlusion. Remineralization was observed in 368B and 1840B, and 1840B exhibited the fastest remineralization. CONCLUSIONS: Dentinal tubule remineralization induced by the BGN@MSN biocomposite can be used to stabilize long-term prognosis in dentin hypersensitivity. The 1840B induced the most efficient remineralization, and its smaller size and larger surface area were effective for remineralization. CLINICAL RELEVANCE: The BGN@MSN biocomposite with its smaller size and larger surface area was more effective for remineralization and dentinal tubule sealing.

In-Vitro Mechanical Performance Study of Biodegradable Polylactic Acid/Hydroxyapatite Nanocomposites for Fixation Medical Devices.

Osteoconductive, biocompatible, and resorbable organic/inorganic composites are most commonly used in fixation medical devices, such as suture anchors and interference screws, because of their unique physical and chemical properties. Generally, studies on biodegradable composites have focused on their mechanical properties based on the composition and the individual roles of organic and inorganic biomaterials. In this study, we prepared biodegradable organic/inorganic nanocomposite materials using the solvent mixing process and conventional molding. We used polylactic acid (PLA) as the matrix and nano-sized hydroxyapatite (nano-HAp) as the osteoconductive filler. The content of nano-HAp was varied in 0-30 wt% and its influence on the In-Vitro mechanical performance of PLA/HAp nanocomposites was evaluated. The In-Vitro mechanical properties of nanocomposites were evaluated using standardized tensile and flexural tests after different immersion times in simulated body fluid.

Polylactic Acid/Nanostructured Si-Substituted ß-Tricalcium Phosphate Composites for Biodegradable Fixation Medical Devices.

Organic/inorganic biocomposite materials for biodegradable fixation medical devices require osteoconductivity, biocompatibility, and adequate mechanical properties with biodegradation behavior. The objective of this study was to investigate the effect of Si ions substituted in ß-tricalcium phosphate (ß-TCP) on the mechanical properties of organic/inorganic biocomposites. Biodegradable composite materials were prepared with polylactic acid (PLA) as the matrix and nano Si-substituted ß-TCP as the osteoconductive filler by solvent mixing and conventional molding. The nanostructured Si-substituted ß-TCP powders were synthesized by co-precipitation, controlling the quantity of Si ions. The amount of nanostructured Si-substituted ß-TCP powders in composites was varied in the 0-40 wt% range and the material properties were compared with those of pure ß-TCP/PLA composites. The influence of Si ions on the mechanical properties of the composites was evaluated by tensile and flexural tests.

Influence of Starting Powders on Hydroxyapatite Coatings Fabricated by Room Temperature Spraying Method.

Three types of raw materials were used for the fabrication of hydroxyapatite coatings by using the room temperature spraying method and their influence on the microstructure and in vitro characteristics were investigated. Starting hydroxyapatite powders for coatings on titanium substrate were prepared by a heat treatment at 1100 °C for 2 h of bovine bone, bone ash, and commercial hydroxyapatite powders. The phase compositions and Ca/P ratios of the three hydroxyapatite coatings were similar to those of the raw materials without decomposition or formation of a new phase. All hydroxyapatite coatings showed a honeycomb structure, but their surface microstructures revealed different features in regards to surface morphology and roughness, based on the staring materials. All coatings consisted of nano-sized grains and had dense microstructure. Inferred from in vitro experiments in pure water, all coatings have a good dissolution-resistance and biostability in water.

The Role of Magnesium Ion Substituted Biphasic Calcium Phosphate Spherical Micro-Scaffolds in Osteogenic Differentiation of Human Adipose Tissue-Derived Mesenchymal Stem Cells.

This study was investigated the role of magnesium (Mg2+) ion substituted biphasic calcium phosphate (Mg-BCP) spherical micro-scaffolds in osteogenic differentiation of human adipose tissue-derived mesenchymal stem cells (hAT-MSCs). Mg-BCP micro-scaffolds with spherical morphology were successfully prepared using in situ co-precipitation and spray drying atomization process. The in vitro cell proliferation and differentiation of hAT-MSCs were determined up to day 14. After in vitro biological tests, Mg-BCP micro-scaffolds with hAT-MSCs showed more enhanced osteogenicity than pure hAT-MSCs as control group by unique biodegradation of TCP phase and influence of substituted Mg2+ ion in biphasic nanostructure. Therefore, these results suggest that Mg-BCP micro-scaffolds promote osteogenic differentiation of hAT-MSCs.

Emission Directionality of 3D-Printed Photonic Nanowires.

Photonic devices can be advanced by increasing the density of the integrated optical components. As the integration density increases, the potential for signal interference between adjacent components, optical crosstalk, becomes a concern. To address the crosstalk issue, it is crucial to identify the emission directionality of the integrated optical components. In this study, we investigate the emission directionality of 3D printed light-emitting nano/microwires. We experimentally and numerically showed that when the diameter is reduced below the single-mode cutoff, the emission becomes noticeably directional. In addition, our demonstrations on pairs of closely positioned wires show that optical crosstalk can be effectively avoided by reducing the diameter to the nanoscale to exploit the strong directionality of its emission. We expect that our study can be applied to various fundamental research and applications in the fields of photonics, optical communication, sensing, and imaging, where the directionality of the emissions is crucial.

Effect of annealing temperature on electrochemical luminescence properties of nanoporous fluorine-doped tin oxide films.

Nanoporous Fluorine-doped tin oxide (FTO) materials were synthesized by sol-gel combustion method for electrochemical luminescence (ECL) application. The influence of annealing temperature on the structures and morphology of the nanoporous FTO films was examined by X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmittance and BET specific surface measurements. The naoporous FTO-based ECL cell is composed of FTO glass/nanoporous FTO/Ru(bpy)2+ electrolyte/FTO glass. The peak intensity of emitting light from the cell was obtained at the wavelength of about 615 nm, which corresponds to dark orange color. At 5 V bias, ECL efficiency of the cell using the 550 degrees C annealed FTO was about 975 cd/m2, which is much higher than those of other cells. The result shows that the nanoporous FTO layer was more effective for increasing ECL intensities. The sol-gel combustion method at annealing temperature of 550 degrees C could be employed to synthesize the nanoporous FTO materials with high porosity and ECL performance.

The effect of kaempferol on the dentin bonding stability through matrix metalloproteinases inhibition and collagen crosslink in dentin biomodification.

Background/purpose: Naturally derived collagen crosslinkers with matrix metalloproteinases (MMPs) inhibitory activity for dentin bonding have been previously studied. One of these crosslinkers is flavonoids. The purpose of this study was to investigate whether dentin pretreatment with kaempferol (KEM), one of the flavonoids, enhances dentin bond stability and nanoleakage at the dentin-resin interface through MMPs inhibition and collagen crosslinking. Materials and methods: The experimental KEM-containing solution was used to pretreat demineralized dentin prior to the application of a universal adhesive. KEM is a natural flavonoid and those which did not take the experimental solution served as the control group (CON). Microtensile bond strength (µTBS) and nanoleakage tests were conducted before and after the thermocycling to evaluate the influence of KEM on dentin bond strength. The MMPs inhibition activity of KEM was analyzed via MMPs zymography using a confocal microscopy. Fourier-transform infrared (FTIR) spectroscopy was used to demonstrate that KEM inhibits MMPs and enhances collagen crosslinking. Results: The µTBS values of KEM group exhibited a higher bond strength after thermocycling. At the resin-dentin interface, the KEM group did not exhibit any signs of nanoleakage after thermocycling. Furthermore, MMPs zymography confirmed that there was a relatively low activity of MMPs in the presence of KEM. In FTIR analysis, the PO4 peak representing the cross-link between dentin and collagen was significantly higher in the KEM group. Conclusion: Our findings suggest that pretreatment with KEM enhances the dentin bonding stability at the resin-dentin interface by acting as a collagen crosslinker and MMPs inhibitor.

Three-Dimensional Printing of Structural Color Using a Femtoliter Meniscus.

Structural colors are produced by the diffraction of light from microstructures. The collective arrangement of substructures is a simple and cost-effective approach for structural coloration represented by colloidal self-assembly. Nanofabrication methods enable precise and flexible coloration by processing individual nanostructures, but these methods are expensive or complex. Direct integration of desired structural coloration remains difficult because of the limited resolution, material-specificity, or complexity. Here, we demonstrate three-dimensional printing of structural colors by direct writing of nanowire gratings using a femtoliter meniscus of polymer ink. This method combines a simple process, desired coloration, and direct integration at a low cost. Precise and flexible coloration is demonstrated by printing the desired structural colors and shapes. In addition, alignment-resolved selective reflection is shown for displayed image control and color synthesis. The direct integration facilitates structural coloration on various substrates, including quartz, silicon, platinum, gold, and flexible polymer films. We expect that our contribution can expand the utility of diffraction gratings across various disciplines such as surface-integrated strain sensors, transparent reflective displays, fiber-integrated spectrometers, anticounterfeiting, biological assays, and environmental sensors.

Synthesis and Characterization of Mesoporous Aluminum Silicate and Its Adsorption for Pb (II) Ions and Methylene Blue in Aqueous Solution.

Aluminum silicate powder was prepared using two different syntheses: (1) co-precipitation and (2) two-step sol-gel method. All synthesized powders were characterized by various techniques including XRD, FE-SEM, FT-IR, BET, porosimeter, and zetasizer. The particle morphology of the synthesized aluminum silicate powder was greatly different depending on the synthesis. The synthesized aluminum silicate powder by co-precipitation had a low specific surface area (158 m2/g) and the particle appeared to have a sharp edge, as though in a glassy state. On the other hand, synthesized aluminum silicate powder by the two-step sol-gel method had a mesoporous structure and a large specific surface area (430 m2/g). The aluminum silicate powders as adsorbents were characterized for their adsorption behavior towards Pb (II) ions and methylene blue in an aqueous solution performed in a batch adsorption experiment. The maximum adsorption capacities of Pb (II) ions and methylene blue onto the two-step sol-gel method powder were over four-times and seven-times higher than that of the co-precipitation powder, respectively. These results show that the aluminum silicate powder synthesized with a two-step sol-gel method using ammonia can be a potential adsorbent for removing heavy metal ions and organic dyes from an aqueous solution.

Simultaneous Substitution of Fe and Sr in Beta-Tricalcium Phosphate: Synthesis, Structural, Magnetic, Degradation, and Cell Adhesion Properties.

ß-tricalcium phosphate is a promising bone graft substitute material with biocompatibility and high osteoinductivity. However, research on the ideal degradation and absorption for better clinical application remains a challenge. Now, we focus on modifying physicochemical properties and improving biological properties through essential ion co-substitution (Fe and Sr) in ß-TCPs. Fe- and Sr-substituted and Fe/Sr co-substituted ß-TCP were synthesized by aqueous co-precipitation with substitution levels ranging from 0.2 to 1.0 mol%. The ß-TCP phase was detected by X-ray diffraction and Fourier transform infrared spectroscopy. Changes in Ca-O and P-O bond lengths of the co-substituted samples were observed through X-ray photoelectron spectroscopy. The results of VSM represent the M-H graph having a combination of diamagnetic and ferromagnetic properties. A TRIS-HCl solution immersion test showed that the degradation and resorption functions act synergistically on the surface of the co-substituted sample. Cell adhesion tests demonstrated that Fe enhances the initial adhesion and proliferation behavior of hDPSCs. The present work suggests that Fe and Sr co-substitution in ß-TCP can be a candidate for promising bone graft materials in tissue engineering fields. In addition, the possibility of application of hyperthermia for cancer treatment can be expected.

Dentin Biomodification with Flavonoids and Calcium Phosphate Ion Clusters to Improve Dentin Bonding Stability.

The purpose of this study was to evaluate the effects of flavonoids and calcium phosphate ion clusters (CPIC) on dentin bonding stability. Seven experimental solutions were synthesized using icaritin (ICT), fisetin (FIS), silibinin (SIB), CPIC, and combinations of one of three flavonoids and CPIC (ICT + C, FIS + C, SIB + C). The experimental solutions were applied to demineralized dentin prior to the application of a universal adhesive. A group without any experimental solution served as a control. Dentin specimens pretreated with the experimental solutions were assayed using Fourier transform infrared (FTIR) spectroscopy. The microtensile bond strength (µTBS) and nanoleakage were evaluated at 24 h and after 10,000 thermocycles. FIS and ICT + C showed significantly higher µTBS than the control group at 24 h. CPIC, ICT + C, FIS + C, and SIB + C showed significantly higher µTBS than the control group after thermocycling. After thermocycling, silver infiltration into the hybrid layer and interfacial gaps was more noticeable in the control group than in the other groups. The FTIR spectra revealed the formation of apatitic minerals in the demineralized dentin in the flavonoid and CPIC combination groups. The pretreatment of demineralized dentin with flavonoids and CPIC improved dentin bonding stability. The flavonoid and CPIC combinations preserved dentin bond strength.

Lithium doped biphasic calcium phosphate: Structural analysis and osteo/odontogenic potential in vitro.

Biphasic calcium phosphate (BCP) is generally considered a good synthetic bone graft material with osteoinductive potential. Lithium ions are trace elements that play a role in the bone-remodeling process. This study aimed to investigate the effects of lithium ions on the phase, crystal structure, and biological responses of lithium doped BCPs and to identify improvements in their osteogenic properties. Lithium-doped BCP powders with different doping levels (0, 5, 10, and 20 at%) were synthesized via the co-precipitation method. We found that the four types of lithium-doped BCP powders showed different phase compositions of hydroxyapatite and ß-tricalcium phosphate. In addition, lithium ions favored entering the ß-tricalcium phosphate structure at the Ca (4) sites and calcium vacancy sites [VCa(4)] up to 10 at%. This substitution improves the crystal stabilization by filling the vacancies with Ca2+ and Li+ in all Ca sites. However, when the concentration of Li ions was higher than 10 at%, lithium-induced crystal instability resulted in the burst release of lithium ions, and the osteogenic behavior of human dental pulp stem cells did not improve further. Although lithium ions regulate osteogenic properties, it is important to determine the optimal amount of lithium in BCPs. In this study, the most effective lithium doping level in BCP was approximately 10 at% to improve its biological properties and facilitate medical applications.

A remineralizing orthodontic etchant that utilizes calcium phosphate ion clusters.

This study aimed to investigate whether a phosphoric acid (H3PO4) solution containing calcium phosphate ion clusters (CPICs) could minimize enamel damage during long-term bracket bonding by dissolving the enamel surface and promoting enamel remineralization. The experimental design is as follows: first, three experimental etchants (H3PO4, CPICs-incorporated H3PO4 solution-I, and CPICs-incorporated H3PO4 solution-II) and two bonding resins (conventional orthodontic resin and self-adhesive orthodontic resin) were used in combination to create six groups, respectively. Each of these six groups was then divided into two sub-groups based on the presence or absence of thermocycling (TC). Twenty samples were assigned to each of the 12 groups (independent variables), and thus a total of 240 metal bracket-attached human premolars were used in this experiment. Bracket debonding was performed on each of 20 premolars in 12 groups, and shear bond strength (SBS) and adhesive remnant index (ARI) values were measured as dependent variables. Next, the three experimental etchants were applied (independent variables) to each of the three enamel samples, and the remineralization of the enamel surface was investigated as a dependent variable. The enamel surface was observed using electron scanning and atomic force microscopy. Furthermore, X-ray diffraction, energy dispersive spectroscopy (EDX) spectrum X-ray spectroscopy, and elemental mapping were performed, and the Knoop microhardness scale was measured. Therefore, the experiment was performed in two steps: SBS and ARI measurements for 12 groups, followed by observation of the enamel surface and microhardness measurements, according to the three types of etchants. As a result of the experiment, first, when the bracket was debonded, SBS did not decrease, and residual adhesive was hardly observed in the C2A group (before TC), C2A, and C1C groups (after TC) (p < 0.001). Second, the experimental etchant containing CPICs achieved remineralization while demineralizing the enamel. This was verified through SEM/EDX, element mapping, XRD, and AFM. Also, the roughness and microhardness of the enamel surface were better in the remineralized surface by the experimental etchant containing CPICs (p < 0.017). The CPICs-incorporated H3PO4 solution reduced ARI while maintaining SBS during bracket debonding, regardless of whether TC was performed or the type of resin. The etchant containing CPICs was also shown to remineralize the enamel and increase its microhardness.

Enhanced antimicrobial and remineralizing properties of self-adhesive orthodontic resin containing mesoporous bioactive glass and zwitterionic material.

Abstract Background/purpose: Self-adhesive resins (SARs) do not require additional restorative adhesives and provide adequate adhesion to mineralized dental structures by shortening the bonding time in clinics where moisture control and isolation are difficult. The aim of this study was to evaluate the mechanical and biological properties of SARs containing mesoporous bioactive glass nanoparticles (MBNs) and 2-methacryloyloxyethyl phosphorylcholine (MPC) and to determine their antibacterial and remineralization effects. Materials and methods: MBNs and MPC were added to SARs to improve their physical properties and remineralization ability. The experimental resins assessed in this study were SARs mixed with 3%MPC, 5%MPC, 1%MBN+3%MPC, or 3%MBN+3%MPC. The shear bond strength, microhardness, adhesive remnant index, ion dissolution, degree of conversion, and antibacterial properties of the SARs were evaluated. To assess the remineralization properties, micro-computed tomography analysis was performed after pH cycling. Results: Increasing the MBN content in SAR resulted in higher microhardness compared to the control SAR. The shear bond strength decreased in the SAR+5%MPC group and increased in the SAR+1%MBN+3%MPC and SAR+3%MBN+5%MPC groups. Conclusion: Our findings suggest that SARs containing MBNs and MPC have antibacterial and remineralization effects on the enamel.

Optical Manipulation of Incident Light for Enhanced Photon Absorption in Ultrathin Organic Photovoltaics.

We attempted to improve the photon absorption of the photoactive layer in organic photovoltaic (OPV) devices by device engineering without changing their thickness. Soft nanoimprinting lithography was used to introduce a 1D grating pattern into the photoactive layer. The increase in photocurrent caused by the propagating surface plasmon-polariton mode was quantitatively analyzed by measuring the external quantum efficiency in transverse magnetic and transverse electric modes. In addition, the introduction of an ultrathin substrate with a refractive index of 1.34 improved photon absorption by overcoming the mismatched optical impedance at the air/substrate interface. As a result, the power conversion efficiency (PCE) of an ultrathin OPV with a 400 nm grating period was 8.34%, which was 11.6% higher than that of an unpatterned ultrathin OPV, and the PCE was 3.2 times higher at a low incident light angle of 80°, indicating very low incident light angle dependence.

In Situ Formed Ag-Li Intermetallic Layer for Stable Cycling of All-Solid-State Lithium Batteries.

With the timely advent of the electric vehicle era, where battery stability has emerged as a major issue, all-solid-state batteries (ASSBs) have attracted significant attention as the game changer owing to their high stability. However, despite the introduction of a densely packed solid electrolyte (SE) layer, when Li is used to increase the energy density of the cell, the short-circuit problem caused by Li protrusion is unavoidable. Furthermore, most strategies to control nonuniform Li growth are so complicated that they hinder the practical application of ASSBs. To overcome these limitations, this study proposes an Ag-Li alloy anode via mass-producible roll pressing method. Unlike previous studies reporting solid-solution-based metal alloys containing a small amount of lithiophilic Ag, the in situ formed and Ag-enriched Ag-Li intermetallic layer mitigates uneven Li deposition and maintains a stable SE/Ag-Li interface, facilitating reversible Li operation. Contrary to Li cells showing frequent initial short-circuit, the cell incorporating the Ag-Li anode exhibits a better capacity retention of 94.3% for 140 cycles, as well as stable cycling even under 12 C. Through a facile approach enabling the fabrication of a large-area anode with controllable Li growth, this study provides practical insight for developing ASSBs with stable cyclabilities.

Morphologies of nano-sized apatite formed on titanium substrate by biomimetic process.

The apatite was formed on the titanium plates with NaOH and heat treatments by biomimetic process. The influence of titanium surface microstructure on the apatite formation onto titanium substrate in SBF solution was investigated. After biomimetic process, nano-sized apatite layers were found on the Ti plates with NaOH and heat treatments. However, the morphologies of formed apatite on substrate had different shapes such as coated, load-like, and linked. The morphology of apatite formed by biomimetic process would be affected by alkaline treatment, and substrate morphology and phase.