Defect-Rich, Highly Porous PtAg Nanoflowers with Superior Anti-Poisoning Ability for Efficient Methanol Oxidation Reaction.

The design of efficient and sustainable Pt-based catalysts is the key to the development of direct methanol fuel cells. However, most Pt-based catalysts still exhibit disadvantages including unsatisfied catalytic activity and serious CO poisoning in the methanol oxidation reaction (MOR). Herein, highly porous PtAg nanoflowers (NFs) with rich defects are synthesized by using liquid reduction combining chemical etching. It is demonstrated that the proportion of precursors determines the inhomogeneity of alloy elements, and the strong corrosiveness of nitric acid to silver leads to the eventual porous flower-like structure. Impressively, the optimal etched Pt1 Ag2 NFs have the mixed defects of surface steps, dislocations, and bulk holes, and their mass activity (1136 mA mgPt-1 ) is 2.6 times higher than that of commercial Pt/C catalysts, while the ratio of forward and backward peak current density (If /Ib ) can reach 3.2, exhibiting an excellent anti-poisoning ability. Density functional theory calculations further verify their high anti-poison properties from both an adsorption and an oxidation perspective of CO intermediate. The introduction of Ag makes it easier for CO to be oxidized and removed. This study provides a facile approach to prepare rich defects and porous alloy with excellent MOR performance and superior anti-poisoning ability.

PtCuRu Nanoflowers with Ru-Rich Edge for Efficient Fuel-Cell Electrocatalysis.

Enhancing the catalytic activity of Pt-based alloy by a rational structural design is the key to addressing the sluggish kinetics of direct alcohol fuel cells. Herein, a facile one-pot method is reported to synthesize PtCuRu nanoflowers (NFs). The synergetic effect among Pt, Cu, and Ru can lower the d-band center of Pt, regulate the morphology, generate Ru-rich edge, and allow the exposure of more high index facets. The optimized Pt0.68 Cu0.18 Ru0.14 NFs exhibit outstanding electrocatalytic performances and excellent anti-poisoning abilities. The specific activities for the methanol oxidation reaction (MOR) (7.65 mA cm-2 ) and ethanol oxidation reaction (EOR) (7.90 mA cm-2 ) are 6.0 and 7.1 times higher than commercial Pt/C, respectively. The CO stripping experiment and the chronoamperometric (5000 s) demonstrate the superior anti-poisoning property and durability performance. Density functional theory calculations confirm that high metallization degree leads to the decrease of d-band center, the promotion of oxidation of CO, and improvement of the inherent activity and anti-poisoning ability. A Ru-rich edge exposes abundant high index facets to accelerate the reaction kinetics of rate-determining steps by decreasing the energy barrier for forming *HCOOH (MOR) and CC bond breaking (EOR).

A Highly Controlled Organic-Inorganic Encapsulation Nanocomposite with Versatile Features toward Wearable Device Applications.

Ultraviolet-curable polyurethane acrylate (PUA) materials can be used in a number of important applications spanning from microfluidics, surface patterning to wearable technology. For the first time, the potential of encapsulation of modified zirconia (ZrO2 ) nanoparticles is reported in PUA-based hybrid films aimed to facilitate profoundly enhanced hardness and refractive index. By successfully manipulating the interfacial reaction conditions between ZrO2 nanoparticles and PUA film, the PUA-based nanocomposites exhibit an ultrahigh hardness of 9 and superior refractive index of 1.64 (589.3 nm). The outcomes obtained pave the way for seamless application of nanozirconia/PUA as a potent encapsulating material that provides structurally morphable, water resistant, and optically transparent light emitting diodes toward wearables devices in healthcare.

Studies of bicalutamide-excipients interaction by combination of molecular docking and molecular dynamics simulation.

While the effects of hydrophilic excipients in enhancing the dissolution rate of water-insoluble drugs have been validated, the underlying mechanism remains poorly understood, particularly at a molecular level. In this work, a combination of docking calculations and MD simulations was applied to investigate the molecular interactions between bicalutamide (BIC) and each of three excipients: lactose (LAC), hydroxypropyl methylcellulose (HPMC), and mannitol (MAN). The calculated results indicated that BIC interacted with HPMC and MAN mainly by Lennard-Jones (LJ) interactions but with LAC mainly by Coulomb (Coul) interactions. There was no hydrogen bond formed between BIC and excipient. It was shown that BIC/LAC had the biggest total solvent accessible surface area with the biggest hydrophilic area and formed the most hydrogen bonds between excipient and water. In addition to the structure analyses, BIC/LAC had both the lowest interaction energy between BIC and excipient and the lowest interaction energy between BIC/excipient and water. All these led to the best dissolution performance of BIC/LAC, which could correspond to the experimental results of dissolution test. The present study suggests that a combination of docking calculations and MD simulations, which aims at complementing the experimental work, could provide a molecular insight into the interaction between drug and excipient. It also holds the great potential to simplify the optimization process of drug delivery system and reduce both time and costs.

Spray-drying-assisted fabrication of CaF2/SiO2 nanoclusters for dental restorative composites.

OBJECTIVE: The objective of this study is to develop novel CaF2/SiO2 nanoclusters (NCs) fillers, which can endow the dental resin composites (DRCs) with excellent mechanical properties, stable and sustained fluoride ion release, and good antibacterial activity. METHODS: The CaF2/SiO2 NCs were efficiently fabricated by assembling CaF2/SiO2 nanoparticles (NPs) as building blocks with a spray-drying technology. CaF2/SiO2 NCs with different SiO2 coating amounts (20 wt%, 50 wt% and 80 wt%) were incorporated into the DRCs at the filler content of 55 wt% for the measurement of mechanical properties including flexural strength, flexural modulus, compressive strength, and hardness. The effect of the filling amount of CaF2/50SiO2 NCs (50 represents 50 wt% SiO2 coating amount) in the DRCs was investigated, while CaF2/50SiO2 NPs were adopted as comparison group. The fluoride ion release and antibacterial activity of the DRCs with the optimal mechanical performances were evaluated. Furthermore, the statistical analyses were performed for mechanical properties. RESULTS: Spherical CaF2/50SiO2 NCs with an average size of 2.4 µm were obtained at the feed rate of 7.4 mL/min and the CaF2/50SiO2 NPs solid content of 2 wt% in the suspension. The optimum comprehensive performances of the DRCs can be achieved by filling 55 wt% CaF2/50SiO2 NCs. Compared with CaF2/50SiO2 NPs, the filling amount of CaF2/50SiO2 NCs was increased by 5 wt% (50-55 wt%), and under the same filling amount of 50 wt%, the flexural strength, flexural modulus, compressive strength, and hardness of the DRCs containing CaF2/50SiO2 NCs were improved by 9.8%, 17.7%, 7.5% and 69.8%, respectively. Furthermore, the DRCs filled with 50 wt% CaF2/50SiO2 NCs exhibited more cumulative F-release by 126% and more stable F-release rate than the counterpart filled with 50 wt% CaF2/50SiO2 NPs after immersed for 1800 h. And 55 wt% CaF2/50SiO2 NCs filled DRCs could inhibit the growth of S. mutans, reaching an antibacterial ratio of 93%. SIGNIFICANCE: The spray-dried CaF2/50SiO2 NCs are promising fillers for the development of high-performance multifunctional DRCs.

Mechanical behavior and reinforcement mechanism of nanoparticle cluster fillers in dental resin composites: Simulation and experimental study.

OBJECTIVES: In dental resin composites (DRCs), the structure of fillers has a great impact on the mechanical behavior. The purpose of this study is to gain an in-depth understanding of the reinforcement mechanism and mechanical behavior of DRCs with nanoparticle clusters (NCs) fillers, thereby providing a guidance for the optimal design of filler structures for DRCs. METHODS: This work pioneers the use of discrete element method (DEM) simulations combined with experiments to study the mechanical behavior and reinforcement mechanism of DRCs with NCs fillers. RESULTS: The uniaxial compressive strength (UCS) of NCs-reinforced DRCs have an improvement of 9.58 % and 15.02 % in comparison with nanoparticles (NPs) and microparticles (MPs), respectively, because of the ability of NCs to deflect cracks and absorb stress through gradual fracturing. By using NCs and NPs as co-fillers, the internal defects of DRCs can be reduced, resulting in a further improvement of UCS of DRCs by 6.21 %. Furthermore, the mechanical properties of DRCs can be effectively improved by increasing the strength of NCs or reducing the size of NCs. SIGNIFICANCE: This study deepens the understanding of relationship between filler structure and mechanical behavior in DRCs at the mesoscale and provides an avenue for the application of DEM simulations in composite materials.

Efficient prediction of the packing density of inorganic fillers in dental resin composites for excellent properties.

OBJECTIVE: The purpose of this study is to develop a mathematical model for efficient prediction of the packing density of different filler formulations in dental resin composites (DRCs), and to study properties of DRCs at the maximum filler loading (MFL), thereby providing an effective guidance for the design of filler formulations in DRCs to obtain excellent properties. METHODS: The packing density data generated by discrete element model (DEM) simulation were used to re-derive the parameters of 3-parameter model. The modifier effect was also induced to modify the 3-parameter model. DRCs with 10 filler formulations were selected to test properties at the MFL. The packing densities of binary and ternary mixes in DRCs were calculated by 3-parameter model to explore the regularity of composite packing. RESULTS: The predicted packing density was validated by simulation and experimental results, and the prediction error is within 1.40 vol%. The optimization of filler compositions to obtain a higher packing density is beneficial to enhancing the mechanical properties and reducing the polymerization shrinkage of DRCs. In binary mixes, the maximum packing density occurs when the volume fraction of small fillers is 0.35-0.45, and becomes higher with the reduction of particle size ratio. In ternary mixes, the packing density can reach the maximum value when the volume fractions of large and small fillers are in the 0.5-0.75 and 0.15-0.4 ranges, respectively. SIGNIFICANCE: The modified 3-parameter model can provide an effective method to design the multi-level filler formulations of DRCs, thereby improving the performance of the materials.

Antibacterial activity and reinforcing effect of SiO2-ZnO complex cluster fillers for dental resin composites.

The accumulation of bacteria at the margin of dental resin composites is the main reason for secondary caries, which may further cause failure of prosthodontics. Therefore, antibacterial activity is highly required. However, the addition of antibacterial agents or fillers weakens the mechanical or aesthetic properties of composites. In this work, regular-shaped SiO2-ZnO complex clusters (CCs) constructed by spray-drying technology can enhance the antibacterial activity while maintaining the mechanical and aesthetic properties of dental resin composites. The results show that the regular shape and closely packed structure of nanoparticle clusters were not corrupted by the introduction of ZnO particles. As compared to resin composites filled with SiO2 nanoparticle clusters, the comprehensive performances of composites containing SiO2-ZnO CCs were further improved, and the composites filled with 70 wt% Si66Zn4 (CCs composed of 66/70 SiO2 and 4/70 of ZnO) exhibited superior antibacterial capability (antibacterial ratio >99.9%) and acceptable depth of cure, degree of conversion, and biocompatibility. The cooperation of different fillers is highly essential for resin composites to achieve enhanced multifunctional performance.

A new method for predicting the maximum filler loading of dental resin composites based on DEM simulations and experiments.

OBJECTIVE: The inorganic fillers in dental resin composites can enhance their mechanical properties and reduce polymerization shrinkage. When the usage amount of inorganic fillers is closed to maximum filler loading (MFL), the composites will usually achieve optimal performances. This study aims to develop a method that can predict the MFL of dental resin composites for the optimization of filler formulations. METHODS: A method based on discrete element method (DEM) simulations and experiments was firstly developed to predict the MFL of spherical silica particles for single-level and multi-level filling. RESULTS: The results indicate that the presence of modifier can increase the MFL, and the MFL increment can be exponentially changed with the content of the modifier. Compared with the single-level filling, the addition of secondary fillers is beneficial to increase the MFL, and the increment can be affected by the particle size and size ratio. The prediction results show a good agreement with the experiment results. SIGNIFICANCE: The accuracy of prediction results indicates a great potential of DEM simulations as a numerical experimental method in studying the MFL, and provides an effective method for the optimization of filler formulations.

Cellulose derived nitrogen and phosphorus co-doped carbon-based catalysts for catalytic reduction of p-nitrophenol.

The cellulose, which is one of the most abundant solid by-products of agriculture and forestry industry, has been successfully tested for the synthesis of nitrogen and phosphorus co-doped carbon-based metal-free catalysts (NPC) via freeze-drying the mixture of cellulose crystallite and ammonium phosphate, followed by annealing of the hydrogel under nitrogen atmosphere at 800 °C for 2 h. Different techniques including TEM, SEM, FTIR and XPS spectroscopy have been applied to characterize the as-prepared NPC, which presents flake-like morphology with N and P doping levels of 4.3 atom% and 10.66 atom%, respectively. The NPC exhibits excellent catalytic activity for the reduction of p-nitrophenol (p-NP). The turnover frequency (TOF) of the reduction of p-NP is as high as 2 × 10-5 mmol·mg-1·min-1 and the apparent kinetic rate constant was calculated as 0.0394 min-1 at room temperature. The catalytic mechanism is proposed by combining the density functional theory calculation and analysis of the experimental results. These findings open up new possibilities of valorization for cellulose-based by-product and treatment of p-NP-based wastewater.

Preparation and characterization of porous hollow silica nanoparticles for drug delivery application.

Porous hollow silica nanoparticles (PHSNP) with a diameter of 60-70 nm and wall thickness of approximately 10nm were synthesized by using CaCO(3) nano-particles as the inorganic template. The characterization of PHSNP by TEM and BET indicated that PHSNP were uniform spherical particles with good dispersion, and had a specific surface area of 867 m(2)/g. The as-synthesized PHSNP were subsequently employed as drug carrier to investigate in vitro release behavior of cefradine in simulated body fluid. UV-spectrometry and TG analyses were performed to determine the amount of cefradine entrapped in the carrier. The BJH pore size distribution of PHSNP before and after entrapping cefradine was examined. Cefradine release profile from PHSNP followed a three-stage pattern and exhibited a delayed release effect.

Micronization of atorvastatin calcium by antisolvent precipitation process.

Amorphous atorvastatin calcium (AC) ultrafine powder has been successfully prepared by antisolvent precipitation and spray drying process, in which hydroxypropyl methylcellulose (HPMC) was employed to control the particle size and morphology. The effects of experimental parameters, such as stirring time, drug concentration and drying methods, on particle size and morphology were investigated. The average particle size of AC obviously increased from 410 nm to 1200 nm as the stirring time changed from 30s to 60 min. The enhancement of drug concentration favored to decrease the particle size from 410 nm to 240 nm. After spray drying process, ultrafine AC powder was obtained, which had good dispersibility and narrow particle size distribution of 1-3 microm. The as-prepared ultrafine AC was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TG), differential scanning calorimetry (DSC), specific surface area and dissolution test. The XRD analyses indicated that the ultrafine AC was amorphous. In the dissolution tests, the amorphous AC ultrafine powder exhibited enhanced dissolution property when compared to the raw material.