Developments in Atomistic and Nano Structure Evolution Mechanisms of Molten Slag Using Atomistic Simulation Methods.

Molten slag has different properties depending on its composition. The relationship between its composition, structure, and properties has been the focus of attention in industrial manufacturing processes. This review describes the atomistic scale mechanisms by which oxides of different compositions affect the properties and structure of slag, and depicts the current state of research in the atomic simulation of molten slag. At present, the research on the macroscopic properties of molten slag mainly focuses on viscosity, free-running temperature, melting point, and desulphurization capacity. Regulating the composition has become the most direct and effective way to control slag properties. Analysis of the microevolution mechanism is the fundamental way to grasp the macroscopic properties. The microstructural evolution mechanism, especially at the atomic and nanoscale of molten slag, is reviewed from three aspects: basic oxides, acidic oxides, and amphoteric oxides. The evolution of macroscopic properties is analyzed in depth through the evolution of the atomic structure. Resolution of the macroscopic properties of molten slag by the atomic structure plays a crucial role in the development of fundamental theories of physicochemistry.

Revelation of adhesive proteins affecting cellular contractility through reference-free traction force microscopy.

Over the past few decades, the critical role played by cellular contractility associated mechanotransduction in the regulation of cell functions has been revealed. In this case, numerous biomaterials have been chemically or structurally designed to manipulate cell behaviors through the regulation of cellular contractility. In particular, adhesive proteins including fibronectin, poly-L-lysine and collagen type I have been widely applied in various biomaterials to improve cell adhesion. Therefore, clarifying the effects of adhesive proteins on cellular contractility has been valuable for the development of biomaterial design. In this study, reference-free traction force microscopy with a well-organized microdot array was designed and prepared to investigate the relationship between adhesive proteins, cellular contractility, and mechanotransduction. The results showed that fibronectin and collagen type I were able to promote the assembly of focal adhesions and further enhance cellular contraction and YAP activity. In contrast, although poly-L-lysine supported cell spreading and elongation, it was inefficient at inducing cell contractility and activating YAP. Additionally, compared with cellular morphogenesis, cellular contraction was essential for YAP activation.

Copious Dislocations Defect in Amorphous/Crystalline/Amorphous Sandwiched Structure P-NiMoO4 Electrocatalyst toward Enhanced Hydrogen Evolution Reaction.

The design and synthesis of efficient, inexpensive, and long-term stable heterostructured electrocatalysts with high-density dislocations for hydrogen evolution reaction in alkaline media and seawater are still a great challenge. An amorphous/crystalline/amorphous sandwiched structure with abundant dislocations were synthesized through thermal phosphidation strategies. The dislocations play an important role in the hydrogen evolution reactions. Copious dislocation defects, combined with cracks, and the synergistic interfacial effect between crystalline phase and amorphous phase regulate the electronic structure of electrocatalyst, provide more active sites, and thus endow the electrocatalysts with excellent catalytic activity under alkaline water and seawater. The overpotentials of P-NiMoO4 at 10 mA/cm2 in 1 M KOH aqueous solution and seawater are 45 and 75 mV, respectively. Additionally, the P-NiMoO4 electrocatalyst exhibits long-term stability over 100 h. This study provides a simple approach for synthesizing amorphous/crystalline/amorphous sandwiched non-noble-metal electrocatalysts with abundant dislocations for hydrogen evolution reaction.

Artificial Optoelectronic Synapse Based on Violet Phosphorus Microfiber Arrays.

Memristor-based artificial synapses are regarded as the most promising candidate to develop brain-like neuromorphic network computers and overcome the bottleneck of Von-Neumann architecture. Violet phosphorus (VP) as a new allotrope of available phosphorus with outstanding electro-optical properties and stability has attracted more and more attention in the past several years. In this study, large-scale, high-yield VP microfiber vertical arrays have been successfully developed on a Sn-coated graphite paper and are used as the memristor functional layers to build reliable, low-power artificial synaptic devices. The VP devices can well mimic the major synaptic functions such as short-term memory (STM), long-term memory (LTM), paired-pulse facilitation (PPF), spike timing-dependent plasticity (STDP), and spike rate-dependent plasticity (SRDP) under both electrical and light stimulation conditions, even the dendritic synapse functions and simple logical operations. By virtue of the excellent performance, the VP artificial synapse devices can be conductive to building high-performance optic-neural synaptic devices simulating the human-like optic nerve system. On this basis, Pavlov's associative memory can be successfully implemented optically. This study provides a promising approach for the design and manufacture of VP-based artificial synaptic devices and outlines a direction with multifunctional neural devices.

Effects of Thermal-Strain-Induced Atomic Intermixing on the Interfacial and Photoluminescence Properties of InGaAs/AlGaAs Multiple Quantum Wells.

Quantum-well intermixing (QWI) technology is commonly considered as an effective methodology to tune the post-growth bandgap energy of semiconductor composites for electronic applications in diode lasers and photonic integrated devices. However, the specific influencing mechanism of the interfacial strain introduced by the dielectric-layer-modulated multiple quantum well (MQW) structures on the photoluminescence (PL) property and interfacial quality still remains unclear. Therefore, in the present study, different thicknesses of SiO2-layer samples were coated and then annealed under high temperature to introduce interfacial strain and enhance atomic interdiffusion at the barrier-well interfaces. Based on the optical and microstructural experimental test results, it was found that the SiO2 capping thickness played a positive role in driving the blueshift of the PL peak, leading to a widely tunable PL emission for post-growth MQWs. After annealing, the blueshift in the InGaAs/AlGaAs MQW structures was found to increase with increased thickness of the SiO2 layer, and the largest blueshift of 30 eV was obtained in the sample covered with a 600 nm thick SiO2 layer that was annealed at 850 °C for 180 s. Additionally, significant well-width fluctuations were observed at the MQW interface after intermixing, due to the interfacial strain introduced by the thermal mismatch between SiO2 and GaAs, which enhanced the inhomogeneous diffusion rate of interfacial atoms. Thus, it can be demonstrated that the introduction of appropriate interfacial strain in the QWI process is of great significance for the regulation of MQW band structure as well as the control of interfacial quality.

Evaluative effectiveness of follicular output rate, ovarian sensitivity index, and ovarian response prediction index for the ovarian reserve and response of low-prognosis patients according to the POSEIDON criteria: a retrospective study.

The aim was to explore the implications of follicular output rate (FORT), ovarian sensitivity index (OSI), ovarian response prediction index (ORPI), and follicle-to-oocyte index (FOI) in low-prognosis patients defined by POSEIDON criteria. In total, 4030 fresh in vitro fertilization (IVF) cycles from January 2013 to October 2021 were included in this retrospective cohort analysis and were categorized into four groups based on the POSEIDON criteria. The FORT between Groups 1 and 2 (0.61 ± 0.34 vs. 0.65 ± 0.35, P = 0.081) and Groups 3 and 4 (1.08 ± 0.82 vs. 1.09 ± 0.94, P = 0.899) were similar. The OSI in the order from the highest to the lowest were 3.01 ± 1.46 in Group 1, 2.28 ± 1.09 in Group 2, 1.54 ± 1.04 in Group 3, and 1.34 ± 0.96 in Group 4 (P < 0.001). The trend in the ORPI values was consistent with that in the OSI. FORT, OSI, ORPI, and FOI complemented each other and offered excellent effectiveness in reflecting ovarian reserve and response, but they were not good predictors of clinical pregnancy rate (CPR) from IVF.

Atomic-scale insights into the interfacial charge transfer in a NiO/CeO2 heterostructure for electrocatalytic hydrogen evolution.

To understand the underlying mechanism of the interfacial charge transfer and local chemical state variation in the nonprecious-based hydrogen evolution reaction (HER) electrocatalysts, a model system of the NiO/CeO2 heterostructure was chosen for investigation using a combination of the advanced electron microscopic characterization and first-principles calculations. The results directly proved that interfacial charge transfer occurs from Ni to Ce, leading to reduction in the valence state of Ce and increased formation of VO. This would optimize ΔGH* and facilitate the hydrogen evolution process, resulting in outstanding HER performance in 1 M KOH with a low overpotential of 99 mV at the current density of 10 mA•cm-2 and a modest Tafel slope of 78.4 mV•dec-1 for the NiO/CeO2 heterostructure sample. Therefore, the improved HER performance could be attributed to the synergistic coupling interactions and electron redistribution at the interface of NiO and CeO2. These results concretely demonstrate the direct determination of the interfacial structure of the heterostructure and provide atomistic insights to unravel the underlying mechanism of interfacial charge transfer induced HER performance improvement.

Polyoxometalate-Viologen Thermochromic Hybrids for Organic Amine Detectors and Memristors with Temperature-Regulating Resistance Switching Characteristics.

There are relatively few reports on the combination of viologen and polyoxometalates (POMs). Herein, we successfully synthesized three viologen-POM-based compounds by in situ transformation of ligands under hydrothermal conditions, namely, {MII(1,4-cby)2[H2(γ-Mo8O26)]}·nH2O (1: M = Ni, n = 4; 2: M = Co, n = 6), and [NiII(1,3-cby)(H2O)4(ß-Mo8O26)0.5]·2H2O (3) (1,4-cby·Cl = 1-(4-carboxy-benzyl)-[4,4']bipyridinyl-1-ium, 1,3-cby·Cl = 1-(3-carboxy-benzyl)-[4,4']bipyridinyl-1-ium). Isostructural compounds 1 and 2 exhibit two-dimensional (2D) layer structures with POMs as linking nodes, while compound 3 shows a one-dimensional (1D) metal-organic chain with dissociative POM anions. When the temperature increases, compounds 1-3 show good reversible thermochromism properties and also have a fluorescence quenching effect. Moreover, compounds 1-3 can also be used as detectors for organic amines, especially in the atmosphere of ammonia, ethylenediamine, and diethylamine with an obvious discoloration effect. In addition, compound 1 was used as a material for the preparation of memristors with superior properties (distinct temperature-adjusted resistive switching properties). It shows bipolar resistive switching (RS) behavior at different temperatures of 20, 50, and 100 °C. The results show that the 1-based memristor has good thermal stability, which is important for high-temperature environment applications. It also shows that crystalline viologen-POM-based compounds are ideal candidates for making memristors.

Synthesis of Fibrous Phosphorus Micropillar Arrays with Pyro-Phototronic Effects.

The bottom-up preparation of two-dimensional material micro-nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.[1] However, to date, there are no bottom-up micro-nano structure preparation methods for crystalline phosphorus allotropes.[1c, 2] Herein, we present the bottom-up preparation of fibrous phosphorus micropillar (FP-MP) arrays via a low-pressure gas-phase transport (LP-CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self-powered photodetectors (PD) of FP-MP arrays with pyro-phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom-up preparation of other crystalline allotropes of phosphorus.

Mixed-Dimensional van der Waals Heterostructure for High-Performance and Air-Stable Perovskite Nanowire Photodetectors.

An organic-inorganic hybrid perovskite nanowire (NW), CH3NH3PbI3, shows great potential for high-performance photodetectors due to its excellent photoresponse. However, the inefficient carrier collection between the one-dimensional (1D) NWs and metallic electrodes, as well as degradation of the perovskite, limits the viability of the CH3NH3PbI3 NWs for commercial production. Here, we demonstrate a photodetector with a mixed-dimensional van der Waals heterostructure of hexagonal boron nitride (hBN)/graphene (Gr)/1D CH3NH3PbI3, which exhibits excellent responsivity and specific detectivity of up to 558 A/W and 2.3 × 1012 Jones, owing to the improved carrier extraction at the electrical contact between Gr and the NW. As for the atomic encapsulation of hBN, the device is extremely robust and maintains its outstanding performance for more than 2 months when exposed to air. Moreover, benefitting from the 1D geometry of the CH3NH3PbI3 NW, our device is highly sensitive to polarized light. The mixed-dimensional van der Waals heterostructure, hBN/Gr/1D CH3NH3PbI3, would provide a novel idea and protocol for fabricating high-performance and air-stable photoelectronic devices based on organic-inorganic hybrid perovskite NWs.

Atomic-Scale Insights into the Interfacial Polarization Effect in the InGaN/GaN Heterostructure for Solar Cells.

The model system of the InGaN/GaN quantum wells (QWs), based on the first principles calculation, was chosen to understand the underlying mechanism of interfacial polarization and its synergic effect with the built-in electric field (Bef) at the p-n junction in solar cells (SLs). The polarized electric field (Pef) was generated due to the redistribution of electrons and holes at the interface; moreover, the Pef of InGaN/GaN heterostructure on the semipolar (01-11) GaN surface was consistent with that of on the N-polar (000-1) surface, which is on the lines of the Bef and favors the electron-hole separation efficiency in SLs. Furthermore, the growth of high-quality InGaN/GaN QWs on the semipolar (01-11) GaN surface was achieved. Such an atomic-scale investigation provides a fundamental understanding of the polarization charge-induced Pef and its interaction coupling with Bef at the p-n junction, which could be generalized to polar material-based SLs.

Mid-infrared photoluminescence revealing internal quantum efficiency enhancement of type-I and type-II InAs core/shell nanowires.

Internal quantum efficiency (IQE) is an important figure of merit for photoelectric applications. While the InAs core/shell (c/s) nanowire (NW) is a promising solution for efficient quantum emission, the relationship between the IQE and shell coating remains unclear. This Letter reports mid-infrared PL measurements on InAs/InGaAs, InAs/AlSb, and InAs/GaSb c/s NWs, together with bare InAs NWs as a reference. Analyses show that the IQE is depressed by a shell coating at 9 K but gets improved by up to approximately 50% for the InGaAs shell coating at 40 -140 K and up to approximately 20% beyond 110 K for the AlSb shell. The effect is ascribed not only to the crystal quality but more importantly to the radial band alignment. The result indicates the high-temperature IQE improvement of the type-I and type-II c/s NWs and the appropriateness of the mid-infrared PL analyses for narrow-gap NW evaluation.

New Insights into the Traditional Charge Compensation Theory: Amphoteric Behavior of TiO2 under the Guidance of Supply-Demand Relationship.

Polymerization degree theory and traditional charge compensation theory are the most fundamental principles to understand the structure and properties of oxide melts. It can well explain the behavior characteristics of acidic oxides and basic oxides in a melt. However, the amphoteric behavior of oxides cannot be explained well by these two theories. Herein, the octahedral connection mode and the behavior of the amphoteric transition of TiO2 are analyzed by molecular dynamics simulation, and then, a calculation model which can quantitatively calculate the amphoteric transition of the oxide is established by analyzing a large number of data. On the basis of the model, a novel theory of supply and demand is put forward, which can explain the amphoteric transition behavior of oxides very well. To a great extent, the supply and demand theory makes up for the deficiency of the atomic structure theory of oxide melts and provides mechanism explanation and model prediction for the oxide amphoteric transformation behavior.

Electrochemical Performance of Graphene Oxide/Black Arsenic Phosphorus/Carbon Nanotubes as Anode Material for LIBs.

As a new two-dimensional material, black arsenic phosphorus (B-AsP) has emerged as a promising electrode for lithium-ion batteries (LIBs) due to its large theoretical capacity and ability to absorb large amounts of Li atoms. However, the poor electronic conductivity and large volume expansion during the lithiation/delithiation process have largely impeded the development of B-AsP electrodes. In this study, graphene oxide (GO)/B-AsP/carbon nanotubes (CNTs) with remarkable lithium-storage property were fabricated via CVD and ultrasound-assisted method. The electrochemical behavior of the GO/B-AsP/CNTs was investigated as an anode in lithium-ion batteries. From the results, as a new-type anode for LIBs, GO/B-AsP/CNTs composite demonstrated a stable capacity of 1286 and 339 mA h g-1 at the current density of 0.1 and 1 A g-1, respectively. The capacity of GO/B-AsP/CNTs was 693 mA h g-1 after 50 cycles, resulting in capacity retention of almost 86%. In addition, the stable P-C and As-C bonds were formed between B-AsP, GO, and CNTs. Thus, volume expansion of B-AsP was alleviated and the capacity was increased due to the confining effect of GO and CNTs.

Influence of Colonies' Morphological Cues on Cellular Uptake Capacity of Nanoparticles.

High transmembrane delivery efficiency of nanoparticles has attracted substantial interest for biomedical applications. It has been proved that the desired physicochemical properties of nanoparticles were efficient for obtaining a high cellular uptake capacity. On the other hand, biophysical stimuli from in situ microenvironment were also indicated as another essential factor in the regulation of cellular uptake capacity. Unfortunately, the influence of colony morphology on cellular uptake capacity was rarely analyzed. In this study, micropatterned PDMS stencils containing circular holes of 800/1,200 µm in diameter were applied to control colonies' size. The amino-modified nanoparticles were cocultured with micropatterned colonies to analyze the influence of colonies' morphology on the cellular uptake capacity of nanoparticles. Consequently, more endocytosed nanoparticles in larger colonies were related with a bigger dose of nanoparticles within a larger area. Additionally, the high cell density decreased the membrane-nanoparticles' contacting probability but enhanced clathrin-mediated endocytosis. With these contrary effects, the cells with medium cell density or located in the peripheral region of the micropatterned colonies showed a higher cellular uptake capacity of nanoparticles.

Mid-infrared photoluminescence revealing internal quantum efficiency enhancement of type-I and type-II InAs core/shell nanowires: publisher's note.

This publisher's note contains corrections to Opt. Lett.47, 5208 (2022)10.1364/OL.473154.

FeNi2P three-dimensional oriented nanosheet array bifunctional catalysts with better full water splitting performance than the full noble metal catalysts.

The 3D (three-dimensional) oriented nanosheet array FeNi2P electrocatalyst grown on carbon cloth (FeNi2P/CC) is explored in this work. This unique 3D oriented nanosheet array structure can expose more catalytic active sites, promote the penetration of electrolyte solution on the catalyst surface, and facilitate the transfer of ions, thus speeding up the kinetic process of Hydrogen evolution reaction (HER) and Oxygen evolution reaction (OER). At the current densities of 10 mA/cm2 in 1 M KOH solution, the HER overpotential (71 mV) of the FeNi2P/CC self-supporting electrode is very close to that of noble metal HER catalyst of 20% Pt/C (54 mV), and its OER overpotential (210 mV) is 34% lower than that of the precious metal OER catalyst of RuO2 (318 mV), demonstrating the excellent electrocatalytic performance of the FeNi2P/CC catalyst. Moreover, the cell voltage for full water splitting (at 10 mA/cm2 current densities) of the FeNi2P/CC bifunctional electrode cell is 1.52 V, which is 3.8% lower than that of the full noble-metal electrode reference cell (RuO2 || Pt/C, 1.58 V), suggesting that this FeNi2P/CC bifunctional catalyst is likely to replace precious metals to reduce the costs in full water splitting application. According to density functional theory (DFT) calculation results, the introduction of iron atom can change the electronic structure of the Ni2P, so it can reduce the adsorption energy of hydrogen and oxygen, and facilitate the adsorption and desorption of hydrogen and oxygen on the surface of the catalyst, improving its performance of HER and OER.

Controllable preparation of crystalline red phosphorus and its photocatalytic properties.

Single-element phosphorus has received extensive attention in recent years because of its remarkable photocatalytic properties. In the present experiment, amorphous red phosphorus was controllably transformed into [P12(4)]P2[and Hittorf's phosphorus structures by performing bismuth catalysis. The temperature-controllable chemical vapor transport reaction realized the conversion of more than 90% of amorphous red phosphorus to single-phase crystalline red phosphorus. Under very mild ultrasonic treatment, the high-quality [P12(4)]P2[microbelts and Hittorf's phosphorus microrods were stripped into a few layers of nanobelts and sheet-like structures, respectively. As non-metallic catalysts, their rapid photocatalytic degradations of pollutants (methyl orange) and high hydrogen evolution rates revealed the rapid charge transfer and application potential of the crystalline red phosphorus catalyst. The results of this work could provide new ideas for the development of phosphorus-based crystalline photocatalytic systems.

The pro-inflammatory response of macrophages regulated by acid degradation products of poly(lactide-co-glycolide) nanoparticles.

Poly(lactide-co-glycolide) (PLGA) shows great potentials in biomedical applications, in particular with the field of biodegradable implants and control release technologies. However, there are few systematic and detailed studies on the influence of PLGA degradation behavior on the immunogenicity. In this study, in order to develop a method for dynamically assessing the immunological response of PLGA throughout the implantation process, PLGA particles are fabricated using an o/w single-emulsion method. The physicochemical characterizations of the prepared PLGA particles during in vitro hydrolytic degradation are investigated. Then, a series of immunological effects triggered by PLGA by-products formed with degradation process are evaluated, including cell viability, apoptosis, polarization and inflammatory reaction. THP-1 human cell line is set as in vitro cell model. Our results show that PLGA degradation-induced acid environment decreases cell viability and increases cell apoptosis, which is a potential factor affecting cell function. In particular, the macrophages exhibit up-regulations in both M1 subtype related surface markers and pro-inflammatory cytokines with the degradation process of PLGA, which indicates the degradation products of PLGA can convert macrophages to the pro-inflammatory (M1) polarization state. All these findings provide the mechanism of PLGA-induced inflammation and lay the foundation for the design of next-generation PLGA-based biomaterials endowed with immunomodulatory functions.

Surfactant-mediated morphology evolution and self-assembly of cerium oxide nanocrystals for catalytic and supercapacitor applications.

Surfactant plays a remarkable role in determining the growth process (facet exposition) of colloidal nanocrystals (NCs) and the formation of self-assembled NC superstructures, the underlying mechanism of which, however, still requires elucidation. In this work, the mechanism of surfactant-mediated morphology evolution and self-assembly of CeO2 nanocrystals is elucidated by exploring the effect that surfactant modification has on the shape, size, exposed facets, and arrangement of the CeO2 NCs. It is directly proved that surfactant molecules determine the morphologies of the CeO2 NCs by preferentially bonding onto Ce-terminated {100} facets, changing from large truncated octahedra (mostly {111} and {100} exposed), to cubes (mostly {100} exposed) and small cuboctahedra (mostly {100} and {111} exposed) by increasing the amount of surfactant. The exposure degree of the {100} facets largely affects the concentration of Ce3+ in the CeO2 NCs, thus the cubic CeO2 NCs exhibit superior oxygen storage capacity and excellent supercapacitor performance due to a high fraction of exposed active {100} facets with great superstructure stability.