Integrated influence of sulfide modification on the reactivity of nanoscale zero-valent iron towards decabromodiphenyl ether under an electromagnetic field.

Individual application of sulfide modification and electromagnetic field (EMF) can enhance the reactivity of nanoscale zero-valent iron (nZVI), yet the potential of both in combination is not clear. This work found that the reactivity of nZVI towards decabromodiphenyl ether was significantly enhanced by the combined effect of sulfidation and EMF. The specific reaction rate constant of nZVI increased by 7 to 10 times. A series of characterization results revealed that the sulfidation level not only affects the inherent reactivity but also the magnetic-induced heating (MIH) and corrosion (MIC) of nZVI. These collectively influence the degradation efficiency of nZVI under EMF. Sulfidation generally diminished the MIH effect. The low degree of sulfidation (S/Fe = 0.1) slightly reduced the MIC effect by 21.4%. However, the high degree of sulfidation (S/Fe = 0.4) led to significantly enhanced MIC effect by 107.1%. For S/Fe = 0.1 and 0.4, the overall enhancement in the reactivity resulting from EMF was alternately dominated by the contributions of MIH and MIC. This work provides valuable insights into the MIH and MIC effects about the sulfidation level of nZVI, which is needed for further exploration and optimization of this combined technology.

Effects of isotropic strain on the structure and transport properties of half-Heusler alloy BiBaK: a first-principles investigation.

In this study, using density functional and Boltzmann transport theories, we systematically investigated the effects of tensile and compressive strains on the elastic properties, phonon dispersion relation, electronic structure, and transport properties of the half-Heusler compound BiBaK. We calculated the elastic constants and phonon dispersion curves for BiBaK, which demonstrated its mechanical and thermodynamic stability, respectively, under different isotropic strains. Further, calculations showed that the electronic structure and energy bandgap of BiBaK changed with the application of isotropic strain. A high power factor and low thermal conductivity are key to improving the performance of thermoelectric materials. The figure of merit of BiBaK is 0.6 when it is unstrained and reaches a maximum value of 0.93 at -9% compressive strain and a temperature of 1200 K, indicating that under isotropic compressive strain, BiBaK compounds are efficient thermoelectric materials for high-temperature applications.

Fabrication of porous polyimide as cathode for high performance lithium-ion battery.

Herein, we report the preparation of porous polyimide (PI) with a cost-effective synthesis process by polycondensation between melamine and dianhydride monomers. The prepared porous PI served as a cathode for lithium-ion batteries (LIBs), and delivers a high discharge platform of 2.1 V and satisfactory electrochemical performance. Thus, the porous PI cathode provides another choice for LIBs.

Exploring structural, mechanical, and thermoelectric properties of half-Heusler compounds RhBiX (X = Ti, Zr, Hf): A first-principles investigation.

In this study, the full potential linearization enhanced plane wave method in density functional theory is used. Additionally, the structure, mechanical, and thermoelectric properties of half-Heusler compounds RhBiX (X = Ti, Zr, Hf) are investigated for the first time. The indirect semiconductors RhBiTi and RhBiZr have 0.89 and 1.06 eV bandgap energies, respectively. In contrast, RhBiHf is a direct bandgap semiconductor with a bandgap energy of 0.33 eV. The thermoelectric parameters such as Seebeck coefficient, power factor, electronic conductivity, lattice thermal conductivity, electronic thermal conductivity, and figure of merit ZT, are studied with the semi-classical Boltzmann transport theory. When T = 300 K, RhBiTi, RhBiZr, and RhBiHf show small lattice thermal conductivities, i.e., 10.60, 10.15, and 7.71 W mK-1, respectively, which are consistent with related other studies. The maximum ZT values of RhBiTi, RhBiZr, and RhBiXHf are 0.91, 0.94, and 0.79 at 900 K, respectively. Furthermore, we observed that RhBiX (X = Ti, Zr, Hf) alloy is a thermoelectric material with great potential.

Changes in hip joint contact stress during a gait cycle based on the individualized modeling method of "gait-musculoskeletal system-finite element".

OBJECTIVE: To construct a comprehensive simulation method of "gait-musculoskeletal system (MS)-finite element (FE)" for analysis of hip joint dynamics characteristics and the changes in the contact stress in the hip throughout a gait cycle. METHODS: Two healthy volunteers (male and female) were recruited. The 3D gait trajectories during normal walking and the CT images including the hip and femur of the volunteers were obtained. CT imaging data in the DICOM format were extracted for subjected 3D hip joint reconstruction. The reconstructed 3D model files were used to realize the subject-specific registration of the pelvis and thigh segment of general musculoskeletal model. The captured marker trajectory data were used to drive subject-specific musculoskeletal model to complete inverse dynamic analysis. Results of inverse dynamic analysis were exported and applied as boundary and load settings of the hip joint finite element in ABAQUS. Finally, the finite element analysis (FEA) was performed to analyze contact stress of hip joint during a gait cycle of left foot. RESULTS: In the inverse dynamic analysis, the dynamic changes of the main hip-femoral muscle force with respect to each phase of a single gait cycle were plotted. The hip joint reaction force reached a maximum value of 2.9%BW (body weight) and appeared at the end of the terminal stance phase. Twin peaks appeared at the initial contact phase and the end of the terminal stance phase, respectively. FEA showed the temporal changes in contact stress in the acetabulum. In the visual stress cloud chart, the acetabular contact stress was mainly distributed in the dome of the acetabulum and in the anterolateral area at the top of the femoral head during a single gait cycle. The acetabular contact area was between 293.8 and 998.4 mm2, and the maximum contact area appear at the mid-stance phase or the loading response phase of gait. The maximum contact stress of the acetabulum reached 6.91 MPa for the model 1 and 6.92 MPa for the model 2 at the terminal stance phase. CONCLUSIONS: The "Gait-MS-FE" technology is integrated to construct a comprehensive simulation framework. Based on human gait trajectories and their CT images, individualized simulation modeling can be achieved. Subject-specific gait in combination with an inverse dynamic analysis of the MS provides pre-processing parameters for FE simulation for more accurate biomechanical analysis of hip joint.

First-principles study of pressure-induced phase transitions, mechanical and thermodynamic properties of ThBC.

First-principles calculations and particle swarm optimization algorithm are combined to predict the crystal structures in the pressure range from 0 to 100 GPa. Four phases of ThBC are determined, including theP4122,Cmcm,CmceandImmmphases, in which theCmcm,CmceandImmmphases are newly predicted structures. The mechanical, electronic and thermodynamic properties of the four phases are investigated. According to the enthalpy-pressure and volume-pressure curves, the phase transition pressure from theP4122 phase to theCmcmphase is 15 GPa, theCmcmto theCmceis 36 GPa and theCmceto theImmmis 69 GPa. All the transitions belong to the first-order phase transition. Based on the calculated elastic constants, theP4122,Cmcm,CmceandImmmphases exhibit brittle nature. The Young's moduli show that theP4122 phase has the largest degree of anisotropy, and theImmmphase has the smallest. The calculated density of states reveal that theP4122,Cmcm,CmceandImmmphases are all metallic.

Computational Screening of 3 d Transition Metal Atoms Anchored on Defective Graphene for Efficient Electrocatalytic N2 Fixation.

The synthesis of ammonia (NH3 ) through the electrochemical reduction of molecular nitrogen (N2 ) is a promising strategy for significantly reducing energy consumption compared to traditional industrial processes. Herein, we report the design of a series of monovacancy and divacancy defective graphenes decorated with single 3d transition metal atoms (TM@MVG and TM@DVG; TM=Sc-Zn) as electrocatalysts for the nitrogen-reduction reaction (NRR) aided by density functional theory (DFT) calculations. By comparing energies for N2 adsorption as well as the free energies associated with *N2 activation and *N2 H formation, we successfully identified V@MVG, with the lowest potential of -0.63 V, to be an effective catalytic substrate for the NRR in an enzymatic mechanism. Electronic properties, including Bader charges, charge density differences, partial densities of states, and crystal orbital Hamilton populations, are further analyzed in detail. We believe that these results help to explain recent observations in this field and provide guidance for the exploration of efficient electrocatalysts for the NRR.

Density functional theory study of transition metal single-atoms anchored on graphyne as efficient electrocatalysts for the nitrogen reduction reaction.

Ammonia (NH3) is the main raw material for the organic chemical industry and a critical feedstock for the fertilizer industry with great significance for the global economy. The NH3 demand has gradually increased with modern society development. Moreover, the electrocatalytic nitrogen reduction reaction (NRR) is a promising NH3 synthesis technology. However, the design of efficient electrocatalysts for the NRR is still challenging. In this study, we systematically analyzed transition metal (TM) single-atoms (Ti, V, Cr, Mn, Zr, Nb, and Mo) anchored on graphyne (GY) as NRR catalysts using density functional theory calculations. The calculation results for the first and last hydrogenation steps (*NNH formation and *NH3 desorption, respectively) revealed that Mn@GY (with an end-on configuration) and V@GY (with a side-on configuration) were the most suitable catalytic substrates for the NRR. The free-energy profiles of the TM@GY catalysts indicated that Mn@GY was the best NRR electrocatalyst owing to its distal pathway with a minimum free-energy barrier of 0.36 eV. In addition, the electronic properties, namely the Bader charge, charge density difference, partial density of states, and crystal orbital Hamilton population, of the TM@GY catalysts were analyzed in detail, and the results further confirmed that Mn@GY was an efficient electrocatalyst. The insights obtained from this comprehensive study can provide useful guidelines for designing new and efficient electrocatalysts.

Long noncoding RNA UCA1 promotes osteosarcoma metastasis through CREB1-mediated epithelial-mesenchymal transition and activating PI3K/AKT/mTOR pathway.

Increasing evidences have demonstrated that Long noncoding RNAs (lncRNAs) are key regulatory RNAs that participate in multiple biological processes. LncRNA urothelial carcinoma-associated 1 (UCA1) is a newly identified lncRNA and functions as a regulator of growth in several cancers. However, the biological function and molecular mechanism of UCA1 in the metastasis of osteosarcoma remain unclear. In this study, we firstly found UCA1 is upregulated in both osteosarcoma tissues and cell lines, and increased UCA1 is associated with higher tumor stage, larger tumor size and poorer prognosis. Then for the first time, we demonstrated that UCA1 promotes the invasion and metastasis of osteosarcoma both in vitro and in vivo. Further mechanistic investigation showed that UCA1 directly interactes with miR-582 and suppresses its expression. Moreover, UCA1 increases CREB1 expression by functioning as a ceRNA against miR-582, thus promoting the EMT process via CREB1-mediated PI3K/AKT/mTOR pathway and finally leading to osteosarcoma metastasis. These findings may extend the function of UCA1 in osteosarcoma progression and provide a promising therapeutic target for osteosarcoma treatment.

Enhanced His@AuNCs oxidase-like activity by reduced graphene oxide and its application for colorimetric and electrochemical detection of nitrite.

Enzyme-mimicking (nanozyme)-based biosensors are attractive owing to their unique catalytic efficiency, multifunctionality, and tunable activity, but examples of oxidase-like nanozymes are quite rare. Herein, we demonstrated that histidine-capped gold nanoclusters (His@AuNCs) possessed intrinsic oxidase-like activity, which could directly oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to blue colored ox-TMB without H2O2. The assembly of reduced graphene oxide (RGO) with His@AuNCs could further improve its oxidase-like activity and the His@AuNCs/RGO nanocomposites had a lower Michaelis constant (Km) and higher catalytic constant (Kcat) for TMB oxidation. Furthermore, compared to other nanomaterials, the as-prepared His@AuNCs/RGO also exhibited enhanced electrocatalytic activity toward TMB. Interestingly, nitrite inhibited the catalytic (chromogenic) and electrocatalytic processes of His@AuNCs/RGO in the oxidation of TMB. The oxidase-like and electrocatalytic activity of His@AuNCs/RGO was evaluated with nitrite and TMB as substrates, and the results indicated that TMB and nitrite might share the same catalytic active sites. On the basis of these findings, a colorimetric and electrochemical sensor was developed with the His@AuNCs/RGO composite as an oxidase mimic for determination of nitrite with linear ranges of 10-500 µM and 2.5-5700 µM, respectively. The developed method was successfully applied to the detection of nitrites in real samples. The present work suggests that the oxidase-like nanozyme is not only suitable for colorimetric assay but also for development of electrochemical sensors in bioanalysis. Graphical abstract The colorimetric and electrochemical detection of nitrite using His@AuNCs/RGO.

Pressure-induced structural transformations and polymerization in ThC2.

Thorium-carbon systems have been thought as promising nuclear fuel for Generation IV reactors which require high-burnup and safe nuclear fuel. Existing knowledge on thorium carbides under extreme condition remains insufficient and some is controversial due to limited studies. Here we systematically predict all stable structures of thorium dicarbide (ThC2) under the pressure ranging from ambient to 300 GPa by merging ab initio total energy calculations and unbiased structure searching method, which are in sequence of C2/c, C2/m, Cmmm, Immm and P6/mmm phases. Among these phases, the C2/m is successfully observed for the first time via in situ synchrotron XRD measurements, which exhibits an excellent structural correspondence to our theoretical predictions. The transition sequence and the critical pressures are predicted. The calculated results also reveal the polymerization behaviors of the carbon atoms and the corresponding characteristic C-C bonding under various pressures. Our work provides key information on the fundamental material behavior and insights into the underlying mechanisms that lay the foundation for further exploration and application of ThC2.

Structural Phase Transition of ThC Under High Pressure.

Thorium monocarbide (ThC) as a potential fuel for next generation nuclear reactor has been subjected to its structural stability investigation under high pressure, and so far no one reported the observation of structure phase transition induced by pressure. Here, utilizing the synchrotron X-ray diffraction technique, we for the first time, experimentally revealed the phase transition of ThC from B1 to P4/nmm at pressure of ~58 GPa at ambient temperature. A volume collapse of 10.2% was estimated during the phase transition. A modulus of 147 GPa for ThC at ambient pressure was obtained and the stoichiometry was attributed to the discrepancy of this value to the previous reports.

High-level expression and characterization of a chimeric lipase from Rhizopus oryzae for biodiesel production.

BACKGROUND: Production of biodiesel from non-edible oils is receiving increasing attention. Tung oil, called "China wood oil" is one kind of promising non-edible biodiesel oil in China. To our knowledge, tung oil has not been used to produce biodiesel by enzymatic method. The enzymatic production of biodiesel has been investigated extensively by using Rhizopus oryzae lipase as catalyst. However, the high cost of R. oryzae lipase remains a barrier for its industrial applications. Through different heterologous expression strategies and fermentation techniques, the highest expression level of the lipase from R. oryzae reached 1334 U/mL in Pichia pastoris, which is still not optimistic for industry applications. RESULTS: The prosequence of lipases from Rhizopus sp. is very important for the folding and secretion of an active lipase. A chimeric lipase from R. oryzae was constructed by replacing the prosequence with that from the R. chinensis lipase and expressed in P. pastoris. The maximum activity of the chimera reached 4050 U/mL, which was 11 fold higher than that of the parent. The properties of the chimera were studied. The immobilized chimera was used successfully for biodiesel production from tung oil, which achieved higher FAME yield compared with the free chimeric lipase, non-chimeric lipase and mature lipase. By response surface methodology, three variables, water content, methanol to tung oil molar ratio and enzyme dosage were proved to be crucial parameters for biosynthesis of FAME and the FAME yield reached 91.9±2.5% at the optimized conditions by adding 5.66 wt.% of the initial water based on oil weight, 3.88 of methanol to tung oil molar ratio and 13.24 wt.% of enzyme concentration based on oil weight at 40°C. CONCLUSIONS: This is the first report on improving the expression level of the lipase from R. oryzae by replacing prosequences. The immobilized chimera was used successfully for biodiesel production from tung oil. Using tung oil as non-edible raw material and a chimeric lipase from R. oryzae as an economic catalyst make this study a promising one for biodiesel applications.

Mechanical properties of nickel-titanium archwire used in the final treatment phase of Tip-Edge Plus technique: an in vitro study.

BACKGROUND: As the only active component in final treatment phase of Tip-Edge Plus technique, the activation of nickel-titanium orthodontic archwires is one of the factors that affect the torque expression. It is necessary to evaluate the mechanical properties of the nickel-titanium wire used in the final treatment phase in simulated oral environments to forecast the treatment outcomes. METHODS: The mechanical properties of 171 thermal nickel-titanium wires of 0.35 mm (0.014-in) in diameters with different deflection of 40 mm in length were investigated with three-point bending test. The samples were divided into 2 groups: as-received and bended groups. In the bended group, samples were divided into 7 subgroups according to the amounts of deflection and named by the canine angulations (-25°, -19°, -13°, -7°, -1°, +5°, +11°). The deflection of wires was made by inserting the wires into the deep tunnel of Tip-Edge Plus brackets positioned in plaster casts with different canine angulations to mimic the use of nickel-titanium wires in the final treatment phase. Immersed the bended group in artificial saliva (pH 6.8) and preserved at 37.0°C. Eight durations of incubation were tested: 1 to 8 weeks. Three analogous samples of each group and subgroups were tested per week. Stiffness (YS:E) and the load-deflection characteristics of unloading plateau section were obtained. RESULTS: Significant changes in specific mechanical properties were observed in long-term immersed and large deflected wires compared with as-received groups. Both immersion time and deflection affected the mechanical properties of wires in the simulated oral environment, and the two factors had synergistic effect. In groups -25°, -19° and -13°, stiffness (YS:E) increased then decreased and average plateau force and ratio of variance decreased then increased correspondingly at specific time. CONCLUSIONS: In the final treatment phase of Tip-Edge Plus technique, the mechanical properties of nickel-titanium wire are associated with the using time and amounts of deflection and it may affect treatment outcomes. As the main reason for wire deflection, canine crown angulation plays an important role in the wire performance. It may be wise to focus on the canine crown angulations and using time in clinic with Tip-Edge Plus technique and make proper adjustment to help to make sure the treatment outcomes.