A comparative DFT study of HCHO decomposition on different terminations of the Co3O4(110) surface.

Density functional theory calculations have been performed to compare the HCHO decomposition on Co3O4(110)-A and (110)-B terminations. The results showed that the energy barriers of the two C-H bond cleavages of HCHO on the (110)-A termination were lower than those on the (110)-B termination, suggesting that the (110)-A termination had stronger HCHO decomposition ability than the (110)-B termination. Electronic structures revealed that the stronger HCHO decomposition ability of the (110)-A termination might be ascribed to the strong covalent bond between HCHO and the (110)-A termination, as well as the higher d-band center of Co3+ ions on the (110)-A termination. Furthermore, we proposed that the preparation of Co3O4 under oxygen-rich growth conditions was beneficial to HCHO decomposition because the (110)-A termination was more stable under oxygen-rich conditions.

Wear Behavior of the Multiheterostructured AZ91 Mg Alloy Prepared by ECAP and Aging.

The microstructure design based on the development of heterostructure provides a new way for high strength and ductility Mg alloys. However, the wear property, as an important service performance, of Mg alloys with heterostructure is scarcely investigated. In this work, a high strength and ductility AZ91 Mg alloy with multiheterostructure was prepared via a processing route combined industrial-scale equal channel angular pressing (ECAP) and aging. The multiheterostructure consists of the heterogeneous grain structure and heterogeneous precipitates. The dry sliding wear behavior of this multiheterostructured (MH) alloy is investigated compared to the as-cast alloy. The impacts of the applied load and duration time on the wear volume and coefficient of friction (COF) are analyzed, and the wear mechanism is further discussed. The result indicates that although the MH alloy exhibits high-desirable strength-ductility synergy, it shows a poorer wear resistance but a relatively lower COF compared to the as-cast alloy at the present condition. The wear mechanism of both alloys mainly involves abrasive wear, as well as mild adhesion, delamination, and oxidation. In comparison, the MH alloy shows relatively severe adhesion, delamination, and oxidation. The poor wear resistance of the MH alloy at the present dry sliding wear condition is linked to the abundant grain boundaries and fine precipitates. Therefore, one should reasonably use the MH Mg alloy considering the service conditions to seek advantages and avoid disadvantages.

Enhancement of Mechanical Properties and Rolling Formability in AZ91 Alloy by RD-ECAP Processing.

In this study, the influence of rotary-die equal channel angular pressing (RD-ECAP) processing on the mechanical properties and rolling formability of AZ91 alloys was investigated. The as-cast and pre-homogenized AZ91 alloys were pre-processed by RD-ECAP for 16 passes at 573 K and subjected to post-ECAP rolling at 573 K with a rolling speed of 10 m/min. The microstructure and deformation characteristics of the AZ91 alloys were characterized. Results demonstrated that fine-grained AZ91 alloys with improved strength and ductility were obtained via the high-pass RD-ECAP processing, indicating a good plastic formability. The ECAP-ed alloys were easily rolled at 573 K from 4.5 mm to 1.1 mm in thickness without edge cracking. After rolling, heterogeneous grain structures were observed with large numbers of twins and shear bands that created strong basal textures. The rolled AZ91 alloys exhibited higher tensile strength and appropriate elongation. The post-ECAP rolling was successfully used in the high productivity of AZ91 rolled plates with good mechanical properties.

Promoted Anodizing Reaction and Enhanced Coating Performance of Al-11Si Alloy: The Role of an Equal-Channel-Angular-Pressed Substrate.

In this paper, the effect of the equal-channel-angular-pressed (ECAPed) substrate on the coating formation and anticorrosion performance of the anodized Al-11Si alloy was systematically investigated. The ECAP process dramatically refines both Al and Si phases of the alloy. The parallel anodizing circuit is designed to enable a comparative study of anodizing process between the cast and the ECAPed alloys by tracking their respective anodizing current quota. The optimum coatings of both alloys were obtained after anodization for 30 min. The ECAPed alloy attained a thicker, more compact, and more uniform coating. Energetic crystal defects in the fine Al grains of the ECAPed substrate promote the anodizing reaction and lead to the thicker coating. Fragmented and uniformly distributed fine Si particles in the ECAPed alloy effectively suppress the coating cracks, enhancing the compactness of the coating. Overall, the ECAP-coated sample exhibits the best anticorrosion performance, which is evidenced by the concurrently enhanced prevention of coating and improved corrosion resistance of the substrate.

Coupling Effect of Porosity and Cell Size on the Deformation Behavior of Al Alloy Foam under Quasi-Static Compression.

Closed-cell AlCu5Mn alloy foam with porosity range of ~45⁻90% were fabricated by the melt-foaming route. The pore structure of the fabricated Al alloy foam was analyzed and the coupling effect of porosity and cell size on the quasi-static compression behavior of the foam was investigated. The results show that the cell size of the foam decreases with the porosity decline from the view of the contribution rate to the porosity and the hierarchical pore structure characteristics becomes obvious when the foam porosity is low; the compression stress⁻strain curves of the foams with high porosity (>74%) are serrated due to the large cell size being easy to deform and more strain needed to let the stress recover. Meanwhile, the compression curve of the foams with low porosity (<74%) are smooth without serration, which is attributed to the hierarchical pore structure and less strain needed to let the stress recovery.

Lower range of molecular weight of xanthan gum inhibits apoptosis of chondrocytes through MAPK signaling pathways.

LRWXG has previously been reported to have a protective effect on chondrocytes, preventing apoptosis induced by oxidative stress. In this study, we were aimed at determining whether LRWXG exerts its anti-apoptotic activity through the MAPK signaling pathways in chondrocytes. Our results show that, at the cellular level, apoptosis of chondrocytes in the groups treated by LRWXG decreases compared with groups treated by inhibitors alone and model group under conditions of oxidative stress in a dose-dependent manner. Mechanistically at the molecular level, LRWXG regulates the MAPK pathway induced by oxidative stress: The levels of phosphorylation of JNK and p38 proteins in the groups treated by LRWXG are lower than model group, while compared with corresponding groups of inhibitors, there are no significant difference; For other related proteins, LRWXG reduces the levels of the apoptosis-related proteins BAX and cleaved caspase-3, and increases the level of anti-apoptotic protein BCL2. In addition, LRWXG can significantly reduce the levels of inflammatory-related factors such as COX2, PEG2, TNFα and IL1ß, and inhibits the expression of MMPs, increasing the content of type II collagen. The results of this research strongly suggest that LRWXG exerts its anti-apoptotic activity via regulating the MAPK signaling pathways in vitro.

Development of High-Performance Enamel Coating on Grey Iron by Low-Temperature Sintering.

In this study, we report on a low-temperature sintered enamel coating with a high-strength bonding and wear-resistance that protected a grey cast iron substrate. The SiO2⁻Al2O3⁻B2O3 composited prescription for the enamel coating was modified by the partial substitutions of SiO2 for B2O3 and alkali metals for Li2O. The optimized enamel coating was prepared by sintering at a relatively low temperature (730 °C) for seven minutes. Due to the composition of both the amorphous and crystalline phases, the enamel coating presented sufficient hardness and excellent wear resistance. The wear volume loss and the specific wear rate of the enamel coating were obviously lower than that of the metal substrate. The enamel coating can effectively improve the service life of the grey cast iron substrate in a complex frictional environment.

Rebuilding the Strain Hardening at a Large Strain in Twinned Au Nanowires.

Metallic nanowires usually exhibit ultrahigh strength but low tensile ductility, owing to their limited strain hardening capability. Here, our larger scale molecular dynamics simulations demonstrated that we could rebuild the highly desirable strain hardening behavior at a large strain (0.21 to 0.31) in twinned Au nanowires by changing twin orientation, which strongly contrasts with the strain hardening at the incipient plastic deformation in low stacking-fault energy metals nanowires. Because of this strain hardening, an improved ductility is achieved. With the change of twin orientation, a competing effect between partial dislocation propagation and twin migration is observed in nanowires with slant twin boundaries. When twin migration gains the upper hand, the strain hardening occurs. Otherwise, the strain softening occurs. As the twin orientation increases from 0° to 90°, the dominating deformation mechanism shifts from slip-twin boundary interaction to dislocation slip, twin migration, and slip transmission in sequence. Our work could not only deepen our understanding of the mechanical behavior and deformation mechanism of twinned Au nanowires, but also provide new insights into enhancing the strength and ductility of nanowires by engineering the nanoscale twins.

Chemical bonding and Cu diffusion at the Cu/Ta2N interface: a DFT study.

Ta2N is an effective diffusion barrier material to prevent undesired Cu diffusion in ultra-large scale integration circuits. Previous theoretical work has reported the interesting result that at the Cu/Ta2N interface the Cu layer preferentially bonded with the Ta layer but not the N layer of Ta2N. However, this result was calculated from largely lattice mismatched interface models. To confirm this theoretical result and unravel the cause of strong Cu-Ta bonding at the Cu/Ta2N interface, in this study density functional theory calculations, on the basis of super-cell models, were performed to investigate the Cu(111)/Ta2N(001) interface. We firstly calculated interface cohesive energies and confirmed that the Cu layer preferentially bonded with the Ta layer of Ta2N. Then, electronic structure calculations revealed that the chemical bonding of the Cu-Ta bond at the Cu(111)/Ta2N(001) interface was primarily covalent in character, providing a proper explanation for the close integration of the Cu layer and Ta layer. Lastly, Cu diffusion investigations revealed that Ta2N was able to effectively prevent Cu diffusion. Furthermore, we found that the N layer of Ta2N played the critical role in preventing Cu diffusion.

Adipose tissue-derived stem cells in combination with xanthan gum attenuate osteoarthritis progression in an experimental rat model.

The current study explored the efficacy of an intra-articular (IA) injection of allogeneic adipose tissue-derived stem cells (ADSCs) combined with xanthan gum (XG) in a rat osteoarthritis (OA) model. We confirmed that XG significantly inproved proliferation of ADSCs in a dose dependent manner in vitro. The rat OA model was induced by an anterior cruciate ligament transection (ACLT), and at 4 weeks after surgery, rats were divided into four groups: the XG-ADSCs group, the ADSCs group, the XG group and the phosphate-buffered saline (PBS) group. A single dose of 1 × 106 allogeneic ADSCs suspended in 1% XG, ADSCs suspended in PBS, 1% XG alone or PBS alone was injected into the OA joint of rats in the respective treatment groups. Rats were sacrificed at 8 weeks after surgery. Treatment outcomes were evaluated by weight-bearing control of the hind limbs, gross morphological analysis, histological analysis and specific staining of articular cartilage, and measurement of inflammatory factors in synovial fluid. For the rats in the XG-ADSC-s and ADSCs-treated groups, the weight-bearing percentage of the right hind limb was significantly increased compared to that in the PBS group and was sustained over 4 weeks. However, the positive effect in the XG-ADSCs group was significantly greater than that in the ADSCs group. For the rats in the XG group, the efficacy decreased during the third week after surgery. The articular cartilage was relatively normal in the XG-ADSCs group, and moderate degeneration was observed in the ADSCs and XG groups. ADSCs and XG-ADSC treatments significantly decreased the concentrations of IL-1ß, TNF-α, MMP-3 and MMP-13 in synovial fluid; however, the attenuating effect of the XG-ADSCs treatment was significantly enhanced compared with that of the ADSCs treatment alone. These results indicate that a single IA injection of allogeneic ADSCs combined with XG efficiently attenuated OA progression with a therapeutic effect that was significantly greater than that of either ADSCs or XG alone. IA injection of XG-ADSCs might be an effective treatment for OA in humans.

Nanoindentation Induced Deformation and Pop-in Events in a Silicon Crystal: Molecular Dynamics Simulation and Experiment.

Silicon has such versatile characteristics that the mechanical behavior and deformation mechanism under contact load are still unclear and hence are interesting and challenging issues. Based on combined study using molecular dynamics simulations and experiments of nanoindentation on Si(100), the versatile deformation modes, including high pressure phase transformation (HPPT), dislocation, median crack and surface crack, were found, and occurrence of multiple pop-in events in the load-indentation strain curves was reported. HPPTs are regard as the dominant deformation mode and even becomes the single deformation mode at a small indentation strain (0.107 in simulations), suggesting the presence of a defect-free region. Moreover, the one-to-one relationship between the pop-in events and the deformation modes is established. Three distinct mechanisms are identified to be responsible for the occurrence of multiple pop-in events in sequence. In the first mechanism, HPPTs from Si-I to Si-II and Si-I to bct5 induce the first pop-in event. The formation and extrusion of α-Si outside the indentation cavity are responsible for the subsequent pop-in event. And the major cracks on the surface induces the pop-in event at extreme high load. The observed dislocation burst and median crack beneath the transformation region produce no detectable pop-in events.

Decreasing Bio-Degradation Rate of the Hydrothermal-Synthesizing Coated Mg Alloy via Pre-Solid-Solution Treatment.

In this study, we report an effective approach, pre-solid solution (SS) treatment, to reduce the in-vitro bio-degradation rate of the hydrothermal-synthesizing coated Mg-2Zn-Mn-Ca-Ce alloy in Hanks' solution. Pre-SS treatment alters the microstructure of alloys, which benefits the corrosion resistances of the substrate itself and the formed coating as well. The micro-galvanic corrosion between the secondary phase (cathode) and the α-Mg phase (anode) is relieved due to the reduction of the secondary phase. Meanwhile, coating formed on the SS-treated alloy was compacter than that on as-cast alloy, which provides better protection against initial corrosion.

Low molecular weight xanthan gum suppresses oxidative stress-induced apoptosis in rabbit chondrocytes.

We have previously reported the application of low molecular weight XG(LM-XG), with molecular weights ranging from 1×106Da to 1.5×106Da for treating osteoarthritis. In this study, we investigated the anti-apoptotic activity of LM-XG under oxidative stress conditions, activated by hydrogen peroxide (H2O2)-treated chondrocytes in vitro. Chondrocytes were pretreated with various doses of LM-XG (0, 10, 100, 500, or 1000µg/mL) or 1000µg/mL sodium hyaluronate for 12h, and then exposed to 0.5mmol/L H2O2 for another 12h. After treatment, chondrocyte viability was evaluated using a cell counting kit-8; DNA fragmentation was detected using Hoechst33258 staining; the percentage of DNA fragmentation was evaluated using the diphenylamine DNA assay kit; the apoptosis rate was evaluated using flow cytometry; chondrocyte ultra-microscopic morphology was observed using transmission electron microscopy; intracellular reactive oxygen species levels were observed and quantified using 2,7-dichlorofuorescin diacetate, mitochondrial permeability transition analysis was performed using MitoTracker Red CMXRos and 4',6-diamidino-2-phenylindole staining; and finally, caspase-3 activity was detected by western blot. The results showed that, compared with H2O2-treated chondrocytes, LM-XG improved cell viability, decreased the percentage of DNA fragmentation, reduced the apoptosis rate, decreased the levels of intracellular reactive oxygen species and mitochondrial permeability transition, reverted the morphological damage, and downregulated cleaved caspase-3 levels. These results demonstrate that LM-XG has anti-apoptotic activity in H2O2-treated chondrocytes.

Culture-expanded allogenic adipose tissue-derived stem cells attenuate cartilage degeneration in an experimental rat osteoarthritis model.

Mesenchymal stem cell (MSC)-based cell therapy is a promising avenue for osteoarthritis (OA) treatment. In the present study, we evaluated the efficacy of intra-articular injections of culture-expanded allogenic adipose tissue-derived stem cells (ADSCs) for the treatment of anterior cruciate ligament transection (ACLT) induced rat OA model. The paracrine effects of major histocompatibility complex (MHC)-unmatched ADSCs on chondrocytes were investigated in vitro. Rats were divided into an OA group that underwent ACLT surgery and a sham-operated group that did not undergo ACLT surgery. Four weeks after surgery mild OA was induced in the OA group. Subsequently, the OA rats were randomly divided into ADSC and control groups. A single dose of 1 × 106 ADSCs suspended in 60 µL phosphate-buffered saline (PBS) was intra-articularly injected into the rats of the ADSC group. The control group received only 60 µL PBS. OA progression was evaluated macroscopically and histologically at 8 and 12 weeks after surgery. ADSC treatment did not cause any adverse local or systemic reactions. The degeneration of articular cartilage was significantly weaker in the ADSC group compared to that in the control group at both 8 and 12 weeks. Chondrocytes were co-cultured with MHC-unmatched ADSCs in trans-wells to assess the paracrine effects of ADSCs on chondrocytes. Co-culture with ADSCs counteracted the IL-1ß-induced mRNA upregulation of the extracellular matrix-degrading enzymes MMP-3 and MMP-13 and the pro-inflammatory cytokines TNF-α and IL-6 in chondrocytes. Importantly, ADSCs increased the expression of the anti-inflammatory cytokine IL-10 in chondrocytes. The results of this study indicated that the intra-articular injection of culture-expanded allogenic ADSCs attenuated cartilage degeneration in an experimental rat OA model without inducing any adverse reactions. MHC-unmatched ADSCs protected chondrocytes from inflammatory factor-induced damage. The paracrine effects of ADSCs on OA chondrocytes are at least part of the mechanism by which ADSCs exert their therapeutic activity.

Low molecular weight xanthan gum for treating osteoarthritis.

Osteoarthritis (OA) is one of the most common chronic diseases and characterized by degradation of articular cartilage. We have previously reported xanthan gum (XG) injection preparation with high molecular weights (Mw) in ranging from 3×106Da to 5×106Da (HM-XG) could enhance the viscosity of synovial fluid, protect joint cartilage in rabbit, and the therapeutical effect has no significance difference with an existing clinical medication (sodium hyaluronate, SH) at the same injection frequency (once weekly for 5 weeks). Herein, we prepared a XG injection preparation with a low Mw (LM-XG) in ranging from 1×106Da to 1.5×106Da, and evaluated the therapeutical effect for OA therapy at once every 2 weeks for 5 weeks with an SH at once weekly for 5 weeks as reference. The model of OA was induced using anterior cruciate ligament transection (ACLT) in a rabbit in vivo and also using sodium nitroprusside (SNP) in cell culture in vitro. The results showed that LW-XG could also protect cartilage from damage, decrease the concentration of nitric oxide (NO) in synovial fluid and reverse the amplification of the knee joint width similar to HM-XG as our previously reported. At the cellular level, LW-XG promotes proliferation while decreases apoptosis of chondrocytes. Mechanistically at the molecular level, these effects are elicited via down-regulation of the protein levels of caspase-3 and bax and up-regulation of the protein levels of bcl-2 in cartilage in both in vivo and in vitro. These results showed that LW-XG maybe become an excellent candidate long-acting drug for treating OA.

Theoretical study on the surface stabilities, electronic structures and water adsorption behavior of the Ta3N5(110) surface.

A recent experiment revealed that the Ta3N5 semiconductor with orientation along the (110) surface exhibited improved photoelectrochemical activities, but the role of the (110) surface in the improved photoelectrochemical activity remains unclear. In this study, density functional theory calculations were performed to investigate the surface stabilities, surface electronic structures and water splitting behavior of the Ta3N5(110) surface with and without oxygen impurities. The results showed that, on the clean and oxygen impurity containing (110) surfaces, the energy barriers of water splitting were as low as 0.05 and 0.06 eV, respectively, suggesting that the Ta3N5(110) surface is a promising candidate for water splitting. The lower energy barriers of water splitting on the Ta3N5(110) surface may be ascribed to the easy migration of the H atom from the surface Ta atom to the nearby N atom. Furthermore, the surface energies and surface electronic structures revealed that the Ta3N5(110) surface contained less oxygen impurities, which is in accordance with the experimental observations.

Effects of oxygen impurities and nitrogen vacancies on the surface properties of the Ta3N5 photocatalyst: a DFT study.

Surface defects and impurities play important roles in the photocatalytic performance of semiconductors. In this study, DFT calculations are performed to investigate the effects of oxygen impurities and nitrogen vacancies on the surface stability and electronic structures of Ta3N5(100), (010) and (001) low-index surfaces. The results show that, for each surface, the oxygen impurities and nitrogen vacancies are beneficial and harmful, respectively, to the surface stability of Ta3N5. The oxygen impurities and nitrogen vacancies have mainly two effects on the surface electronic structures of Ta3N5. One is saturating surface states on the clean surface, and the other is inducing the downshift of conduction band minimum. In addition, the Ta3N5(100) surface with oxygen impurities is expected to have the strongest reduction ability in practice, providing useful guidance for further investigations of Ta3N5 in the photocatalytic hydrogen evolution.

Unraveling the mechanism of 720 nm sub-band-gap optical absorption of a Ta3N5 semiconductor photocatalyst: a hybrid-DFT calculation.

The Ta3N5 semiconductor photocatalyst possesses a 720 nm (about 1.72 eV) sub-band-gap optical absorption but the mechanism of this optical absorption is still controversial. In this study, the hybrid density functional theory calculations are performed to unravel the mechanism of 720 nm sub-band-gap optical absorption of Ta3N5. By studying the possible optical absorption initiated by the ON impurity and the VN defect, we find that the 720 nm sub-band-gap optical absorption of Ta3N5 may be ascribed to the electron transition from V(·)(N) to V(···)(N). In addition, we propose that the 720 nm sub-band-gap optical absorption can be used to qualitatively evaluate the photocatalytic water splitting ability of Ta3N5.