Dynamic Behavior of Intermediate Adsorbates to Control Activity and Product Selectivity in Heterogeneous Catalysis: Methanol Decomposition on Pt/TiO2(110).

Dynamic behavior of intermediate adsorbates, such as diffusion, spillover, and reverse spillover, has a strong influence on the catalytic performance in oxide-supported metal catalysts. However, it is challenging to elucidate how the intermediate adsorbates move on the catalyst surface and find active sites to give the corresponding products. In this study, the effect of the dynamic behavior of methoxy intermediate on methanol decomposition on a Pt/TiO2(110) surface has been clarified by combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. The methoxy intermediates were formed by the dissociative adsorption of methanol molecules on Pt nanoparticles at room temperature followed by spillover to the TiO2(110) support surface. TPD results showed that the methoxy intermediates were thermally decomposed at >350 K on the Pt sites to produce CO (dehydrogenation) and CH4 (C-O bond scission). A decrease of the Pt nanoparticle density lowered the activity for the decomposition reaction and increased the selectivity toward CH4, which indicates that the reaction is controlled by diffusion and reverse spillover of the methoxy intermediates. Time-lapse STM imaging and DFT calculations revealed that the methoxy intermediates migrate on the five-fold coordinated Ti (Ti5c) sites along the [001] or [11¯0] direction with the aid of hydrogen adatoms bonded to the bridging oxygens (Obr) and can move over the entire surface to seek and find active Pt sites. This work offers an in-depth understanding of the important role of intermediate adsorbate migration in the control of the catalytic performance in oxide-supported metal catalysts.

Cooperative Catalysis of Vibrationally Excited CO2 and Alloy Catalyst Breaks the Thermodynamic Equilibrium Limitation.

Using nonthermal plasma (NTP) to promote CO2 hydrogenation is one of the most promising approaches that overcome the limitations of conventional thermal catalysis. However, the catalytic surface reaction dynamics of NTP-activated species are still under debate. The NTP-activated CO2 hydrogenation was investigated in Pd2Ga/SiO2 alloy catalysts and compared to thermal conditions. Although both thermal and NTP conditions showed close to 100% CO selectivity, it is worth emphasizing that when activated by NTP, CO2 conversion not only improves more than 2-fold under thermal conditions but also breaks the thermodynamic equilibrium limitation. Mechanistic insights into NTP-activated species and alloy catalyst surface were investigated by using in situ transmission infrared spectroscopy, where catalyst surface species were identified during NTP irradiation. Moreover, in in situ X-ray absorption fine-structure analysis under reaction conditions, the catalyst under NTP conditions not only did not undergo restructuring affecting CO2 hydrogenation but also could clearly rule out catalyst activation by heating. In situ characterizations of the catalysts during CO2 hydrogenation depict that vibrationally excited CO2 significantly enhances the catalytic reaction. The agreement of approaches combining experimental studies and density functional theory (DFT) calculations substantiates that vibrationally excited CO2 reacts directly with hydrogen adsorbed on Pd sites while accelerating formate formation due to neighboring Ga sites. Moreover, DFT analysis deduces the key reaction pathway that the decomposition of monodentate formate is promoted by plasma-activated hydrogen species. This work enables the high designability of CO2 hydrogenation catalysts toward value-added chemicals based on the electrification of chemical processes via NTP.

Interfacial Structure of Water as a New Descriptor of the Hydrogen Evolution Reaction.

Driven by the persisting poor understanding of the sluggish kinetics of the hydrogen evolution reaction (HER) on Pt in alkaline media, a direct correlation of the interfacial water structure and activity is still yet to be established. Herein, using Pt and Pt-Ni nanoparticles we first demonstrate a strong dependence of the proton donor structure on the HER activity and pH. The structure of the first layer changes from the proton acceptors to the donors with increasing pH. In the base, the reactivity of the interfacial water varied its structure, and the activation energies of water dissociation increased in the sequence: the dangling O-H bonds < the trihedrally coordinated water < the tetrahedrally coordinated water. Moreover, optimizing the adsorption of H and OH intermediates can re-orientate the interfacial water molecules with their H atoms pointing towards the electrode surface, thereby enhancing the kinetics of HER. Our results clarified the dynamic role of the water structure at the electrode-electrolyte interface during HER and the design of highly efficient HER catalysts.

LncRNA-MALAT1 Promotes Angiogenesis of Thyroid Cancer by Modulating Tumor-Associated Macrophage FGF2 Protein Secretion.

Tumor-associated macrophages (TAMs) in the tumor microenvironment have been associated with enhanced tumor progression. In this study, we investigated the role and molecular mechanisms of MALAT1 in TAMs derived from thyroid cancer. The expression of MALAT1 and FGF2 in thyroid cancer tissues and cells were measured by quantitative real-time PCR and Western blot. TAMs were transfected with indicated constructs. Then the culture medium (CM) from TAMs was harvested for assay. Secreted FGF2 protein levels and TNF-α, IL-12, and IL-10 levels were detected by ELISA. The cell proliferation, migration, and invasion of FTC133 cells were determined with a CCK-8 assay and a Transwell assay, respectively. In addition, HUVEC vasculature formation was measured by matrigel angiogenesis assay. The higher levels of MALAT-1 and FGF2 were observed in thyroid cancer tissues and in thyroid cancer cells compared to that in the control. Besides, in the presence of si-MALAT1, the levels of TNF-α and IL-12 were significantly up-regulated whereas IL-10 was down-regulated in the CM from TAMs. Moreover, down-regulation of MALAT1 in TAMs reduced proliferation, migration, and invasion of FTC133 cells and inhibited angiogenesis. However, overexpression of FGF2 blocked the effects of MALAT1 siRNAs on cell migration, invasion, and angiogenesis. Our results suggest that MALAT1-mediated FGF2 protein secretion from TAMs inhibits inflammatory cytokines release, promotes proliferation, migration, and invasion of FTC133 cells and induces vasculature formation. J. Cell. Biochem. 118: 4821-4830, 2017. © 2017 Wiley Periodicals, Inc.

Seeds and Potentials Mediated Synthesis of High-Index Faceted Gold Nanocrystals with Enhanced Electrocatalytic Activities.

Because high-index facets (HIFs) possess high surface energy, the metal nanoparticles enclosed with HIFs are eliminated during their growth in a conventional shape-controlled synthesis due to the thermodynamics that drives the particles minimizing their total surface energy. This study develops a double-step potential method to prepare an unprecedentedly stellated Au nanocrystals (NCs) bounded by high-index {711} and {331} facets in deep eutectic solvent (DES) medium. The formation of Au NCs bounded by HIFs was systematically studied. It has demonstrated that the shapes of Au NCs are strongly dependent on the size of seeds and the growth potentials as well as the urea adsorbates in the DES. By adjusting the size of seeds and the growth potentials, the stellated Au NCs can be transformed into concave hexoctahedra (HOH) with high-index {421} facets and concave trisoctahedra (TOH) with high-index {991} facets. The electrocatalytic activities of the as-prepared Au NCs are evaluated by glucose oxidation. Thanks to HIFs having high density of atomic steps and kinks, the stellated, TOH, and HOH Au NCs exhibit higher electrocatalytic activity than that of the polycrystalline Au electrode, demonstrating that the steps and kinks serve as the active sites and play an important role in glucose electro-oxidation.

Green tea catechins: a fresh flavor to anticancer therapy.

Green tea catechins have been extensively studied for their cancer preventive effects. Accumulating evidence has shown that green tea catechins, like (-)-epigallocatechin-3-gallate, have strong anti-oxidant activity and affect several signal transduction pathways relevant to cancer development. Here, we review the biological properties of green tea catechins and the molecular mechanisms of their anticancer effects, including the suppression of cancer cell proliferation, induction of apoptosis, and inhibition of tumor metastasis and angiogenesis. We summarize the efficacy of a single catechin and the synergetic effects of multiple catechins. We also discuss the enhanced anticancer effects of green tea catechins when they are combined with anticancer drugs. The information present in this review might promote the development of strategy for the co-administration of green tea catechins with other anticancer drugs to increase the potency of currently available anticancer medicine. This new strategy should in turn lower the cytotoxicity and cost of anticancer treatment.

A comparative study of CO adsorption on tetrahexahedral Pt nanocrystals and interrelated Pt single crystal electrodes by using cyclic voltammetry and in situ FTIR spectroscopy.

This study focuses on CO adsorption at tetrahexahedral Pt nanocrystals (THH Pt NCs) by using cyclic voltammetry and in situ FTIR spectroscopy. Since the electrochemically prepared THH Pt NCs in this study are enclosed by {730} facets which could be considered by a subfacet configuration of 2{210} + {310}, we have also studied CO adsorption on the interrelated Pt(310) and Pt(210) single crystal electrodes as a comparison. Cyclic voltammetry results demonstrated that CO adsorbs dominantly on the (100) sites of THH Pt NCs at low CO coverage (θ(CO)≤ 0.135), while on both (100) and (110) sites at higher CO coverage. On ordered Pt(310) and Pt(210), i.e. they were flame annealed and then cooled in H(2) + Ar, CO adsorption also illustrates relative priority on (100) sites at low CO coverage; while at high CO coverage or on oxygen-disordered Pt(310) and Pt(210) when they were cooled in air after flame annealing, the adsorption of CO presents a weak preference on (100) sites of Pt(310) and even no preference at all on (100) sites of Pt(210). In situ FTIR spectroscopic studies illustrated that CO adsorption on THH Pt NCs yields anomalous infrared effects (AIREs), which are depicted by the Fano-like IR feature on a dense distribution (60 µm(-2)) and the enhancement of abnormal IR absorption on a sparse distribution (22 µm(-2)) of THH Pt NCs on glassy carbon substrate. Systematic investigation of CO coverage dependence of IR features revealed that, on THH Pt NCs, the IR band center (ν(COL)) of linearly bonded CO (COL) is rapidly shifted to higher wavenumbers along with the increase of CO coverage to 0.184, yielding a fast linear increase rate with a high slope (dν(COL)/dθ(IR)(CO) = 219 cm(-1)); when θ > 0.184, the increase of ν(COL) with θCO slows down and deviates drastically from linearity. In contrast, the ν(COL) on the ordered Pt(310) electrode maintains a linear increase with θ(IR)(CO) for the whole range of θ(IR)(CO) variation, and gives a much smaller increase rate of slope 74.3 cm(-1). The significant differences in CO adsorption behavior on THH Pt NCs and on interrelated Pt single crystal planes demonstrated clearly the unique properties of nanoparticles enclosed by high-index facets.

Mangiferin facilitates islet regeneration and ß-cell proliferation through upregulation of cell cycle and ß-cell regeneration regulators.

Mangiferin, a xanthonoid found in plants including mangoes and iris unguicularis, was suggested in previous studies to have anti-hyperglycemic function, though the underlying mechanisms are largely unknown. This study was designed to determine the therapeutic effect of mangiferin by the regeneration of ß-cells in mice following 70% partial pancreatectomy (PPx), and to explore the mechanisms of mangiferin-induced ß-cell proliferation. For this purpose, adult C57BL/6J mice after 7-14 days post-PPx, or a sham operation were subjected to mangiferin (30 and 90 mg/kg body weight) or control solvent injection. Mangiferin-treated mice exhibited an improved glycemia and glucose tolerance, increased serum insulin levels, enhanced ß-cell hyperplasia, elevated ß-cell proliferation and reduced ß-cell apoptosis. Further dissection at the molecular level showed several key regulators of cell cycle, such as cyclin D1, D2 and cyclin-dependent kinase 4 (Cdk4) were significantly up-regulated in mangiferin-treated mice. In addition, critical genes related to ß-cell regeneration, such as pancreatic and duodenal homeobox 1 (PDX-1), neurogenin 3 (Ngn3), glucose transporter 2 (GLUT-2), Forkhead box protein O1 (Foxo-1), and glucokinase (GCK), were found to be promoted by mangiferin at both the mRNA and protein expression level. Thus, mangiferin administration markedly facilitates ß-cell proliferation and islet regeneration, likely by regulating essential genes in the cell cycle and the process of islet regeneration. These effects therefore suggest that mangiferin bears a therapeutic potential in preventing and/or treating the diabetes.

Recent Progress on Durable Metal-N-C Catalysts for Proton Exchange Membrane Fuel Cells.

It is essential for the widespread application of proton exchange membrane fuel cells (PEMFCs) to investigate low-cost, extremely active, and long-lasting oxygen reduction catalysts. Initial performance of PGM-free metal-nitrogen-carbon (M-N-C) catalysts for oxygen reduction reaction (ORR) has advanced significantly, particularly for Fe-N-C-based catalysts. However, the insufficient stability of M-N-C catalysts still impedes their use in practical fuel cells. In this review, we focus on the understanding of the structure-stability relationship of M-N-C ORR catalysts and summarize valuable guidance for the rational design of durable M-N-C catalysts. In the first section of this review, we discuss the inherent degrading mechanisms of M-N-C catalysts, such as carbon corrosion, demetallation, H2 O2 attack, etc. As we gain a thorough comprehension of these deterioration mechanisms, we shift our attention to the investigation of strategies that can mitigate catalyst deterioration and increase its stability. These strategies include enhancing the anti-oxidation of carbon, fortifying M-N bonds, and maximizing the effectiveness of free radical scavengers. This review offers a prospective view on the enhancement of the stability of non-noble metal catalysts.

Automatic classification of fetal heart rate based on a multi-scale LSTM network.

Introduction: Fetal heart rate monitoring during labor can aid healthcare professionals in identifying alterations in the heart rate pattern. However, discrepancies in guidelines and obstetrician expertise present challenges in interpreting fetal heart rate, including failure to acknowledge findings or misinterpretation. Artificial intelligence has the potential to support obstetricians in diagnosing abnormal fetal heart rates. Methods: Employ preprocessing techniques to mitigate the effects of missing signals and artifacts on the model, utilize data augmentation methods to address data imbalance. Introduce a multi-scale long short-term memory neural network trained with a variety of time-scale data for automatically classifying fetal heart rate. Carried out experimental on both single and multi-scale models. Results: The results indicate that multi-scale LSTM models outperform regular LSTM models in various performance metrics. Specifically, in the single models tested, the model with a sampling rate of 10 exhibited the highest classification accuracy. The model achieves an accuracy of 85.73%, a specificity of 85.32%, and a precision of 85.53% on CTU-UHB dataset. Furthermore, the area under the receiver operating curve of 0.918 suggests that our model demonstrates a high level of credibility. Discussion: Compared to previous research, our methodology exhibits superior performance across various evaluation metrics. By incorporating alternative sampling rates into the model, we observed improvements in all performance indicators, including ACC (85.73% vs. 83.28%), SP (85.32% vs. 82.47%), PR (85.53% vs. 82.84%), recall (86.13% vs. 84.09%), F1-score (85.79% vs. 83.42%), and AUC(0.9180 vs. 0.8667). The limitations of this research include the limited consideration of pregnant women's clinical characteristics and disregard the potential impact of varying gestational weeks.

Phosphorus-Doping Enables the Superior Durability of a Palladium Electrocatalyst towards Alkaline Oxygen Reduction Reactions.

The sluggish kinetics of oxygen reduction reactions (ORRs) require considerable Pd in the cathode, hindering the widespread of alkaline fuel cells (AFCs). By alloying Pd with transition metals, the oxygen reduction reaction's catalytic properties can be substantially enhanced. Nevertheless, the utilization of Pd-transition metal alloys in fuel cells is significantly constrained by their inadequate long-term durability due to the propensity of transition metals to leach. In this study, a nonmetallic doping strategy was devised and implemented to produce a Pd catalyst doped with P that exhibited exceptional durability towards ORRs. Pd3P0.95 with an average size of 6.41 nm was synthesized by the heat-treatment phosphorization of Pd nanoparticles followed by acid etching. After P-doping, the size of the Pd nanoparticles increased from 5.37 nm to 6.41 nm, and the initial mass activity (MA) of Pd3P0.95/NC reached 0.175 A mgPd-1 at 0.9 V, slightly lower than that of Pd/C. However, after 40,000 cycles of accelerated durability testing, instead of decreasing, the MA of Pd3P0.95/NC increased by 6.3% while the MA loss of Pd/C was 38.3%. The durability was primarily ascribed to the electronic structure effect and the aggregation resistance of the Pd nanoparticles. This research also establishes a foundation for the development of Pd-based ORR catalysts and offers a direction for the future advancement of catalysts designed for practical applications in AFCs.

Bio-catalytic nanoparticle shaping for preparing mesoscopic assemblies of semiconductor quantum dots and organic molecules.

We report a unique bio-catalytic nanoparticle shaping (BNS) method for preparing a variety of mesoscopic particles by a facile process. For example, the BNS method affords mesoscopic QD assembly dispersions. Large-size sedimentations (>1 µm) of QDs are first formed using oligo-L-lysine linkers. These then undergo controlled enzymatic cleavage of the linkers using trypsin, which surprisingly leads to mesoscopic particles about 84 nm in size with a narrow size distribution. A detailed mechanism of the BNS method is investigated using tetrakis(4-carboxyphenyl)porphyrin (TCPP), instead of QDs, as a probe molecule. Interestingly, the BNS method can also be applied to other combinations of enzymes and enzymatically degradable linkers, such as hyaluronidase with hyaluronan. As a potential application, the mesoscopic particles of QDs and oligo-lysine exhibit their ability to act as a drug delivery carrier originating from the features of both QDs and oligo-lysine. The BNS method demonstrates the universality and versatility of preparing mesoscopic particles and opens new doors for studying QD assemblies and molecular-based mesoscopic particles.

Highly Stable Pt-Based Oxygen Reduction Electrocatalysts toward Practical Fuel Cells: Progress and Perspectives.

The high cost and poor reliability of cathodic electrocatalysts for the oxygen reduction reaction (ORR), which requires significant amounts of expensive and scarce platinum, obstructs the broad applications of proton exchange membrane fuel cells (PEMFCs). The principles of ORR and the reasons for the poor stability of Pt-based catalysts are reviewed. Moreover, this paper discusses and categorizes the strategies for enhancing the stability of Pt-based catalysts in fuel cells. More importantly, it highlights the recent progress of Pt-based stability toward ORR, including surface-doping, intermetallic structures, 1D/2D structures, rational design of support, etc. Finally, for atomic-level in-depth information on ORR catalysts in fuel cells, potential perspectives are suggested, such as large-scale preparation, advanced interpretation techniques, and advanced simulation. This review aims to provide valuable insights into the fundamental science and technical engineering for practical Pt-based ORR electrocatalysts in fuel cells.

Monomicelle-Directed Engineering of Strained Carbon Nanoribbons as Oxygen Reduction Catalyst.

To date, precisely tailoring local active sites of well-defined earth-abundant metal-free carbon-based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C-C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin-polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O-containing intermediates. Thus, the constructed metal-free carbon nanoribbons (CNRs-C) with high-curved edges exhibit outstanding ORR activity with half-wave potentials of 0.78 and 0.9 V in 0.5 m H2 SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N-doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk ) is 18 times higher than that of the planar one and the N-doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C-C bonds for boosting ORR.

Lipoic acid prevents steroid-induced osteonecrosis in rabbits.

The objective of this study was to investigate in vivo effects of lipoic acid (LA) in preventing steroid-induced osteonecrosis and the possible pathway in a rabbit model. Sixty rabbits were divided into 2 groups: rabbits were intraperitoneally injected with LA aqueous solution at 36 mg/kg of body weight per day for 4 weeks in Group A and rabbits were injected with physiologic saline (PS) as a control in Group B. At 2 weeks after starting treatment, they were intramuscularly injected once with 20 mg/kg of methylprednisolone acetate (MPSL). The femora were histopathologically examined for the presence of osteonecrosis. The plasma levels of total cholesterol (TC), low-density lipoprotein (LDL), high-density lipoprotein (HDL), glutathione (GSH), endothelin (ET) and malondialdehyde (MDA) were assayed at 2 weeks after the injection of MPSL. The incidence of osteonecrosis was significantly higher in Group B (73.1%) than in Group A (20.8%). The GSH level was higher in Group A than in Group B after the LA injection. The plasma MDA and ET levels were lower in Group A than in Group B at 2 weeks after the MPSL administration. Lipoic acid can prevent the development of steroid-induced osteonecrosis in rabbits. Inhibited oxidative stress and amendment of vascular endothelial dysfunction is a possible mechanism for this effect.

Concave Pt-Zn Nanocubes with High-Index Faceted Pt Skin as Highly Efficient Oxygen Reduction Catalyst.

High dosage of expensive Pt to catalyze the sluggish oxygen reduction reaction (ORR) on the cathode severely impedes the commercialization of proton exchange membrane fuel cells. Therefore, it is urgent to cut down the Pt catalyst by efficiently improving the ORR activity while maintaining high durability. Herein, magic concave Pt-Zn nanocubes with high-index faceted Pt skin (Pt78 Zn22 ) are proposed for high-efficiency catalysis toward proton exchange membrane fuel cells. These unique structural features endow the Pt-skin Pt78 Zn22 /KB with a mass activity of 1.18 mA µgPt -1 and a specific activity of 3.64 mA cm-2 for the ORR at 0.9 V (vs RHE). Meanwhile, the H2 -O2 fuel cell assembled by this catalyst delivers an ultrahigh peak power density of ≈1449 mW cm-2 . Both experiments and theoretical calculations show that the electronic structure of the surface is adjusted, thereby shortening the length of the Pt-Pt bond and reducing the adsorption energy of OH*/O* on the Pt surface. This work demonstrates the synergistic effect of the oxidation-resistant metal Zn and the construction of Pt-rich surface engineering. Also, it guides the future development of catalysts for their practical applications in energy conversion technologies and beyond.

Evolution of Cu single atom catalysts to nanoclusters during CO2 reduction to CO.

We synthesized Cu single atoms embedded in a N-doped porous carbon catalyst with a high Faradaic efficiency of 93.5% at -0.50 V (vs. RHE) for CO2 reduction to CO. The evolution of Cu single-atom sites to nanoclusters of about 1 nm was observed after CO2 reduction at a potential lower than -0.30 V (vs. RHE). The DFT calculation indicates that Cu nanoclusters improve the CO2 activation and the adsorption of intermediate *COOH, thus exhibiting higher catalytic activity than CuNx sites. The structural instability observed in this study helps in understanding the actual active sites of Cu single atom catalysts for CO2 reduction.

Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation.

Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well-defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high-spin (dxy 2 dyz 1 dxz 1 d z 2 1 d x 2 - y 2 1 ) to medium-spin (dxy 2 dyz 2 dxz 1 d z 2 1 ), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4 , and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2 . As a result, FeMoPPc with medium-spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high-spin FeN4 and MoPPc with MoN4 , respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.

Regulating Fe-spin state by atomically dispersed Mn-N in Fe-N-C catalysts with high oxygen reduction activity.

As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O2 reduction preferentially takes place on FeIII in the FeN4 /C system with intermediate spin state which possesses one eg electron (t2g4eg1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the FeIII sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO4), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm-2 and long-term durability in reversible zinc-air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts.

[Protein gene product 9.5-immunoactive nerve fibers and its clinical significance in endometriotic peritoneal lesions].

OBJECTIVE: To investigate the association between distribution of protein gene product (PGP) 9.5-immunoactive nerve fibers in peritoneal endometriotic lesions and disease-associated pain symptoms. METHODS: Thirty two peritoneal endometriotic lesions from patients with endometriosis (16 cases with pain and 16 cases without pain) and matched with 20 peritoneal tissues from patients with uterine leiomyoma without endometriosis were stained immunohistochemically for PGP9.5-immunoactive nerve fibers. RESULTS: The positive rate and density of PGP9.5-immunoreactive nerve fibers in peritoneal endometriotic leision were 62% (10/16) and (3.8+/-1.7)/mm2 in endometriosis patients with pain, which were significantly higher than 19% (3/16) and (1.7+/-0.5)/mm2 in endometriosis patients without pain (P<0.05) and 25% (5/20) and (1.3+/-0.6)/mm2 in peritoneal tissues in women without endometriosis (P<0.05). However, no differences were found between endometriosis patients without pain and women without endometriosis (P>0.05). Moreover, the density of PGP9.5-immunoreactive nerve fibers in peritoneal lesions in endometriosis patients with pain was positively correlated with the severity of pain (r=0.855, P<0.05). In addition, the density of PGP9.5-immunoreactive nerve fibers in peritoneal lesions was statistically higher in endometriosis patients with chronic pelvic pain and (or) dysmenorrhea than those in endometriosis patients with other type of pain (P<0.05), which was not associated with active lesion, site and staging (P>0.05). CONCLUSION: It suggested that PGP9.5-immunoreactive nerve fibers might confer the mechanism of pelvic pain with endometriosis.