Sulfur-bridge ligands altering the microenvironment of single-atom CoN3S sites to boost the oxygen reduction reaction.

We report here an asymmetric N,S-coordinated cobalt-based single-atom catalyst with sulfur (S)-bridge ligands (Co-N/S-C) for the oxygen reduction reaction (ORR). The Co-N/S-C exhibits a half-wave potential (E1/2) of 0.908 V versus RHE, outperforming most state-of-the-art ORR catalysts. Theoretical calculations indicate that the CoN3SC10-S moiety facilitates the ORR kinetics by optimizing the adsorption of intermediates. This work provides new insights into the design of single-atom catalysts for electrocatalysis through heteroatom-bridge ligand engineering.

Observation of 4th-order water oxidation kinetics by time-resolved photovoltage spectroscopy.

Artificial photo-driven water oxidation has been proposed over half a century through a four-charge involved multiple-step oxygen evolution process. However, the knowledge of the intrinsic activity, such as the rate-law of the water oxidation reactions, has been inadequately studied. Up to date, the highest order reported is the third one under photoelectrochemical condition. In this work, we identified the fourth-order charge decay reactions on hematite by using a time-resolved surface photovoltage probe technique. A theoretical turnover frequency (TOF) > 100 nm-2·s-1 can be expected for O2 molecules when the hole density >0.1 nm-2. This work demonstrates a facile and robust method to investigate the high-order reaction kinetics. More excitingly, this research built the bridge between the rate-law, rate-determining step, and energy barrier of intermediates.

Metasequoia-like Nanocrystal of Iron-Doped Copper for Efficient Electrocatalytic Nitrate Reduction into Ammonia in Neutral Media.

It is of significance to design catalysts for achieving high-performance electrochemical nitrate reduction to ammonia (NRA) in mild neutral media. However, the faradaic efficiency and selectivity are still far from satisfactory. Here, the fabrication of an efficient catalyst was achieved by rationally doping Fe to Cu into a metasequoia-like nanocrystal of CuFe for NRA in neutral media. Fe doping was found to deepen energy level of the Cu 3d band, favorably tuning adsorption energies of reaction intermediates to promote the NRA. At an applied potential of -0.7 V vs. the reversible hydrogen electrode, the CuFe with approximately 2 % Fe doping content delivered a catalytic current density of 55.6 mA cm-2 , which was 2.1 times that of the Cu material. The CuFe also exhibited a faradaic efficiency up to 94.5 %, and a good selectivity of 86.8 %.

One-step synthesis of IrOx-decorated ultrathin NiFe LDH nanosheets for efficient oxygen evolution reaction.

The oxygen evolution reaction (OER) is a vital proton donor for various clean energy technologies. Here, we synthesized IrOx-decorated ultrathin NiFe-LDH nanosheets (thickness 1-2 nm) by a one-step co-precipitation method. The IrOx was uniformly dispersed on the surface of ultrathin NiFe-LDH nanosheets, greatly increasing the active sites and the electric conductivity for NiFe-LDH. As a result, the IrOx/U-NiFe-LDH exhibited excellent OER performance with a low overpotential (236 mV) and a Tafel slope (74.3 mA dec-1).

Recent Advances of Two-Dimensional (2 D) MXenes and Phosphorene for High-Performance Rechargeable Batteries.

The design and development of advanced electrode materials for high-performance rechargeable batteries have been subjected to extensive studies. Very recently, two-dimensional (2 D) nanomaterials have become promising candidates for batteries, owing to their unique physicochemical properties. In particular, MXenes and phosphorene, which exhibit tailored electrical conductivity and ion storage capability, have attracted increasing attention. This Review presents a comprehensive summary of recent advances in the development of 2 D MXenes and phosphorene as electrode materials for high-performance batteries. Their physicochemical properties, including structural configurations and electronic properties of MXenes and direct band gap and anisotropic properties of phosphorene, are firstly discussed. Then, synthesis methods of the two materials are introduced. Thereafter, their applications as electrode materials in batteries, including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), potassium-ion batteries (PIBs), lithium-sulfur (Li-S) batteries, and metal-air batteries, are summarized and discussed in detail. An emphasis is placed on analyzing performance enhancement mechanisms to elucidate fundamental understanding. Finally, future challenges and opportunities for MXenes and phosphorene as electrode materials for batteries are considered.

Co3O4-CeO2/C as a Highly Active Electrocatalyst for Oxygen Reduction Reaction in Al-Air Batteries.

Developing high-performance and low-cost electrocatalysts for oxygen reduction reaction (ORR) is still a great challenge for Al-air batteries. Herein, CeO2, a unique ORR promoter, was incorporated into ketjenblack (KB) supported Co3O4 catalyst. We developed a facile two-step hydrothermal approach to fabricate Co3O4-CeO2/KB as a high-performance ORR catalyst for Al-air batteries. The ORR activity of Co3O4/KB was significantly increased by mixing with CeO2 nanoparticles. In addition, the Co3O4-CeO2/KB showed a better electrocatalytic performance and stability than 20 wt % Pt/C in alkaline electrolytes, making it a good candidate for highly active ORR catalysts. Co3O4-CeO2/KB favored a four-electron pathway in ORR due to the synergistic interactions between CeO2 and Co3O4. In full cell tests, the Co3O4-CeO2/KB exhibited a higher discharge voltage plateau than CeO2/KB and Co3O4/KB when used in cathode in Al-air batteries.

Nickel cobalt oxide/carbon nanotubes hybrid as a high-performance electrocatalyst for metal/air battery.

High-performance, low cost catalyst for oxygen reduction reaction (ORR) remains a big challenge. Herein, nanostructured NiCo2O4/CNTs hybrid was proposed as a high-performance catalyst for metal/air battery for the first time. The well-formed NiCo2O4/CNTs hybrid was studied by steady-state linear polarization curves and galvanostatic discharge curves in comparison with CNTs-free NiCo2O4 and commercial carbon-supported Pt. Because of the synergistic effect, NiCo2O4/CNTs hybrid exhibited significant improvement of catalytic performance in comparison with NiCo2O4 or CNTs alone, even outperforming Pt/C hybrid in ORR process. In addition, the benefits of Ni incorporation were demonstrated by the improved catalytic performance of NiCo2O4/CNTs compared to Co3O4/CNTs, which should be attributed to improved electrical conductivity and new, highly efficient, active sites created by Ni cation incorporation into the spinel structure. NiCo2O4/CNTs hybrid could be used as a promising catalyst for high power metal/air battery.

Dynamic alterations of connexin43, matrix metalloproteinase-2 and tissue inhibitor of matrix metalloproteinase-2 during ventricular fibrillation in canine.

The aim of this study is to investigate the dynamic alterations of cardiac connexin 43 (Cx43), matrix metalloproteinase-2 (MMP-2) and tissue inhibitor of metalloproteinase-2 (TIMP-2) in the setting of different ventricular fibrillation (VF) duration. In this study, thirty-two dogs were randomly divided into sham control group, 8-min VF group, 12-min VF group, and 30-min VF group. Cx43 and phosphorylated Cx43 (p-Cx43) in tissues were detected by western blot and immunofluorescence analysis. MMP-2 and TIMP-2 were detected by western blot and immunohistochemistry analysis. The results showed that Cx43 levels in three VF groups were significantly decreased compared with sham control group. p-Cx43 levels in 12-min and 30-min VF groups were significantly reduced compared with sham control group. The ratio of p-Cx43/Cx43 was also decreased in VF groups. Compared with sham controls, no significant difference was observed between the sham control group and 8-min VF group in MMP-2 level, but MMP-2 level increased in 12-min and 30-min VF groups. The ratios of MMP-2/TIMP-2 were higher in VF groups, and were correlated with the duration of VF. A remarkable correlation was observed between the ratio of p-Cx43/Cx43 and MMP-2/TIMP-2 (r = -0.93, P < 0.01). In conclusion, the alteration of Cx43 and/or p-Cx43 levels and the imbalance of MMP-2 and TIMP-2 may contribute to the initiation and/or persistence of VF. Maneuvers managed to modulate Cx43 level or normalize the balance of MMP-2/TIMP-2 are promising to ameliorate prognosis of VF.

ZP123 reduces energy required for defibrillation by preventing connexin43 remodeling during prolonged ventricular fibrillation in swine.

In ventricular fibrillation, the uncoupling of gap junctions slows conduction velocity and increases action-potential dispersion, which slows and diminishes defibrillation. We studied how the peptide ZP123, a gap-junction enhancer, might lower defibrillation-energy requirements during ventricular fibrillation in live pigs. We randomly assigned 33 pigs into 3 groups: ZP123 (receiving a 1-µg/kg bolus and 10 µg/kg/hr of ZP123), control (receiving saline solution), and sham (undergoing a sham operation). After a 30-min administration of agents, ventricular fibrillation was induced and left untreated for 8 min. Biphasic defibrillation of 50 J was increased by 50-J increments as necessary. Defibrillation-energy requirements were defined as the lowest energy required to achieve defibrillation. Electrocardiographic values were obtained before and after the administration of agents. Western blot and immunofluorescence analyses were performed on ventricular myocardial samples. All but one pig survived. The ZP123 treatment did not alter electrocardiographic variables. In the ZP123 group, the average required defibrillation energy was lower than that in the control group (327.28±269.6 vs 610±192.64 J; P=0.015), and the cumulative percentage of successful defibrillation at upper energy levels was higher (P<0.05). Supraventricular rhythm occurred more often in the ZP123 group than in the control group (72.7% vs 50%, P=0.042). Western-blot and immunofluorescence results showed that ZP123 did not alter the total amount of connexin43 but did prevent its dephosphorylation. We conclude that ZP123 can reduce defibrillation-energy requirements by preventing connexin43 remodeling during prolonged ventricular fibrillation.

Imbalance between tissue inhibitor of metalloproteinase 1 and matrix metalloproteinase 9 after cardiopulmonary resuscitation.

AIMS: This study aimed to determine whether (a) there was an imbalance between matrix metalloproteinase 9 (MMP-9) and tissue inhibitor of metalloproteinase 1 (TIMP-1) after cardiopulmonary resuscitation (CPR) in a canine model of prolonged ventricular fibrillation (VF); (b) with the duration of VF, the degree of the imbalance would be greater; and (c) there was a relationship between the level of MMP-9 or TIMP-1 and the cardiac function. METHODS AND RESULTS: Ventricular fibrillation was electrically induced in 24 dogs. The animals were randomly divided into 3 groups (sham control, n = 8; 8-minute VF, n = 8; 12-minute VF, n = 8). Echocardiographic measurement and hemodynamic variables were recorded before VF and after return of spontaneous circulation. Tissue inhibitor of metalloproteinase 1 (TIMP-1) and MMP-9 were analyzed by Western blot and immunohistochemistry. Compared with sham controls, dogs under VF and CPR showed significantly decreased level of TIMP-1 (P < .001), and with the duration of VF, the level of TIMP-1 declined (P < .01). The level of MMP-9 did not achieve statistical significance in the 3 groups (P > .05); however, they were higher in VF and longer duration VF groups. The ratios of TIMP-1/MMP-9 were lower in VF groups (P < .05). There was a negative correlation between TIMP-1 and left atrium dimension and left ventricular diastolic dimensions (r = -0.83 and r = -0.96, respectively; P < .01) and a positive correlation between TIMP-1 and left ventricular ejection fraction (r = 0.85; P < .01). CONCLUSIONS: There was an imbalance between TIMP-1 and MMP-9 after CPR. It may partly contribute to the postresuscitation cardiac dysfunction.

Effect of ZP123, a gap junction modifier, on prolonged ventricular fibrillation in swine.

OBJECTIVES: It was the aim of this study to investigate the effect of ZP123 on prolonged ventricular fibrillation (VF) in swine. METHODS: VF was electrically induced in 20 pigs. The animals randomly received either ZP123 or saline control infusion before VF. After 8 min of untreated VF, cardiopulmonary resuscitation and biphasic defibrillation shocks were applied. VF mean frequency (VF(mf)) and mean amplitude (VF(ma)), hemodynamics, outcome of defibrillation and the rate of return of spontaneous circulation (ROSC) were analyzed. RESULTS: Compared with the control group, VF(mf) was higher but VF(ma) lower during the 8 min of VF in the drug group (11.8 ± 2.1 vs. 10.4 ± 2.0 Hz and 0.24 ± 0.10 vs. 0.31 ± 0.16 mV, respectively; p < 0.05). Hemodynamic variables in the 2 groups were comparable (p > 0.05). The defibrillation threshold was lower and the rate of successful defibrillation was higher in the drug group compared with the control group (92.2 ± 26.4 vs. 133.3 ± 28.9 J and 90 vs. 30%, respectively; p < 0.05). The rate of ROSC was not different between the 2 groups (40 vs. 30%; p > 0.05). CONCLUSION: In prolonged VF, ZP123 could decrease the defibrillation threshold and improve the rate of successful defibrillation. However, it could not improve the rate of ROSC - which may be due to its side effect of decreasing VF(ma).

[Changes in myocardial connexin 43 during ventricular fibrillation].

OBJECTIVE: To observe changes in connexin 43 (Cx43) after ventricular fibrillation (VF) and the effects of rotigaptide (ZP123) on Cx43. METHODS: Thirty domestic pigs were randomly assigned to three groups (10 in each group): sham group, model group and ZP123 group. VF was induced by an 80 V AC transthoracic shock for 5 seconds with the use of subcutaneous needles. Before the induction of VF, animals in ZP123 group were administered with ZP123 (1 µg/kg bolus+10 µg×kg(-1)×h(-1) dissolved in 50 ml normal saline and pumped for 15 minutes ). Those in model group received 50 ml normal saline pumped for 15 minutes. For pigs in sham group VF was not induced and no fluid was given. After 8 minutes of VF, animals were euthanized and myocardial tissues were harvested along the long axis of each left ventricular free wall. Immunofluorescence combined with laser scanning confocal microscope was used to detect the distribution of Cx43. Western blotting was used for quantitative determination of Cx43 protein expression. RESULTS: Immunofluorescence signals for Cx43 in sham group were strong and regularly distributed. In model group, Cx43 signals were weak and distributed in heterogeneity, while in ZP123 group, Cx43 signals were enhanced and their distribution were much more orderly. Compared with sham group, the percentage area and the optical densities (A value) of Cx43 fluorescence signals and Cx43 protein expression were significantly decreased in model group [the percentage area: (0.64±0.36)% vs.(1.27±0.19)%, A value: 15 201± 2 613 vs. 30 634±4 975, Cx43 protein expression: 0.72±0.08 vs. 0.97±0.07, all P<0.05]. The level of Cx43 expression in ZP 123 group [the percentage area (0.96±0.16)%, A value 22 100±4 404, Cx43 protein expression 0.82±0.04] was much higher than model group (all P<0.05). CONCLUSION: During VF, down-regulation of myocardial Cx43 expression occurred, which could be attenuated by administration of ZP123.