Template assisted lithium superoxide growth for lithium-oxygen batteries.

Developing batteries with energy densities comparable to internal combustion technology is essential for a worldwide transition to electrified transportation. Li-O2 batteries are seen as the 'holy grail' of battery technologies since they have the highest theoretical energy density of all battery technologies. Current lithium-oxygen (Li-O2) batteries suffer from large charge overpotentials related to the electronic resistivity of the insulating lithium peroxide (Li2O2) discharge product. One potential solution is the formation and stabilization of a lithium superoxide (LiO2) discharge intermediate that exhibits good electronic conductivity. However, LiO2 is reported to be unstable at ambient temperature despite its favorable formation energy at -1.0 eV per atom. In this paper - based on our recent work on the development of cathode materials for aprotic lithium oxygen batteries including two intermetallic compounds, LiIr3 and LiIr, that are found to form good template interfaces with LiO2 - a simple goodness of fit R factor to gauge how well a template surface structure can support LiO2 growth, is developed. The R factor is a quantitative measurement to calculate the geometric difference in the unit cells of specific Miller Index 2D planes of the template surface and LiO2. Using this as a guide, the R factors for LiIr3, LiIr, and La2NiO4+δ, are found to be good. This guide is attested by simple extension to other noble metal intermetallics with electrochemical cycling data including LiRh3, LiRh, and Li2Pd. Finally, the template concept is extended to main group elements and the R factors for LiO2 (111) and Li2Ca suggest that Li2Ca is a possible candidate for the template assisted LiO2 growth strategy.

Nanostructured Conductive Metal Organic Frameworks for Sustainable Low Charge Overpotentials in Li-Air Batteries.

Lithium-oxygen batteries are among the most attractive alternatives for future electrified transportation. However, their practical application is hindered by many obstacles. Due to the insulating nature of Li2 O2 product and the slow kinetics of reactions, attaining sustainable low charge overpotentials at high rates becomes a challenge resulting in the battery's early failure and low round trip efficiency. Herein, outstanding characteristics are discovered of a conductive metal organic framework (c-MOF) that promotes the growth of nanocrystalline Li2 O2 with amorphous regions. This provides a platform for the continuous growth of Li2 O2 units away from framework, enabling a fast discharge at high current rates. Moreover, the Li2 O2 structure works in synergy with the redox mediator (RM). The conductivity of the amorphous regions of the Li2 O2 allows the RM to act directly on the Li2 O2 surface instead of catalyst edges and then transport through the electrolyte to the Li2 O2 surface. This direct charge transfer enables a small charge potential of <3.7 V under high current densities (1-2 A g-1 ) sustained for a long cycle life (100-300 cycles) for large capacities (1000-2000 mAh g-1 ). These results open a new direction for utilizing c-MOFs towards advanced energy storage systems.

High Performance Air Breathing Flexible Lithium-Air Battery.

Lithium-oxygen (Li-O2 ) batteries possess the highest theoretical energy density (3500 Wh kg-1 ), which makes them attractive candidates for modern electronics and transportation applications. In this work, an inexpensive, flexible, and wearable Li-O2 battery based on the bifunctional redox mediator of InBr3 , MoS2 cathode catalyst, and Fomblin-based oxygen permeable membrane that enable long-cycle-life operation of the battery in pure oxygen, dry air, and ambient air is designed, fabricated, and tested. The battery operates in ambient air with an open system air-breathing architecture and exhibits excellent cycling up to 240 at the high current density of 1 A g-1 with a relative humidity of 75%. The electrochemical performance of the battery including deep-discharge capacity, and rate capability remains almost identical after 1000 cycle in a bending fatigue test. This finding opens a new direction for utilizing high performance Li-O2 batteries for applications in the field of flexible and wearable electronics.

In Situ Formed Ir3Li Nanoparticles as Active Cathode Material in Li-Oxygen Batteries.

Lithium-oxygen (Li-O2) batteries are a promising class of rechargeable Li batteries with a potentially very high achievable energy density. One of the major challenges for Li-O2 batteries is the high charge overpotential, which results in a low energy efficiency. In this work size-selected subnanometer Ir clusters are used to investigate cathode materials that can help control lithium superoxide formation during discharge, which has good electronic conductivity needed for low charge potentials. It is found that Ir particles can lead to lithium superoxide formation as the discharge product with Ir particle sizes of ∼1.5 nm giving the lowest charge potentials. During discharge these 1.5 nm Ir nanoparticles surprisingly evolve to larger ones while incorporating Li to form core-shell structures with Ir3Li shells, which probably act as templates for growth of lithium superoxide during discharge. Various characterization techniques including DEMS, Raman, titration, and HRTEM are used to characterize the LiO2 discharge product and the evolution of the Ir nanoparticles. Density functional calculations are used to provide insight into the mechanism for formation of the core-shell Ir3Li particles. The in situ formed Ir3Li core-shell nanoparticles discovered here provide a new direction for active cathode materials that can reduce charge overpotentials in Li-O2 batteries.

Coordination of elemental sulfur and organic carbon source stimulates simultaneous nitrification and denitrification toward low C/N ratio wastewater.

The feasibility of inducing simultaneous nitrification and denitrification (SND) by S0 for low carbon to nitrogen (C/N) ratio wastewater remediation was investigated. Compared with S0 and/or organics absent systems (-3.4 %∼5.0 %), the higher nitrogen removal performance (18.2 %∼59.8 %) was achieved with C/N ratios and S0 dosages increasing when S0 and organics added simultaneously. The synergistic effect of S0 and organics stimulated extracellular polymeric substances secretion and weakened intermolecular binding force of S0, facilitating S0 bio-utilization and reducing the external organics requirement. It also promoted microbial metabolism (0.16 âˆ¼ 0.24 µg O2/(g VSS·h)) and ammonia assimilation (5.9 %∼20.5 %), thereby enhancing the capture of organics and providing more electron donors for SND. Furthermore, aerobic denitrifiers (15.91 %∼27.45 %) and aerobic denitrifying (napA and nirS) and ammonia assimilating genes were accumulated by this synergistic effect. This study revealed the mechanism of SND induced by coordination of S0 and organics and provided an innovative strategy for triggering efficient and stable SND.

Promotion Effect of Catalpol on Angiogenesis and Potential Mechanisms: A Research Based on Network Pharmacology.

Catalpol, a natural iridoid glycoside, has potential therapeutic benefits, including anti-inflammatory and neuroprotective effects. Investigating catalpol's role in angiogenesis is critical for understanding its potential therapeutic applications, particularly in diseases where modulating angiogenesis is beneficial. This study investigates catalpol's influence on angiogenesis and its mechanisms, combining network pharmacology and in vitro experiments. The target genes corresponding to the catalpol were analyzed by SwissTargetPrediction. Then angiogenesis-related targets were acquired from databases like GeneCards. Subsequently, the Database for Annotation, Visualization and Integrated Discovery was employed for Gene Ontology and pathway analysis, while Cytoscape visualized protein interactions. The effect of catalpol on viability and angiogenesis of HUVECs was further examined using Cell Counting Kit-8 and angiogenesis assays. RT-qPCR and western blot were applied to check the expression of angiogenesis-related proteins. Totally, 312 target genes of catalpol and 823 angiogenesis-related targets were obtained with 56 common targets leading to PPI network analysis, highlighting hub genes (AKT1, EGFR, STAT3, MAPK3, and CASP3). These hub genes were mainly enriched in lipid and atherosclerosis pathway and EGFR-related pathway. The in vitro experimental results showed that catalpol achieved a concentration-dependent increase in HUVECs viability. Catalpol also promoted the migration and angiogenesis of HUVECs and up-regulated the expression of EGFR. EGFR knockdown inhibited the effect of catalpol on HUVECs. Catalpol promotes angiogenesis in HUVECs by upregulating EGFR and angiogenesis-related proteins, indicating its potential therapeutic application in vascular-related diseases.

A KMnO4-Generated Colloidal Electrolyte for Redox Mediation and Anode Protection in a Li-Air Battery.

The rechargeable lithium-oxygen (Li-O2) battery has the highest theoretical specific energy density of any rechargeable batteries and could transform energy storage systems if a practical device could be attained. However, among numerous challenges, which are all interconnected, are polarization due to sluggish kinetics, low cycle life, small capacity, and slow rates. In this study, we report on use of KMnO4 to generate a colloidal electrolyte made up of MnO2 nanoparticles. The resulting electrolyte provides a redox mediator for reducing the charge potential and lithium anode protection to increase cycle life. This electrolyte in combination with a stable binary transition metal dichalcogenide alloy, Nb0.5Ta0.5S2, as the cathode enables the operation of a Li-O2 battery at a current density of 1 mA·cm-2 and specific capacity ranging from 1000 to 10 000 mA·h·g-1 (corresponding to 0.1-1 mA·h·cm-2) in a dry air environment with a cycle life of up to 150. This colloidal electrolyte provides a robust approach for advancing Li-air batteries.

High-Rate Long Cycle-Life Li-Air Battery Aided by Bifunctional InX3 (X = I and Br) Redox Mediators.

Redox mediators (RMs) are solution-based additives that have been extensively used to reduce the charge potential and increase the energy efficiency of Li-oxygen (Li-O2) batteries. However, in the presence of RMs, achieving a long cycle-life operation of Li-O2 batteries at a high current rate is still a major challenge. In this study, we discover a novel synergy among InX3 (X = I and Br) bifunctional RMs, molybdenum disulfide (MoS2) nanoflakes as the air electrode, dimethyl sulfoxide/ionic liquid hybrid electrolyte, and LiTFSI as a salt to achieve long cycle-life operations of Li-O2 batteries in a dry air environment at high charge-discharge rates. Our results indicate that batteries with InI3 operate up to 450 cycles with a current density of 0.5 A g-1 and 217 cycles with a current density of 1 A g-1 at a fixed capacity of 1 A h g-1. Batteries with InBr3 operate up to 600 cycles with a current density of 1 A g-1. These batteries can also operate at a higher charge rate of 2 A g-1 up to 200 cycles (for InBr3) and 160 cycles (for InI3). Our experimental and computational results reveal that while X3- is the source of the redox mediator, LiX at the MoS2 cathode, In3+ reacts on the lithium anode side to form a protective layer on the surface, thus acting as an effective bifunctional RM in a dry air environment. This evidence for a simultaneous improvement in the current rates and cycle life of a battery in a dry air atmosphere opens a new direction for research for advanced energy storage systems.

Accelerating biodegradation of a monoazo dye Acid Orange 7 by using its endogenous electron donors.

Biodegradation of a monoazo dye - Acid Orange 7 (AO7) was investigated by using an internal circulation baffled biofilm reactor. For accelerating AO7 biodegradation, endogenous electron donors produced from AO7 by UV photolysis were added into the reactor. The result shows that AO7 removal rate can be accelerated by using its endogenous electron donors, such as sulfanilic and aniline. When initial AO7 concentration was 13.6mg/L, electron donors generated by 8h UV photolysis were added into the same system. The biodegradation rate 0.4mg0.05h-1 was enhanced 60% than that without adding electron donor. Furthermore, sulfanilic and aniline were found to be the main endogenous electron carriers, which could accelerate the steps of the azo dye biodegradation.

Postoperative plasma D-dimer value for predicting deep venous thrombosis following hip arthroplasty with nadroparin prophylaxis.

The aim of the study was to assess the value of D-dimer as an event predicitor for deep vein thrombosis (DVT) in patients given low molecular weight heparin (LMWH) after total hip arthroplasty (THA). Plasma D-dimer levels were obtained preoperatively and at days 1, 3, and 7 postoperatively in 83 consecutive patients undergoing THA treated with nadroparin prophylaxis plus intermittent pneumatic compression. Unilateral ascending venography was performed at postoperative day 7 or 8. There was a significant difference between the D-dimer levels in the DVT group (28 patients) and non-DVT group (55 patients) on each day (P<0.01). ROC analysis showed the AUC on postoperative days 1, 3 and 7 was 0.706, 0.712 and 0.772 respectively. The D-dimer concentration on postoperative day 1, day 3 or day 7 is of moderate predicting value of DVT in patients undergoing THA, treated with nadroparin prophylaxis plus intermittent pneumatic compression.

Synthesis and relative bioavailability of meptazinol benzoyl esters as prodrugs.

Three meptazinol benzoyl esters (1-3) were synthesized as prodrugs to minimize the first-pass effect of meptazinol and improve the bioavailability. Among these three esters, compound 3 showed better bioavailability than the parent meptazinol. Further, the relative regional bioavailability of prodrug 3 was evaluated using in situ closed loop study in rats, which showed that prodrug 3 has higher absorption efficacy in rat intestine. Thusly, prodrug 3 may be worth for further development.