High buffering capacity cobalt-doped nickel hydroxide electrode as redox mediator for flexible hydrogen evolution by two-step water electrolysis.

Two-step water electrolysis has been proposed to tackle the ticklish H2/O2 mixture problems in conventional alkaline water electrolysis recently. However, low buffering capacity of pure nickel hydroxide electrode as redox mediator limited practical application of two-step water electrolysis system. A high-capacity redox mediator (RM) is urgently needed to permit consecutive operation of two-step cycles and high-efficiency hydrogen evolution. Consequently, a high mass-loading cobalt-doped nickel hydroxide/active carbon cloth (NiCo-LDH/ACC) RM is synthesized via a facile electrochemical method. The proper Co doping can apparently enhance the conductivity and simultaneously remain the high-capacity of the electrode. Density functional theory results further confirms more negative values in redox potential of NiCo-LDH/ACC than Ni(OH)2/ACC on account of the charge redistribution induced by Co doping, which can prevent the parasitic O2 evolution on RM electrode during decoupled H2 evolution step. As a result, the NiCo-LDH/ACC combined the superiorities of high-capacity Ni(OH)2/ACC and high-conductivity Co(OH)2/ACC, and the NiCo-LDH/ACC with 4:1 ratio of Ni to Co presented a large specific capacitance of 33.52F/cm2 for reversible charge-discharge and high buffering capacity with two-step H2/O2 evolution duration of 1740 s at 10 mA/cm2. The necessary input voltage (2.00 V) of the whole water electrolysis was broken into two smaller ones, 1.41 and 0.38 V, for H2 and O2 production, respectively. NiCo-LDH/ACC provided a favorable electrode material for the practical application of two-step water electrolysis system.

Mechanisms and degradation pathways of doxycycline hydrochloride by Fe3O4 nanoparticles anchored nitrogen-doped porous carbon microspheres activated peroxymonosulfate.

Peroxymonosulfate (PMS) based advanced oxidation processes have gained widespread attention in refractory antibiotics treatment. In this study, Fe3O4 nanoparticles anchored nitrogen-doped porous carbon microspheres (Fe3O4/NCMS) were synthesized and applied to PMS heterogeneous activation for doxycycline hydrochloride (DOX-H) degradation. Benefitting from synergy effects of porous carbon structure, nitrogen doping, and fine dispersion of Fe3O4 nanoparticles, Fe3O4/NCMS showed excellent DOX-H degradation efficiency within 20 min via PMS activation. Further reaction mechanisms revealed that the reactive oxygen species including hydroxyl radicals (•OH) and singlet oxygen (1O2) played the dominant role for DOX-H degradation. Moreover, Fe(II)/Fe(III) redox cycle also participated in the radical generation, and nitrogen-doped carbonaceous structures served as the highly active centers for non-radical pathways. The possible degradation pathways and intermediate products accompanying DOX-H degradation were also analyzed in detail. This study provides key insights into the further development of heterogeneous metallic oxides-carbon catalysts for antibiotic-containing wastewater treatment.

Three-dimensional ordered macroporous molybdenum doped NiCoP honeycomb electrode for two-step water electrolysis.

Two-step alkaline water electrolysis is considered a safe and efficient method for producing hydrogen from renewable energy. Reversal of the current polarity in a bifunctional electrocatalyst used as a gas evolution electrode (GEE) in two-step water electrolysis can generate H2/O2 at different times and in different spaces. The design of a bifunctional electrocatalyst with high durability and excellent activity is imperative to achieving continuous, safe, and pure H2 generation via two-step alkaline water electrolysis. Here, we present for the first time a novel 3D Mo-doped NiCo phosphide honeycomb electrocatalyst that was grown on nickel foam (3D Mo-NiCoP/NF) and fabricated using polystyrene as a template. The electrocatalyst exhibited extremely low overpotentials in both the hydrogen evolution reaction (HER; 117 mV at 10 mA/cm2) and the oxygen evolution reaction (OER; 344 mV at 100 mA/cm2). As a bifunctional electrocatalyst for two-step alkaline water electrolysis, the device had a 1.784 V cell voltage at 10 mA/cm2, 95% decoupling efficiency, and ∼83% energy conversion efficiency. Taken together, the use of 3D Mo-NiCoP/NF as a GEE reduced the complexity and lowered the cost of the electrolyzer. The latter could be used to construct highly competitive water-splitting systems for continuous H2 production and green energy harvesting.

Volatile organic compounds degradation by nonthermal plasma: a review.

Volatile organic compounds (VOCs) have posed a severe threat on both ecosystem and human health which thus have gained much attention in recent years. Nonthermal plasma (NTP) as an alternative to traditional methods has been employed to degrade VOC in the atmosphere and wastewater for its high removal efficiency (up to 100%), mild operating conditions, and environmental friendliness. This review outlined the principles of NTP production and the applications on VOC removal in different kinds of reactors, like single/double dielectric barrier discharge, surface discharge, and gliding arc discharge reactors. The combination of NTP with catalysts/oxidants was also applied for VOC degradation to further promote the energy efficiency. Further, detailed explanations were given of the effect of various important factors including input/reactor/external conditions on VOC degradation performance. The reactive species (e.g., high-energy electrons, HO·, O·, N2+, Ar+, O3, H2O2) generated in NTP discharge process have played crucial roles in decomposing VOC molecules; therefore, their variation under different parameter conditions along with the reaction mechanisms involved in these NTP technologies was emphatically explained. Finally, a conclusion of the NTP technologies was presented, and special attention was paid to future challenges for NTP technologies in VOC treatment to stimulate the advances in this topic.

Efficient adsorption and reduction of Cr(VI) from aqueous solution by Santa Barbara Amorphous-15 (SBA-15) supported Fe/Ni bimetallic nanoparticles.

Nanoscale zero-valent iron (nZVI or Fe0) can rapidly reduce Cr(VI) contaminants in the water environment, but the agglomeration and passivation of the Fe0 system have adverse effects on its application. In this study, a novel mesoporous Santa Barbara Amorphous-15 supported Fe/Ni bimetallic composite (SBA-15@Fe/Ni) is proposed to remove Cr(VI). The proposed material can enhance the stability and removal capacity of the nZVI system. The results show that the unique six-way through-hole structure of SBA-15 provides a place for the dispersion of Fe0 particles. Meanwhile, SBA-15 effectively alleviates the accumulation of Fe0 particles. The removal efficiency of SBA-15@Fe/Ni is better than two single systems (SBA-15 and Fe/Ni). The removal efficiency of SBA-15@Fe/Ni towards Cr(VI) can reach 97.62% after 60 min at pH 4.0. SBA-15@Fe/Ni still maintains excellent performance in the presence of various competitive ions (Cl-, SO42-, CO32-, NO3-). At 298 K, the maximum removal capacity of SBA-15@Fe/Ni towards Cr(VI) is 180.99 mg/g. The possible removal process of SBA-15@Fe/Ni towards Cr(VI) is divided into the following steps: First, Cr(VI) is attracted into the vicinity of the SBA-15@Fe/Ni channel by the electrostatic attraction; Second, the reduction of Cr(VI) occurs after contacting with the Fe/Ni system, and its driving force mainly comes from nZVI and Fe(II); Furthermore, the introduction of Ni can promote Cr(VI) reduction through electron transfer and catalytic hydrogenation. In conclusion, adopting SBA-15@Fe/Ni to treat chromium contamination is an effective and promising approach.

Optimization, Characterization, and Anticancer Potential of Silver Nanoparticles Biosynthesized Using Olea europaea.

Green synthesis has attracted significant attention as an eco-friendly, low-cost, energy-efficient, and non-toxic method for preparing silver nanoparticles (AgNPs) for cancer therapy. This study optimized the green synthesis of AgNPs using Olea europaea extracts and evaluated their anticancer potential. The biosynthesized AgNPs were characterized using various methods, showing stable AgNPs with a desirable morphology and high yield, improving the properties of AgNPs for various medicinal applications. The biosynthesized AgNPs were predominantly spherical, with small sizes ranging from 13 to 21 nm and highly stable at -23 and -24 mV. The findings of this study suggest that green-synthesized AgNPs using Olea europaea and sunlight possess significant anticancer activity against cancer cells in vitro. Further investigation of green synthesis would help to form high-quality AgNPs that have promising potential in treating disease and fighting undesirable pathogens.

H∞ State Estimation for BAM Neural Networks With Binary Mode Switching and Distributed Leakage Delays Under Periodic Scheduling Protocol.

This article is concerned with the H∞ state estimation problem for a class of bidirectional associative memory (BAM) neural networks with binary mode switching, where the distributed delays are included in the leakage terms. A couple of stochastic variables taking values of 1 or 0 are introduced to characterize the switching behavior between the redundant models of the BAM neural network, and a general type of neuron activation function (i.e., the sector-bounded nonlinearity) is considered. In order to prevent the data transmissions from collisions, a periodic scheduling protocol (i.e., round-robin protocol) is adopted to orchestrate the transmission order of sensors. The purpose of this work is to develop a full-order estimator such that the error dynamics of the state estimation is exponentially mean-square stable and the H∞ performance requirement of the output estimation error is also achieved. Sufficient conditions are established to ensure the existence of the required estimator by constructing a mode-dependent Lyapunov-Krasovskii functional. Then, the desired estimator parameters are obtained by solving a set of matrix inequalities. Finally, a numerical example is provided to show the effectiveness of the proposed estimator design method.

Interconnected hierarchical nickel-carbon hybrids assembled by porous nanosheets for Cr(VI) reduction with formic acid.

Magnetic carbon materials promise distinct advantages in the decontamination of heavy metal ions. In this work, a novel interconnected hierarchical nickel-carbon (Ni@IHC) hybrid was synthesized by combining the solvothermal method with a one-step pyrolysis under argon atmosphere. Benefitting from 3D flower-like morphology, interconnected porous nanosheets, large surface area, and abundant Ni nanoparticles, Ni@IHC hybrids can remove Cr(VI) within 25 min by using formic acid (FA) as a reductant at 25 ℃. Furthermore, the experimental parameters that can affect the material catalytic performance such as initial Cr(VI) concentration, catalyst dosage, FA concentration, and temperature were also investigated in detail. It was found that highly dispersed Ni nanoparticles contributed significantly to the reduction process. More importantly, the embedded Ni nanoparticles favor fast separation by a magnet and were helpful for the recycles use. This Ni@IHC hybrid was obtained by a facile and easy scale-up method, resulting in the fast transformation of Cr(VI) into Cr(III).

Installation of -SO2F groups onto primary amides.

A protocol of SO2F2-mediated installation of sulfonyl fluoride onto primary amides has been developed providing a new portal to sulfur(VI) fluoride exchange (SuFEx) click chemistry. The generated molecules contain pharmaceutically important amide and -SO2F moieties for application in the discovery of new therapeutics.

Synthetic routes and structure-activity relationships (SAR) of anti-HIV agents: A key review.

The worldwide increase of AIDS, an epidemic infection in constant development has an essential and still requires potent antiretroviral chemotherapeutic agents for reducing the integer of deaths caused by HIV. Thus, there is an urgent need for new anti-HIV drug candidates with increased strength, new targets, superior pharmacokinetic properties, and compact side effects. From this viewpoint, we first review present strategies of anti-HIV drug innovation and the synthesis of heterocyclic or natural compound as anti-HIV agents for facilitating the development of more influential and successful anti-HIV agents.

Space-confined pyrolysis for fabrication of peacods-like Fe3O4@C-Ni nanostructures for catalysis and protein adsorption.

A unique nanostructure of Fe3O4 nanoparticles (NPs)-in/carbon layer/out-Ni NPs was developed and proved to be an efficient catalyst and protein adsorbent. This kind of nanostructure was formed through a space-confined pyrolysis procedure using polydopamine-Ni2+ coated Fe-NTA nanowires as the precursor. A N-doped carbon interlayer derived from polydopamine (PDA) supported a large amount of Ni NPs and entrapped well-defined Fe3O4 NPs, which were obtained through reduction of Ni2+, Fe3+ by carbonized NTA groups and a PDA layer. The contributions of the unique configuration along with the high density of Ni NPs in Fe3O4@C-Ni are significant for improving catalysis and protein adsorption performance, which is expected to be a promising alternative to other conventional catalysts and protein adsorbents. Due to the unique novel nanostructure, this nanocomposite possesses a wide range of applications, not only for catalytic reactions but also for other inhomogeneous reactions.

Radical scavenging and anti-inflammatory activities of (hetero)arylethenesulfonyl fluorides: Synthesis and structure-activity relationship (SAR) and QSAR studies.

A series of (hetero)arylethenesulfonyl fluorides (1-58) were synthesized and screened for their in vitro antioxidant (DPPH, ABTS and DMPD methods) and anti-inflammatory activities. The results revealed that compounds 4, 15, 16, 24, 25, 26, 38, 39, 40, and 54 exhibited excellent antioxidant activity using all the three performed antioxidant methods, which were superior to the standard antioxidants ascorbic acid and gallic acid. Compounds 6-9, 11, 18, 19, 21, 22, 30, 39, 40, 44, 45, 48-50, 54, 55 and 57 displayed promising anti-inflammatory activity, which were better than the reference drug indomethacin. Preliminary structure-activity relationship (SAR) revealed that compounds containing electron donating (OH and OCH3) groups on the phenyl ring possessed excellent antioxidant properties while compounds containing electron-withdrawing (Cl, NO2, F and Br) groups on the phenyl ring were found to be most potent anti-inflammatory agents. The presence of SO2F group played a crucial role in increases both antioxidant and anti-inflammatory activities.

Structural Evolution and Compositional Modulation of ZIF-8-Derived Hybrids Comprised of Metallic Ni Nanoparticles and Silica as Interlayer.

Great efforts on metal-organic framework (MOF) derived nanostructures have been devoted to modulating the compositional and structural complexities to enhance performance in various applications. However, a facile method that can simultaneously manipulate the structures of the MOF-derived material and the chemical component remains a considerable challenge. Here we report a facile strategy to use the polyhedral ZIF-8 as a precursor for synthesizing ZIF-8-derived hybrids with different components and morphologies. The synthesis involves the preparation of ZIF-8 MOF templates and sequential covering of the ZIF-8 with a interlayer of silica and then polydopamine-Ni2+ (PDA-Ni2+) and carbonizing at different high temperatures under a nitrogen atmosphere, finally leading to ZIF-8-derived hybrids with different components and structures. In the whole process, the preliminary ZIF-8 precursor play a crucial role in the morphology and structure of the final carbonized products, which can be considered as templates for silica coating and precursors of N-doped carbon layer and Zn species. We also found that the SiO2 interlayer coating is a crucial procedure for the formation of yolk-shell structured ZIF-8@SiO2@PDA-Ni2+ composites. Owing to the uniformly distributed Ni NPs and unique structures of the composites, the as-prepared Ni-based composites show high performance in the catalysis of 4-nitrophenol as well as enrichment of histidine-rich proteins. In addition, this proposed strategy for the controllable design and synthesis of ZIF-8-derived nanocomposites paves a new way in developing superior active materials in energy storage conversion etc.

Synthetic approaches and pharmaceutical applications of chloro-containing molecules for drug discovery: A critical review.

At present more than 250 FDA approved chlorine containing drugs were available in the market and many pharmaceutically important drug candidates in pre-clinical trials. Thus, it is quite obvious to expect that in coming decades there will be an even greater number of new chlorine-containing pharmaceuticals in market. Chlorinated compounds represent the family of compounds promising for use in medicinal chemistry. This review describes the recent advances in the synthesis of chlorine containing heterocyclic compounds as diverse biological agents and drugs in the pharmaceutical industries for the inspiration of the discovery and development of more potent and effective chlorinated drugs against numerous death-causing diseases.

Facile one-pot synthesis of sulfonyl fluorides from sulfonates or sulfonic acids.

A facile cascade process for directly transforming the abundant and inexpensive sulfonates (or sulfonic acids) to the highly valuable sulfonyl fluorides was developed. This new protocol features mild reaction conditions using readily available and easy-to-operate reagents. A diverse set of sulfonyl fluorides was prepared facilitating the enrichment of the sulfonyl fluoride library.

SO2F2 mediated cascade dehydrogenative Morita-Baylis-Hillman reaction of the C(sp3)-H of primary alcohols with the C(sp2)-H of electron-deficient olefins for the assembly of allylic alcohols.

A cascade dehydrogenative Morita-Baylis-Hillman reaction of the C(sp3)-H of primary alcohols with the C(sp2)-H of electron-deficient olefins for forming allylic alcohols mediated by SO2F2 was developed. This method provides a mild process for the preparation of allylic alcohol moieties without the requirement of transition metals.

Influence of carbonate on sequestration of U(VI) on perovskite.

Cubic perovskite (CaTiO3) was successfully synthesized by a facile solvothermal method and was utilized to sequestrate U(VI) from aqueous solutions. The batch experiments revealed that carbonate inhibited U(VI) sequestration at pH > 6.0 due to the formation of uranyl-carbonate complexes. The maximum sequestration capacity of U(VI) on perovskite was 119.3 mg/g (pH 5.5). The sequestration mechanism of U(VI) on perovskite were investigated by XPS and EXAFS techniques. According to XPS analysis, the presence of U(IV) and U(VI) oxidation states revealed the photocatalytic reduction of U(VI) by perovskite under UV-vis irradiation. In addition, photocatalytic reduction performance significantly decreased in the presence of carbonate. Based on EXAFS analysis, the occurrence of U-Ti and U-U shells revealed the inner-sphere surface complexation and reductive precipitation of U(VI) on perovskite. These findings herein are crucial for the application of perovskite-based composites in the decontamination of U(VI) in aquatic environmental cleanup.

Facile synthesis of metal nanoparticles decorated magnetic hierarchical carbon microtubes with polydopamine-derived carbon layer for catalytic applications.

It is highly desirable but challenging to fabricate a unique hybrid material comprising nanosized copper/cobalt/nickel nanoparticles (NPs) uniformly distributed on magnetic supports. Herein in this work, hierarchical magnetic metal silicate hollow microtubes were prepared using silica coated magnetic N-doped carbon microtubes (NCMTs@Fe3O4@SiO2) as a chemical template; then polydopamine (PDA) was employed to coat onto magnetic metal silicate carbon microtubes (NCMTs@Fe3O4@CuSNTs/CoSNTs/NiSNTs), which can be carbonized to form hierarchical hybrid composites with uniformly-dispersed metallic copper/cobalt/nickel NPs embedded in PDA-derived carbon layers (NCMTs@Fe3O4@SiO2@C/Cu-Co-Ni). Owing to its hierarchical structure, large specific surface area as well as the high density of metal NPs, the resultant NCMTs@Fe3O4@SiO2@C/Ni-Co-Cu could be applied as catalysts towards the reduction of 4-nitrophenol (4-NP). Furthermore, the NCMTs@Fe3O4@SiO2@C/Ni-Co-Cu catalysts could be easily collected and separated by applying an external magnetic field. In particular, it was found that NCMTs@Fe3O4@SiO2@C/Ni exhibited ultra-high catalytic activity on 4-NP reduction in comparison with Cu and Co supported catalysts. In addition, this unique hierarchical structure combined with magnetic recyclability make NCMTs@Fe3O4@SiO2@C/Ni a highly promising candidate for diverse applications.