Synthesis, structure, theoretical calculation and antibacterial property of two novel Zn(II)/Ni(II) compounds based on 3, 5-dichlorosalicylaldehyde thiocarbamide ligand.

Two new compounds namely [Zn(L1)phen]31 and Ni(L1)phen(MeOH) 2 (L1 = 3, 5-dichlorosalicylaldehyde thiosemicarbazone) were synthesized by the slow evaporation method at room temperature. The structure of ligand L1 was determined using 1H NMR and 13C NMR spectra. X-ray single crystal diffraction analysis revealed that compounds 1-2 can form 3D supramolecular network structures through π···π stacking and hydrogen bonding interactions. The DFT calculation shows that the coordination of ligand and metal is in good agreement with the experimental results. Hirshfeld surface analysis revealed that H…H and Cl…H interactions were the predominant interactions in compounds 1-2. Energy framework analysis indicated that dispersion energy played a dominant role in the energy composition of compounds 1-2. The inhibitory effects of compounds 1-2 against Escherichia coli (E. coli) and Methicillin-resistant Staphylococcus aureus (MRSA) were tested using the paper disk diffusion method (1: E. coli: 18 mm, MRSA: 17 mm, 2: E. coli: 15 mm, MRSA: 16 mm). Ion releasing experiments were conducted to assess the ion release capacity of compounds 1-2 (Zn2+, 4 days, 38.33 µg/mL; Ni2+, 4 days, 29.12 µg/mL). Molecular docking demonstrated the interaction modes of compounds 1-2 with UDP-N-acetylenolpyruvoylglucosamine reductase (MurB) and dihydrofolate reductase (DHFR) in bacteria, involving hydrophobic, stacking, hydrogen bonding and halogen bonding interactions. The generation of reactive oxygen species (ROS) in bacteria under the presence of compounds 1-2 were evaluated using a fluorescent dye known as dichlorodihydrofluorescein diacetate (DCFH-DA). Potential antibacterial mechanisms of compounds 1-2 were proposed.

Giant Low-Field Cryogenic Magnetocaloric Effect in a Polycrystalline EuB4O7 Compound.

To deal with the shortage and high price of helium-3 resources, adiabatic demagnetization refrigeration technology as an alternative to helium-3-based refrigeration technology has received much attention. The magnetism and ultralow-temperature magnetocaloric effect (MCE) of the EuB4O7 compound have been investigated. The results of magnetic and quasi-adiabatic demagnetization measurements suggest the absence of a magnetic order above 0.4 K for EuB4O7. The dipolar interaction between the nearest-neighbor Eu atoms has a characteristic energy of about 800 mK, which may induce a large MCE. The maximum magnetic entropy change reaches 22.8, 36.2, and 47.6 J·kg-1 K-1 at µ0H = 0-10 kOe, 0-20 kOe, and 0-50 kOe, respectively. Measurements by a quasi-adiabatic demagnetization device show that the lowest temperature achievable (289 mK) for polycrystalline EuB4O7 is lower than that (362 mK) for the commercial refrigerant Gd3Ga5O12 (GGG) single crystals. The hold time is more than 70 min below 700 mK, with an environment temperature of 2 K, proving that EuB4O7 exhibits superior cooling performance.

Metabolic engineering strategies to enable microbial electrosynthesis utilization of CO2: recent progress and challenges.

Microbial electrosynthesis (MES) is a promising technology that mainly utilizes microbial cells to convert CO2 into value-added chemicals using electrons provided by the cathode. However, the low electron transfer rate is a solid bottleneck hindering the further application of MES. Thus, as an effective strategy, genetic tools play a key role in MES for enhancing the electron transfer rate and diversity of production. We describe a set of genetic strategies based on fundamental characteristics and current successes and discuss their functional mechanisms in driving microbial electrocatalytic reactions to fully comprehend the roles and uses of genetic tools in MES. This paper also analyzes the process of nanomaterial application in extracellular electron transfer (EET). It provides a technique that combines nanomaterials and genetic tools to increase MES efficiency, because nanoparticles have a role in the production of functional genes in EET although genetic tools can subvert MES, it still has issues with difficult transformation and low expression levels. Genetic tools remain one of the most promising future strategies for advancing the MES process despite these challenges.

Embedding Mixed Sorbents in Binder: Solid-Phase Microextraction Coating with Wide Extraction Coverage and Its Application in Environmental Water Analysis.

Solid-phase microextraction (SPME) is a simple and highly effective sample-preparation technique for water analysis. However, the extraction coverage of a given SPME device with a specific coating can be an issue when analyzing multiple environmental contaminants. Therefore, instead of synthesizing one sorbent material with dual or multiple functions, we investigated a new strategy of preparing SPME blades using a homogeneous slurry made by mixing three different sorbent particles─namely, hydrophobic/lipophilic balanced (HLB), HLB-weak cationic exchange (HLB-WCX), and HLB-weak anionic exchange (HLB-WAX)─with a polyacrylonitrile (PAN) binder. The developed coating is matrix compatible, as the binder functions not only as a glue for immobilizing the sorbent particles but also as a porous filter, which only allows small molecules to enter the pores and interact with the particles, thus avoiding contamination from large elements. The results confirmed that the proposed mixed-coating SPME device provides good extraction performance for polar and nonpolar as well as positively and negatively charged compounds. Based on this device, three comprehensive analytical methodologies─high-throughput SPME-LC-MS/MS (for the quantitative analysis of targeted drugs of abuse and artificial sweeteners), in-bottle SPME-LC-high resolution MS (HRMS) (for the untargeted screening of organic contaminants), and on-site drone sampling SPME-LC-HRMS (for on-site sampling and untargeted screening)─were developed for use in environmental water analysis. The resultant data confirm that the proposed strategies enable comprehensive water quality assessment by using a single SPME device.

Metabolic regulation of Shewanella oneidensis for microbial electrosynthesis: From extracellular to intracellular.

Shewanella oneidensis MR-1 (S. oneidensis MR-1) has been shown to benefit from microbial electrosynthesis (MES) due to its exceptional electron transfer efficiency. In this study, genes involved in both extracellular electron uptake (EEU) and intracellular CO2 conversion processes were examined and regulated to enhance MES performance. The key genes identified for MES in the EEU process were mtrB, mtrC, mtrD, mtrE, omcA and cctA. Overexpression of these genes resulted in 1.5-2.1 times higher formate productivity than that of the wild-type strains (0.63 mmol/(L·µg protein)), as 0.94-1.61 mmol/(L·µg protein). In the intracellular CO2 conversion process, overexpression of the nadE, nadD, nadR, nadV, pncC and petC genes increased formate productivity 1.3-fold-3.4-fold. Moreover, overexpression of the formate dehydrogenase genes fdhA1, fdhB1 and fdhX1 in modified strains led to a 2.3-fold-3.1-fold increase in formate productivity compared to wild-type strains. The co-overexpression of cctA, fdhA1 and nadV in the mutant strain resulted in 5.59 times (3.50 mmol/(L·µg protein)) higher formate productivity than that of the wild-type strains. These findings revealed that electrons of MES derived from the electrode were utilized in the energy module for synthesizing ATP and NADH, followed by the synthesis of formate in formate dehydrogenase by the combinatorial effects of ATP, NADH, electrons and CO2. The results provide new insights into the mechanism of MES in S. oneidensis MR-1 and pave the way for genetic improvements that could facilitate the further application of MES.

A Joint Johnson-Cook-TANH Constitutive Law for Modeling Saw-Tooth Chip Formation of Ti-6AL-4V Based on an Improved Smoothed Particle Hydrodynamics Method.

Titanium alloy is a crucial structural material in the modern aerospace field due to its strong corrosion resistance and strength, low density, and reduced sensitivity to vibration load and impact load, as well as its ability to resist expansion in the case of cracks. However, during high-speed cutting of titanium alloy, it is prone to periodic saw-tooth chip formation, which can cause high-frequency fluctuations in the cutting force, aggravate the vibration of the machine tool system, and ultimately reduce the tool's service life and the workpiece's surface quality. In this study, we investigated the influence of the material constitutive law in modeling the Ti-6AL-4V saw-tooth chip formation and proposed a joint material constitutive law JC-TANH which was developed based on the Johnson-Cook constitutive law and the TANH constitutive law. It has two advantages of the two models (JC law and TANH law), which means that it can describe the dynamic properties accurately, the same as the JC model, not only under low strain but also under high strain. The most important thing is that it does not need to fit the JC curve at the early stage of strain changes. Additionally, we established a developed cutting model, which integrates the new material constitutive, and the improved SPH method to predict chip morphology, cutting and thrust forces which are collected by the force sensor; we also compared the data with experimental results. Experimental results show that this developed cutting model can better explain the shear localized saw-tooth chip formation and correctly estimate its morphology as well as the cutting forces.

Interactions between arsenic migration and CH4 emission in a soil bioelectrochemical system under the effect of zero-valent iron.

Dissimilatory soil arsenic (As) reduction and release are driven by microbial extracellular electron transfer (EET), while reverse EET mediates soil methane (CH4) emission. Nevertheless, the detailed biogeochemical mechanisms underlying the tight links between soil As migration and methanogenesis are unclear. This study used a bioelectrochemical-based system (BES) to explore the potential effects of zero-valent iron (ZVI) addition on "As migration-CH4 emission" interactions from chemical and microbiological perspectives. Voltage and ZVI amendment experiments showed that dissolved As was efficiently immobilized with increased CH4 production in the soil BES, As release and CH4 production exhibited a high negative exponential correlation, and reductive As dissolution could be entirely inhibited in the methanogenic stage. Gene quantification and bacterial community analysis showed that in contrast to applied voltage, ZVI changed the spatial heterogeneity of the distribution of electroactive microorganisms in the BES, significantly decreasing the relative abundance of arrA and dissimilatory As/Fe-reducing bacteria (e.g., Geobacter) while increasing the abundance of aceticlastic methanogens (Methanosaeta), which then dominated CH4 production and As immobilization after ZVI incorporation. In addition to biogeochemical activities, coprecipitation with ferric (iron) contributed 77-93% dissolved As removal under ZVI addition. This study will enhance our knowledge of the processes and microorganisms controlling soil As migration and CH4 emission.

Sequential Solid-Phase Microextraction with Biocompatible Coating Materials to Address Displacement Effects in the Quantitative Analysis.

Solid-phase microextraction (SPME) is a simple and effective sample-preparation technique for the analysis of complex samples. However, sample matrices containing high concentrations of nonpolar substances or spiked analytes in free form can cause swelling, saturation, and/or competition phenomena in the coating material. This results in a displacement effect wherein polar analytes with low affinities for the solid coating material are displaced by nonpolar substances in the matrix or spiked analytes with a high affinity. Therefore, the quantitative analysis of polar analytes can be challenging, as the displacement effect causes non-linearity in the calibration curves. This paper presents a comprehensive investigation of the conditions under which the displacement effect occurs and how it influences the quantitative analysis of polar analytes. To remedy this issue, a sequential SPME strategy using two SPME blades with different selectivities is applied. SPME blades offer a large surface area and coating volume─and thus, greater extraction capacity─which may mitigate the displacement effect. In addition, the biocompatible coatings on the SPME blades are comprised of small amounts of sorbent particles embedded by a polyacrylonitrile (PAN) binder, which allows them to be directly immersed into complex matrixes such as biological and food samples, as the PAN acts as a barrier that prevents the adsorption of large macromolecules (e.g., cells and proteins). As such, a C18/PAN-coated blade was applied for the first extraction step, which significantly decreased the concentrations of nonpolar compounds in the sample. In the second step, a hydrophilic-lipophilic balanced (HLB)/PAN-coated blade was employed to extract the polar analytes and any remaining nonpolar analytes. The proposed sequential SPME strategy successfully enabled the quantitative determination of polar and nonpolar drugs of abuse with log P values ranging from 0.16 to 4.98 in biological matrices while also providing good linearities.

Continuous fixation of dissolved arsenite from flooded soil by cooperating ferrihydrite with Geobacter sulfurreducens.

The fixed arsenic in soil is easy to be released into the aquatic environment in the form of arsenite (As(III)) with high toxicity and mobility due to the eutrophication of environment under anaerobic conditions. However, As(III) is difficult to be fixed in situ continuously by traditional methods, especially for the most efficient fixation method by iron ores. Based on that Fe(II) could promote the fixation of As(III), this study investigated the possibility that Geobacter sulfurreducens (G. sulfurreducens) cooperates with ferrihydrite to fix released As(III) from flooded soil in a glass column continuously under anaerobic conditions. During 42 days of operation of reactors that simulated the actual flooded soil environment, the concentration of released As(III) in the reactor with adding G. sulfurreducens and ferrihydrite is always lower than that in reactors with adding ferrihydrite or no treatment. Compared with reactors without treatment, the accumulated content of released As(III) (2455.0 ± 313.1 µg) decreased by 39.4% in the reactor with adding G. sulfurreducens and ferrihydrite on the last day, while that in reactors with adding ferrihydrite only decreased by 11.6%, respectively. These were caused by the cooperation of G. sulfurreducens and ferrihydrite, which increased the relative abundance of iron-reducing microorganisms to inhibit metabolisms of As-reducing microorganisms, inhibited the quick release of As(III) from solid soil, and promoted the release of iron to accelerate the formation of stable secondary ores with As. This study could provide an environmentally friendly method to fix dissolved As(III) pollutants from soil continuously.

Dispersive solid-phase extraction of non-steroidal anti-inflammatory drugs in water and urine samples using a magnetic ionic liquid hypercrosslinked polymer composite.

In this work, Friedel-Crafts alkylation was successfully applied to prepare a magnetic ionic liquid hypercrosslinked polymer composite (Fe3O4@IL-HCP), which was subsequently employed as magnetic solid-phase extraction (MSPE) adsorbent for the isolation and enrichment of trace non-steroidal anti-inflammatory drugs (NSAIDs). The developed composite was comprehensively characterized using various techniques, with the results indicating that it possessed high saturation magnetization (39.44 em g - 1), large specific surface area (175 m2g - 1), and high adsorption capacity for NSAIDs. The adsorption behavior and mechanisms were also investigated in detail. NSAIDs were adsorbed onto the Fe3O4@IL-HCP sorbent via a heterogeneous multilayer process consisting of hydrogen bonding and π-π and electrostatic interactions. Additionally, the composite's large surface area and multiple active sites enabled extraction equilibrium within 6 min. By coupling with high performance liquid chromatography (HPLC), the developed MSPE/HPLC method was applied for the determination of selected NSAIDs in water and urine samples. The developed method displayed wide linear ranges, low limits of detection (0.12-0.30 ng mL-1 and 0.15-1.5 ng mL-1 in water and urine samples, respectively), sufficient recoveries (92.8-109%), and good precision (relative standard deviations ≤ 4.6%). Thus, the findings of this work provide an appealing alternative for the extraction and determination of trace NSAIDs in environmental water and biological samples.

As(III) oxidation and kinetic analysis by Herminiimonas arsenicoxydans-loaded electrospinning activated carbon fiber biofilms.

In this study, an integrated and assembled recyclable biofilm material was prepared by loading Herminiimonas arsenicoxydans (H. arsenicoxydans) onto electrospun biomass-activated carbon nanofibers (denoted as H. arsenicoxydans-BACFs films). The H. arsenicoxydans-BACFs biofilms showed an approximately 50% increase in As(III) removal rate for 50 mg/L during a 48-h incubation. Furthermore, the biofilms demonstrated satisfactory biocompatibility, ideal catalytic As(III) oxidation and excellent recyclability in cyclic reactions (at least 5 runs). The improved catalytic efficiency is mainly due to a large amount of biomass accumulation and biofilms formation on the surface of the BACF films. More important, the BACF films as an electron transport medium from an oxidized state to a reduced state promote the electron transfer of As(III) oxidation of H. arsenicoxydans. The dual factors can synergistically promote As(III) oxidation efficiency. The oxidation process of As(III) in the H. arsenicoxydans-BACFs composite biofilm reactor was more in line with the first-order kinetic equation, and the oxidation rate of As(III) by H. arsenicoxydans-BACF0.4 was the fastest. The H. arsenicoxydans-BACF films outperformed conventional catalytic materials and could represent biomaterials for the remediation of As(III)-contaminated wastewater.

ω-3 and ω-6 Polyunsaturated Fatty Acids Regulate the Proliferation, Invasion and Angiogenesis of Gastric Cancer Through COX/PGE Signaling Pathway.

BACKGROUND: This study aims to investigate the effects of ω-3, ω-6 polyunsaturated fatty acids (PUFAs), and their middle metabolites prostaglandin (PGE)2 and PGE3 on proliferation, invasion, and angiogenesis formation of gastric cancer cells and to explore associated mechanism. METHODS: RT-PCR and ELISA were used to detect the expression of cyclooxygenase (COX)-1 and COX-2 in gastric cancer cell lines. The effect of ω-3, ω-6, PGE2, and PGE3 on the proliferation, invasion, and angiogenesis of gastric cancer cells were measured by cell proliferation, invasion, and angiogenesis assay in vitro. COX-2 small interfering RNA (siRNA) was transfected into gastric cancer cells, and the expression of COX-2 protein was detected by Western blot. COX-2 gene silencing influencing proliferation, invasion, and angiogenesis potential of gastric cancer cells was detected by WST-1, transwell chamber, and angiogenesis assay, respectively. RESULTS: COX-2 was only expressed in MKN74 and MKN45 cells. In gastric cancer cell lines with positive COX-2 expression, ω-6 and PGE2 could significantly enhance the proliferation, invasion, and angiogenesis of gastric cancer cells, and after transfection with COX-2 siRNA, the effects of ω-6 and PGE2 on enhancing the proliferation, invasion, and angiogenesis of gastric cancer cells were significantly attenuated; ω-3 and PEG3 could inhibit the proliferation, invasion, and angiogenesis of gastric cancer cells. In gastric cancer cell lines with negative COX-2 expression, ω-6 and PGE2 had no significant effect on the proliferation, invasion, and angiogenesis of gastric cancer; ω-3 and PGE3 could significantly inhibit the proliferation, invasion, and angiogenesis of gastric cancer. CONCLUSION: ω-6 PUFAs reinforce the metastatic potential of gastric cancer cells via COX-2/PGE2; ω-3 PUFAs inhibit the metastatic potential of gastric cancer via COX-1/PGE3 signaling axis.

An outer membrane photosensitized Geobacter sulfurreducens-CdS biohybrid for redox transformation of Cr(VI) and tetracycline.

Microbe-photocatalyst biohybrids, integrating the optimal attributes of whole-cell catalysts and nanometer photocatalysts, have emerged as a promising strategy for environment-associated applications. However, few such biohybrids have been tested for complex pollution systems. Herein, we constructed an outer membrane photosensitized Geobacter sulfurreducens (G. sulfurreducens)-CdS biohybrid, which enabled to generate stronger photocurrent in response to irradiation and meanwhile achieved an significant promotion for the redox transformation of Cr(VI) and tetracycline compared with that of bare G. sulfurreducens or CdS counterparts. Further analysis revealed that the outer membrane played a significant role in photoelectron transfer. Differential pulse voltammetry (DPV) tests demonstrated that CdS enhanced the catalytic activity of C-type cytochromes on the outer membrane under irradiation, resulting in the increase of electron-hole pairs separation efficiency. The possible degradation pathway of tetracycline was proposed based on determined intermediates, whose toxicities were well evaluated. Importantly, the toxicity of the final detected intermediates was apparently decreased. Overall, this work aims to explore the working mechanisms of the novel G. sulfurreducens-CdS biohybrid system and opens up a new avenue to purifying combined wastewater by microbe-photocatalyst biohybrids.

Immobilization and redistribution process of As(V) during As(V)-bearing ferrihydrite reduction by Geobacter sulfurreducens under the influence of TiO2 nanoparticles.

The redistribution process of arsenate (As(V)) and the variation in As(V) content in different locations must be clarified to ensure low mobility of As(V) during microbial ferrihydrite reduction. In this study, we investigated As(V) immobilization and redistribution processes when ferrihydrite was incubated with Geobacter sulfurreducens in the presence of titanium dioxide (TiO2) nanoparticles. Our study results showed that, As(V) in the aqueous phase and ferrihydrite were redistributed on light minerals (goethite), heavy minerals (ferrihydrite and magnetite), and extracellular polymeric substances (EPS) induced by G. sulfurreducens during ferrihydrite reduction. Interestingly, we found that As(V) in the form of arsenate ion (AsO43-) was adsorbed by the functional groups of the EPS, while the formed FeII3(AsVO4)2 was wrapped in the network structure of EPS. Moreover, the addition of TiO2 nanoparticles did not promote but delayed the entire ferrihydrite reduction, As(V) immobilization and redistribution processes. Furthermore, changes in the aqueous arsenic and iron concentrations are closely related to the formation time of secondary minerals. Our study findings provide new insights into the As(V) immobilization process mediated by G. sulfurreducens under anaerobic conditions.

3D printing of recombinant Escherichia coli/Au nanocomposites as agitating paddles towards robust catalytic reduction of 4-nitrophenol.

Three-dimensional (3D) printing technology has received remarkable attention in manufacturing catalysts with tailored shapes and high precision, particularly facilitating catalyst recovery, maximizing heat/mass transfer, as well as enhancing catalytic performance. Herein, an engineered recombinant Escherichia coli strain (denoted as e-E. coli) with overexpressing metallothionein (a metal-binding protein) was explored to synthesize Au nanoparticles serving as both reducing and stabilizing agents. Then, the mixed inks containing e-E. coli/Au composite and biocompatible polymers (sodium alginate and gelatin) were extruded based on a direct ink writing method followed by chemical crosslinking to form robust 3D grids with square symmetry. To boost the mass transfer and minimize pressure drop, the monolith catalysts were assembled into agitating paddles and used for liquid-phase batch reactions (volume: 1 L). As such, the reaction solutions were mixed internally via the powered "catalytic paddles" with high mechanical strength, excellent reactivity, and easy recyclability, which could be reused at least 7 cycles without performance loss. Our work provides a novel strategy for the fabrication of supported Au catalysts, and the proof-of-concept "catalytic paddles" by 3D printing technology can be applied to other industrial solution-based reactions.

Physiochemical properties, heavy metal leaching characteristics and reutilization evaluations of solid ashes from municipal solid waste incinerator plants.

A clear understanding of the physicochemical, compositional, morphological properties and heavy metal leaching behaviours of municipal solid waste (MSW) incinerated fly ash (FA) and bottom ash (BA) are essential to guide their respective re-utilizations. In this study, FA and BA collected from three MSW incinerator plants located in Xiamen were systematically exploited. Results indicated that FA in the three plants exhibited more porous structures than BA, and the particle sizes of FA and BA were 45-295 µm and >3000 µm, respectively. However, both ashes showed similar main mineralogical crystalline phases of Ca(OH)2, CaCO3 and SiO2, indicative of high feasibilities in manufacturing cement, bricks or construction materials. Additionally, the heavy metal migration of MSW into leachate, flue gas, FA and BA were all specifically measured in this study to provide full data analyses and in-depth understandings of heavy metal migrations, manifesting that the heavy metals of MSW majorly migrated into the FA and BA with clearly discrepant metal ratios and only a very small fraction migrated into the leachate and flue gas. To maximumly reuse both FA and BA, importantly, the green degree and cost-benefit analysis methods were integrated into this study to evaluate their re-utilization alternatives on environmental impacts and economic benefits, and results implied that FA was beneficial for re-utilizing as aggregates in bricks while BA was optimum as paving materials. This study provides overall systematic perspectives on guiding the re-utilization of FA/BA from the MSW incinerators and also considers their environmental and economic benefits for future long-term management.

Co-oxidative removal of arsenite and tetracycline based on a heterogeneous Fenton-like reaction using iron nanoparticles-impregnated biochar.

A highly efficient, eco-friendly and relatively low-cost catalyst is necessary to tackle bottlenecks in the treatment of industrial wastewater laden with heavy metals and antibiotic such as livestock farm and biogas liquids. This study investigated co-oxidative removal of arsenite (As(III)) and tetracycline (TC) by iron nanoparticles (Fe NP)-impregnated carbons based on heterogeneous Fenton-like reactions. The composites included Fe NP@biochar (BC), Fe NP@hydrochar (HC), and Fe NP@HC-derived pyrolysis char (HDPC). The functions of N and S atoms and the loading mass of the Fe NP in the Fe NP@BC in heterogeneous Fenton-like reactions were studied. To sustain its cost-effectiveness, the spent Fe NP@BC was regenerated using NaOH. Among the composites, the Fe NP@BC achieved an almost complete removal of As(III) and TC under optimized conditions (1.0 g/L of dose; 10 mM H2O2; pH 6; 4 h of reaction; As(III): 50 µM; TC: 50 µM). The co-oxidative removal of As(III) and TC by the Fe NP@ BC was controlled by the synergistic interactions between the Fe NPs and the active N and S sites of the BC for generating reactive oxygen species (ROS). After four consecutive regeneration cycles, about 61 and 95% of As(III) and TC removal were attained. This implies that the spent carbocatalyst still has reasonable catalytic activities for reuse. Overall, this suggests that adding technological values to unused biochar as a carbocatalyst like Fe NP@BC was promising for co-oxidative removal of As(III) and TC from contaminated water.

Effects of anode/cathode electroactive microorganisms on arsenic removal with organic/inorganic carbon supplied.

This study reports the effects of an external voltage (0 V, 0.4 V and 0.9 V) on soil arsenic (As) release and sequestration when amended with organic carbon (NaAc) and inorganic carbon (NaHCO3), respectively, in a soil bioelectrochemistry system (BES). The results demonstrated that although an external voltage had no effect on the As removal capacity in an oligotrophic environment fueled with NaHCO3, 93.6% of As(III) in the supernatant was removed at 0.9 V with an NaAc amendment. Interestingly, the content of As detected on the electrodes was higher than that removed from the supernatant, implying a continuous release of soil As under external voltages and rapid adsorption onto the electrodes, especially the cathode. In addition, the species of As on the cathode were similar to those in the supernatant (the As(III)/As(V) ratio was approximately 3:1), indicating that the removal capacity was independent of preoxidation. From the viewpoint of electroactive microorganisms (EABs), the relative abundances of the arrA gene and Geobacter genus were specifically enriched at the anode, thus signifying stimulation of the reduction and release of soil As in the anode region. By comparison, Bacillus was particularly abundant at the cathode, which could contribute to the oxidation and sequestration of As in the cathode region. Additionally, specific extracellular polymeric substances (EPSs) secreted by EABs could combine with As, which was followed by electrostatic attraction to the cathode under the effect of an electric field. Furthermore, the formation of secondary minerals and coprecipitation in the presence of iron (Fe) may have also contributed to As removal from solution. The insights from this study will enable us to further understand the biogeochemical cycle of soil As and to explore the feasibility of in situ As bioremediation techniques, combining the aspects of microbial and physicochemical processes in soil bioelectrochemical systems.

Strategy of Graphdiyne (g-Cn H2n-2 ) Preparation Coupling with the Flower-Like NiAl-LDH Heterojunctions for Efficient Photocatalytic Hydrogen Evolution*.

Graphdiyne (g-Cn H2n-2 ), a novel two-dimension carbon allotrope material composed of a sp- and sp2 -hybrid carbon network, has been widely explored since it was synthesized for the first time by Li's group in 2010. A series distinct and excellent properties bestow graphdiyne excellent performance in many fields. Here, an innovative progress for preparing graphdiyne by using Cu+ contained material as catalyst is reported and the composite CuI-GD is coupled with flower-like NiAl-LDH to produce H2 from photocatalytic water splitting. The results of FTIR and Raman spectroscopy together reveal that graphdiyne nanosheets are synthesized successfully by employing a cross-coupling method. Photocatalytic hydrogen evolution performance shows that the hydrogen production activity of CuI-GD/NiAl-LDH has a 15- and 216-fold enhancement compared with CuI-GD and NiAl-LDH, respectively. A series of characterizations are carried out to expound the underlying reasons in the enhancement of the photocatalytic hydrogen production performance of CuI-GD/NiAl-LDH. Meanwhile, a possible mechanism for the photocatalytic hydrogen evolution process was proposed to understand the interaction among these materials.

Effects of substrate types on the transformation of heavy metal speciation and bioavailability in an anaerobic digestion system.

Chemical speciation can fundamentally affect the potential toxicity and bioavailability of heavy metals. The transformation of heavy metal speciation and change of bioavailability were investigated in an anaerobic digestion (AD) system using four different substrates (pig manure (PM), cattle manure (CAM), chicken manure (CHM) and rice straw (RS)). The results obtained indicated that the total contents of heavy metals in PM, CHM and CAM were higher than in RS and decreased in the order Zn > Cu > Ni > Pb > As > Cd in all substrates. Moreover, the speciation with the largest proportion for each heavy metal was the same both in the different substrates and the biogas residues. Among them, Zn, Ni, Cd and As were mainly in the reducible fraction (F2), while Cu was mainly in the oxidizable fraction (F3) and Pb occurred predominantly in the residual fraction (F4). Our results further indicated that the AD process had a greater effect on the speciation of heavy metals in CHM and PM, but less on CAM and RS. The rates of change in bioavailability followed the order PM > CHM > CAM > RS. Changes in organic matter, humic acid or local metal ion environment as a result of AD were inferred as likely mechanisms leading to the transformation of heavy metal speciation. These results enhanced our understanding of the behavior of heavy metals in AD and provided a new perspective for the treatment and disposal of the substrates.