Atomically Dispersed Cobalt Anchored on Hollow Tubular Carbon Nitride Mediates Direct Electron Transfer and Oxygen-Related Active Species Path for Activation of Permonosulfate.

Atomically dispersed catalysts anchored on nitrogen-rich substrates present promising application potential for the persulfate-based advanced oxidation process. Nevertheless, efficient activation efficiency and a clear activated mechanism of persulfate remain challenging in carbon nitride-based single-atom catalysts (SACs). To these, combined with the regulation strategy of metal-ligand section and carrier's architecture, an atomically dispersed Co single-atom catalyst anchored on regular hollow tubular carbon nitride (Co/TCN SAC) herein was devised and utilized to activate permonosulfate. As a result, Co/TCN SACs show excellent catalytic performance for the degradation of common antibiotics. Combined with X-ray absorption fine structure and theory calculation, it is confirmed that superficially anchored CoO3 sites of the Co2N2O2-CoO3 unit are the catalytic active center for peroxymonosulfate (PMS) activation. The electrochemical test and in situ electron paramagnetic resonance results demonstrate radical (SO4•- and •OH) and nonradical (electron transfer process and 1O2) paths contributing to the superior catalytic performance. In addition, the catalyst exhibits high reaction efficiency and structural stability considering water quality parameters. Finally, a continuous and efficient device was operated on a laboratory scale, which exhibited satisfactory efficiency in continuously removing electron-rich antibiotics such as tetracycline. This work reveals the atomic-level modulation of cobalt atomic sites on hollow tubular carbon nitride and their structure-activity relationship with persulfate activation.

Effect of Chemical Composition of Metal-Organic Crosslinker on the Properties of Fracturing Fluid in High-Temperature Reservoir.

To investigate the effect of the chemical composition of a metal-organic crosslinker on the performances of fracturing fluid in high-temperature conditions, four zirconium (Zr) crosslinkers and one aluminum-zirconium (Al-Zr) crosslinker with a polyacrylamide were used. The crosslinkers possessed the same Zr concentration, but they differed in component amounts and the order of the addition of the crosslinker components, leading to different chemical compositions in the crosslinkers. The fracturing fluids prepared by different tested crosslinkers were compared in terms of properties of rheological behavior, sand-carrying ability, microstructure, and gel breaking characteristics. The results showed that the fracturing fluids prepared by zirconium lactic acid, ethanediamine, and sorbitol crosslinkers offered the slowest viscosity development and highest final viscosity compared to the zirconium lactic acid crosslinker and the zirconium lactic acid and ethanediamine crosslinker. The zirconium sorbitol, lactic acid, and ethanediamine crosslinker exhibited a faster crosslinking rate and a higher final viscosity than the zirconium lactic acid, ethanediamine, and sorbitol crosslinker; the crosslinker showed crosslinking density and crosslinking reactivity, resulting in more crosslinking sites and a higher strength in the fracturing fluid. The Al-Zr-based crosslinker possessed better properties in temperature and shear resistance, viscoelasticity, shear recovery, and sand-carrying ability than the Zr-based crosslinker due to the synergistic crosslinking effect of aluminum and zirconium ions. The tertiary release gelation mechanism of the Al-Zr-based fracturing fluid achieved a temperature resistance performance in the form of continuous crosslinking, avoiding the excessive crosslinking dehydration and reducing viscosity loss caused by early shear damage. These results indicated that the chemical compositions of metal-organic crosslinkers were important factors in determining the properties of fracturing fluids. Therefore, the appropriate type of crosslinker could save costs without adding the additional components required for high-temperature reservoirs.

Rational design and application of broad-spectrum antibodies for Bt Cry toxins determination.

Using the amino acid sequences and analysis of selected known structures of Bt Cry toxins, Cry1Ab, Cry1Ac, Cry1Ah, Cry1B, Cry1C and Cry1F we specifically designed immunogens. After antibodies selection, broad-spectrum polyclonal antibodies (pAbs) and monoclonal antibody (namely 1A0-mAb) were obtained from rabbit and mouse, respectively. The produced pAbs displayed broad spectrum activity by recognizing Cry1 toxin, Cry2Aa, Cry2Ab and Cry3Aa with half maximal inhibitory concentration (IC50) values of 0.12-9.86 µg/mL. Similarly, 1A0-mAb showed broad spectrum activity, recognizing all of the above Cry protein (IC50 values of 4.66-20.46 µg/mL) with the exception of Cry2Aa. Using optimizations studies, 1A10-mAb was used as a capture antibody and pAbs as detection antibody. Double antibody sandwich enzyme-linked immunosorbent assays (DAS-ELISAs) were established for Cry1 toxin, Cry2Ab and Cry3Aa with the limit of detection (LOD) values of 2.36-36.37 ng/mL, respectively. The present DAS-ELISAs had good accuracy and precisions for the determination of Cry toxin spiked tap water, corn, rice, soybeans and soil samples. In conclusion, the present study has successfully obtained broad-spectrum pAbs and mAb. Furthermore, the generated pAbs- and mAb-based DAS-ELISAs protocol can potentially be used for the broad-spectrum monitoring of eight common subtypes of Bt Cry toxins residues in food and environmental samples.

Characterization of the individual domains of the Bacillus thuringiensis Cry2Aa implicates Domain I as a possible binding site to Helicoverpa armigera.

Bacillus thuringiensis (Bt) Cry2Aa is a member of the Cry pore-forming, 3-domain, toxin family with activity against both lepidopteran and dipteran insects. Although domains II and III of the Cry toxins are believed to represent the primary specificity determinant through specific binding to cell receptors, it has been proposed that the pore-forming domain I of Cry2Aa also has such a role. Thus, a greater understanding of the functions of Cry2Aa's different domains could potentially be helpful in the rational design of improved toxins. In this work, cry2Aa and its domain fragments (DI, DII, DIII, DI-II and DII-DIII) were subcloned into the vector pGEX-6P-1 and expressed in Escherichia coli. Each protein was recognized by anti-Cry2Aa antibodies and, except for the DII fragment, could block binding of the antibody to Cry2Aa. Cry2Aa and its DI and DI-II fragments bound to brush border membrane vesicles (BBMV) from H. armigera and also to a ca 150 kDa BBMV protein on a far western (ligand) blot. In contrast the DII, DIII and DII-III fragments bound to neither of these. None of the fragments were stable in H. armigera gut juice nor showed any toxicity towards this insect. Our results indicate that contrary to the general model of Cry toxin activity domain I plays a role in the binding of the toxin to the insect midgut.

Acceleration of the biodegradation of cationic polyacrylamide by the coupling effect of thermophilic microorganisms and high temperature in hyperthermophilic composting.

As a flocculant of sewage sludge, cationic polyacrylamide (CPAM) enters the environment with sludge and exists for a long time, posing serious threats to the environment. Due to the environmental friendliness and high efficiency in the process of organic solid waste treatment, hyperthermophilic composting (HTC) has received increasing attention. However, it is still unclear whether the HTC process can effectively remove CPAM from sludge. In this study, the effects of HTC and conventional thermophilic composting (CTC) on CPAM in sludge were compared and analyzed. At the end of HTC and CTC, the concentrations of CPAM were 278.96 mg kg-1 and 533.89 mg kg-1, respectively, and the removal rates were 72.17% and 46.61%, respectively. The coupling effect of thermophilic microorganisms and high temperature improved the efficiency of HTC and accelerated the biodegradation of CPAM. The diversity and composition of microbial community changed dramatically during HTC. Geobacillus, Thermobispora, Pseudomonas, Brevundimonas, and Bacillus were the dominant bacteria responsible for the high HTC efficiency. To our knowledge, this is the first study in which CPAM-containing sludge is treated using HTC. The ideal performance and the presence of key microorganisms revealed that HTC is feasible for the treatment of CPAM-containing sludge.

Screening and Identification of Anti-Idiotypic Nanobody Capable of Broad-Spectrum Recognition of the Toxin Binding Region of Lepidopteran Cadherins and Mimicking Domain II of Cry2Aa Toxin.

The widespread use of Bacillus thuringiensis toxins as insecticides has brought about resistance problems. Anti-idiotypic nanobody approaches provide new strategies for resistance management and toxin evolution. In this study, the monoclonal antibody generated against the receptor binding region Domain II of Cry2Aa toxin was used as a target to screen materials with insecticidal activity. After four rounds of screening, anti-idiotypic nanobody 1C12 was obtained from the natural alpaca nanobody phage display library. To better analyze the activity of 1C12, soluble 1C12 was expressed by the Escherichia coli BL21 (DE3). The results showed that 1C12 not only binds the midgut brush border membrane vesicles (BBMV) of two lepidopteran species and cadherin CR9-CR11 of three lepidopteran species but also inhibits Cry2Aa toxins from binding to CR9-CR11. The insect bioassay showed that soluble 1C12 caused 25.65% and 23.61% larvae mortality of Helicoverpa armigera and Plutella xylostella, respectively. Although 1C12 has low insecticidal activity, soluble 1C12 possesses the ability to screen a broad-spectrum recognition of the toxin binding region of lepidopteran cadherins and can be used for the identification of the toxin binding region of other lepidopteran cadherins and the subsequent evolution of Cry2Aa toxin. The present study demonstrates a new strategy to screen for the production of novel insecticides.

Generation of anti-idiotypic antibodies mimicking Cry2Aa toxin from an immunized mouse phage display library as potential insecticidal agents against Plutella xylostella.

This study tried to generate anti-idiotypic antibodies (Ab2s) which mimic Cry2Aa toxin using a phage-display antibody library (2.8 × 107 CFU/mL). The latter was constructed from a mouse immunized with F (ab')2 fragments digested from anti-Cry2Aa polyclonal antibodies. The F (ab')2 fragments and Plutella xylostella (P. xylostella) brush border membrane vesicles (BBMV) were utilized as targets for selection. Eight mouse phage-display single-chain variable fragments (scFvs) were isolated and identified by enzyme-linked immunoassay (ELISA), PCR and DNA sequencing after four rounds of biopanning. Among them, M3 exhibited the highest binding affinity with F (ab')2, while M4 bound the best with the toxin binding region of cadherin of P. xylostella (PxCad-TBR). Both of these two fragments were chosen for prokaryotic expression. The expressed M3 and M4 proteins with molecular weights of 30 kDa were purified. The M4 showed a binding affinity of 29.9 ± 2.4 nM with the PxCad-TBR and resulted in 27.8 ± 4.3 % larvae mortality against P. xylostella. Computer-assisted molecular modeling and docking analysis showed that mouse scFv M4 mimicked some Cry2Aa toxin binding sites when interacting with PxCad-TBR. Therefore, anti-idiotypic antibodies generated by BBMV-based screening could be useful for the development of new bio-insecticides as an alternative to Cry2Aa toxin for pest control.

Establishment of novel receptor-antibody sandwich assays to broadly detect Bacillus thuringiensis Cry1 and Cry2 toxins.

Bacillus thuringiensis (Bt) Cry toxins have been widely used in the development of genetically modified organisms (GMOs) for pest control. This work aimed to establish more cost effective and broader detection methods for commonly used Cry toxins. Using ligand blot and bio-layer interferometry, we confirmed that a recombinant toxin-binding fragments derived from Helicoverpa armigera cadherin-like protein (HaCad-TBR) could broadly bind Cry1Ab, Cry1Ac, Cry2Aa, and Cry2Ab with the affinity of 0.149, 0.402, 120, and 4.12 nM, respectively. Based on the affinity results, a novel receptor-antibody sandwich assay broadly detecting Cry1A and Cry2 toxins was developed by using HaCad-TBR as capture molecules, and anti-Cry1A/Cry2A polyclonal antibodies (pAbs) as the detection antibodies. The detection limit (LOD) for Cry1Ab, Cry1Ab, Cry2Aa, and Cry2Ab were 5.30, 5.75, 30.83 and 13.70 ng/mL. To distinguish Cry1A and Cry2A toxins in a singular test, anti-Cry1A pAbs and anti-Cry2A pAbs were labelled with different quantum dots (QDs). The LOD for the four toxins by receptor-QDs-pAbs sandwich assay were calculated to be 1.36, 4.71, 17.48, and 7.54 ng/mL, respectively. The two developed methods were validated by spiked rice and corn samples, suggesting they may potentially be used in monitoring and quantifying Cry toxins in food and environment.

Establishment of monoclonal antibody and scFv immuno-based assay for Cry2Aa toxin in spiked grain samples.

Bacillus thuringiensis (Bt) Cry toxins have been widely used in the development of genetically modified organisms (GMOs) for pest control. This work aimed to establish more cost effective methods for used Cry2Aa toxins. Three immunoassay methods (IC-ELISA, DAS-ELISA, and CLEIA) were successfully developed in this work. The mAb was used as the detecting antibody, for the IC-ELISA, the range of IC20 to IC80 was 1.11 µg/mL - 60.70 µg/mL, and an IC50 of 10.65 µg/mL. For the DAS-ELISA, the limit of detection (LOD) and limit of quantitation (LOQ) were 10.76 ng/mL and 20.70 ng/mL, respectively. For the CLEIA, the LOD and LOQ were 6.17 ng/mL and 7.40 ng/mL, respectively. The scFv-based detections were the most sensitive for detecting Cry2Aa. The LOD and LOQ for the DAS-ELISA were 118.75 ng/mL and 633.48 ng/mL, respectively. The LOD and LOQ for the CLEIA, read as 37.47 ng/mL and 70.23 ng/mL, respectively. The fact that Cry2Aa toxin was recovered in spiked grain samples further demonstrated that the approaches might be used to identify field samples. These methods provided good sensitivity, stability, and applicability for detecting Cry2Aa toxin, promising ultrasensitive monitoring and references for Cry toxins risk assessment.

Fracturing Fluid Polymer Thickener with Superior Temperature, Salt and Shear Resistance Properties from the Synergistic Effect of Double-Tail Hydrophobic Monomer and Nonionic Polymerizable Surfactant.

To develop high-salinity, high-temperature reservoirs, two hydrophobically associating polymers as fracturing fluid thickener were respectively synthesized through aqueous solution polymerization with acrylamide (AM), acrylic acid (AA), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), nonionic polymerizable surfactant (NPS) and double-tail hydrophobic monomer (DHM). The thickener ASDM (AM/AA/AMPS/NPS/DHM) and thickener ASD (AM/AA/AMPS/DHM) were compared in terms of properties of water dissolution, thickening ability, rheological behavior and sand-carrying. The results showed that ASDM could be quickly diluted in water within 6 min, 66.7% less than that of ASD. ASDM exhibited salt-thickening performance, and the apparent viscosity of 0.5 wt% ASDM reached 175.9 mPa·s in 100,000 mg/L brine, 100.6% higher than that of ASD. The viscosity of 0.5 wt% ASDM was 85.9 mPa·s after shearing for 120 min at 120 °C and at 170 s-1, 46.6% higher than that of ASD. ASDM exhibited better performance in thickening ability, viscoelasticity, shear recovery, thixotropy and sand-carrying than ASD. The synergistic effect of hydrophobic association and linear entanglement greatly enhancing the performance of ASDM and the compactness of the spatial network structure of the ASDM was enhanced. In general, ASDM exhibited great potential for application in extreme environmental conditions with high salt and high temperatures.

Comparative Studies on Thickeners as Hydraulic Fracturing Fluids: Suspension versus Powder.

To overcome the problems of long dissolution time and high investment in surface facilities of powder thickeners in hydraulic fracturing, a novel suspension of a thickener as a fracturing fluid was prepared using powder polyacrylamide, nano-silica, and polyethylene glycol by high-speed mixing. The suspension and powder were compared in terms of properties of solubility, rheological behavior, sand carrying, drag reduction, and gel breaking. The results showed that the suspension could be quickly diluted in brine within 5 min, whereas the dissolution time of powder was 120 min. The suspension exhibited better performance in salt resistance, temperature resistance, shear resistance, viscoelasticity, sand carrying, and drag reduction than powder. The powder solution was broken more easily and had a lower viscosity than suspension diluent. These improvements in properties of the suspension were due to the dispersion of nano-silica in the polymer matrix; the mobility of thickener chains was inhibited by the steric hindrance of the nano-silica. Nano-silica particles acted as crosslinkers by attaching thickener chains, which strengthened the network structure of the thickener solution. The presence of hydrogen bonds between the thickener matrix and the nano-silica restricted the local movement of thickener chains, leading to a stronger spatial network. Therefore, this novel suspension showed good potential for fracturing applications.

Temperature- and Salt-Resistant Micro-Crosslinked Polyampholyte Gel as Fluid-Loss Additive for Water-Based Drilling Fluids.

With increasing global energy consumption, oil/gas drilling has gradually expanded from conventional shallow reservoirs to deep and ultra-deep reservoirs. However, the harsh geological features including high temperature and high salinity in ultra-deep reservoirs have become a critical challenge faced by water-based drilling fluids (WDFs), which seriously deteriorate the rheology and fluid loss properties, causing drilling accidents, such as wellbore instability and formation collapse. In this study, a novel temperature- and salt-resistant micro-crosslinked polyampholyte gel was synthesized using N,N-dimethylacrylamide, diallyldimethyl ammonium chloride, 2-acrylamido-2-methylpropanesulfonic acid, maleic anhydride and chemical crosslinking agent triallylamine through free radical copolymerization. Due to the synergistic effect of covalent micro-crosslinking and the reverse polyelectrolyte effect of amphoteric polymers, the copolymer-based drilling fluids exhibit outstanding rheological and filtration properties even after aging at high temperatures (up to 200 °C) and high salinity (saturated salt) environments. In addition, the zeta potential and particle size distribution of copolymer-based drilling fluids further confirmed that the copolymer can greatly improve the stability of the base fluid suspension, which is important for reducing the fluid-loss volume of WDFs. Therefore, this work will point out a new direction for the development of temperature- and salt-resistant drilling fluid treatment agents.

Oxygen vacancy BiO2-x/Bi2WO6 synchronous coupling with Bi metal for phenol removal via visible and near-infrared light irradiation.

The introduction of oxygen-defects has been a versatile strategy to enhance photocatalysis efficiency. In this work, a 2D/3D Bi/BiO2-x/Bi2WO6 heterojunction photocatalyst with rich oxygen-defective was in sequence prepared through a facile solvothermal method, which displays favorable photocatalytic activity towards organic contaminants under visible-NIR light irradiation. The enhancement in photocatalytic performance can be attributed to the synergistic effect between oxygen-vacancy-rich heterojunction and the localized surface plasmon resonance induced by metallic Bi. The functional group interaction, surface morphology, crystal structure, element composition, and tuned bandgap were investigated by FT-IR, SEM, Raman shift, ICP-MS, and XPS technique. The spectrum response performance of the photocatalyst was verified by UV-visible DRS analysis. Results of photodegradation experiments toward organic contaminants showed that the prepared photocatalyst can degrade 90% of phenol in 20 mins under visible-NIR light irradiation, both Z-scheme heterojunction and the introduction of Bi metal contribute to the enhancement in the photocatalytic activity. The results of the DFT calculation suggest that the valence band-edge hybridization within BiO2-x and Bi2WO6 can effectively enhance the photocatalytic performance by increasing the migration efficiencies of electron-hole pairs. Moreover, a possible mechanism was proposed on the results of EIS, ESR and GC-MS tests. This work offers a novel insight for synthesizing efficient visible-NIR light photocatalysis by activating the semiconductors with Bi metal.

3D Bombax-structured carbon nanotube sponge coupling with Ag3PO4 for tetracycline degradation under ultrasound and visible light irradiation.

A novel photocatalytic carbon nanotube sponge with three-dimensional Bombax-structure was fabricated by a facile chemical vapor deposition followed by in situ ion-exchange approach. The as-prepared sponge achieved both high-efficiency adsorption and photocatalysis towards antibiotics, which can remove up to 90% of tetracycline within an hour. The morphology and mechanism of the photocatalytic CNT sponge were explored by multiple measures. Results show the functional groups and high specific surface area of CNT sponge play vital roles in preparing this Bombax-structured Ag3PO4/CNT sponge, the band gap of which can be tuned by varying the ration between Ag3PO4 and CNT. The photodegradation experiments of tetracycline with the assistance of ultrasound irradiation were performed, Ag3PO4/CNT sponge exhibits preferable photocatalytic activity, which can be attributed to both the enhancement of specific surface area of Ag3PO4 and the cavitation effect on CNT surface. The efficiency contributed by ultrasound could account for more than half of the degradation efficiency when the ultrasound power was 100 W. The improvement in transfer efficiency and the delay in charge recombination of Ag3PO4/CNT sponge were further verified by Electrochemical impedance spectra (EIS) and Photoluminescence tests (PL). Reactive free-radical species were detected by the Electron Spin Resonance (ESR). The intermediates and possible pathway were analyzed by gas chromatography-mass spectrometer (GC-MS) technique.

Enhanced hydrolyzed polyacrylamide removal from water by an aerobic biofilm reactor-ozone reactor-aerobic biofilm reactor hybrid treatment system: Performance, key enzymes and functional microorganisms.

Degradation of hydrolyzed polyacrylamide-containing (HPAM-containing) wastewater was investigated in a lab-scale aerobic-ozonic-aerobic hybrid treatment system. When the HPAM concentration was 500 mg L-1 and the ozone dose was 25 g O3/g TOC, the HPAM removal rate reached 90.79%. Experimental results obtained from gel permeation chromatography (GPC) and rheometer indicated that the refractory HPAM was decomposed into small-molecule compounds. High performance liquid chromatography (HPLC) analysis showed that there was no acrylamide (AM) in the effluent of the system. Microbial communities in two aerobic biofilm reactors (ABRs) were analyzed by Illumina MiSeq Sequencing, which indicated that norank_f_Cytophagaceae, Meiothermus, Bacillus, etc. were keystone functional bacterial genera and Methanobacterium, norank_p_Bathyarchaeota, norank_c_Marine_Group_Ⅰ, etc. were dominant functional archaeal groups. To our knowledge, this is the first study to treat HPAM-containing wastewater using an aerobic-ozonic-aerobic hybrid process. Good removal efficiencies and presence of functional microorganisms demonstrated that the hybrid treatment system was practical for treating HPAM-containing wastewater.

An efficient and environmental-friendly dispersant based on the synergy of amphiphilic surfactants for oil spill remediation.

Eliminating the adverse environmental impact of chemical dispersants for oil spill has been a significant challenge since decades ago. Here, we prepared an effective and environmentally-friend dispersant with stable emulsifying capacity by the soybean lecithin and Tween 80. The mean droplet diameters of emulsions prepared by decane decreased from 11.3 to 4.1 µm, the emulsification index of emulsion climbed from 0 to 22.0% by 0.5 wt% dispersant. This dispersant exhibits favorable emulsifying capacity when the temperature ranges from 10 to 40 °C, pH within 5-7, and the concentration of inorganic cation is 30000 mg/L. Fluorescence microscopy analysis, FTIR, and the interfacial tension meter were employed to investigate the interaction between the soybean lecithin and Tween 80, a clear redshift of the hydroxyl group on the lecithin/Tween 80 dispersant and the detected surfactants over the oil-water interface confirm that there exists a synergy between the lecithin and Tween 80 due to the electrostatic attractions, which tremendously contribute to the reduction in the interfacial tension between water and oil. To further understand the influence of the dispersant on the oil hydrocarbon concentration in the water column, visualization simulation with the varying depths were performed. The results showed that the oil hydrocarbon concentration in the water column bottom was proportional to the addition of the dispersant, which facilitates spilled oil dispersing into smaller droplets, accelerates the biodegradation process. Hence, the lecithin/Tween 80 dispersant can be perceived as a promising alternative for oil spill remediation.

Study of displacement efficiency and flow behavior of foamed gel in non-homogeneous porous media.

Field trials have demonstrated that foamed gel is a very cost-effective technology for profile modification and water shut-off. However, the mechanisms of profile modification and flow behavior of foamed gel in non-homogeneous porous media are not yet well understood. In order to investigate these mechanisms and the interactions between foamed gel and oil in porous media, coreflooding and pore-scale visualization waterflooding experiments were performed in the laboratory. The results of the coreflooding experiment in non-homogeneous porous media showed that the displacement efficiency improved by approximately 30% after injecting a 0.3 pore volume of foamed gel, and was proportional to the pore volumes of the injected foamed gel. Additionally, the mid-high permeability zone can be selectively plugged by foamed gel, and then oil located in the low permeability zone will be displaced. The visualization images demonstrated that the amoeba effect and Jamin effect are the main mechanisms for enhancing oil recovery by foamed gel. Compared with conventional gel, a unique benefit of foamed gel is that it can pass through micropores by transforming into arbitrary shapes without rupturing, this phenomenon has been named the amoeba effect. Additionally, the stability of foam in the presence of crude oil also was investigated. Image and statistical analysis showed that these foams boast excellent oil resistance and elasticity, which allows them to work deep within formations.