Deciphering the catalytic activity of nickel anchored on Fe3O4@SiO2@3-CPMS@L as a magnetically recoverable nanocatalyst for the efficacious reduction of 4-nitrophenol, nitrobenzene, and methyl orange.

In this paper, a versatile heterogeneous nanocatalyst was fabricated employing a self-assembly technique. To commence, Fe3O4 MNPs were coated with a thin layer of SiO2 using the stobbers method. Subsequently, the surface was further functionalized with 3-CPMS, followed by a reaction with a Schiff base. Finally, nickel NPs were deposited on the surface through in situ deposition, forming the Fe3O4@SiO2@3-CPMS@L-Ni magnetic nanocatalyst. The architecture of this magnetic nanocatalyst was meticulously characterized through an array of sophisticated techniques: XRD, FT-IR, SEM, TEM, BET and VSM. The XRD diffraction pattern confirmed the presence of Fe3O4 MNPs, SiO2, and Ni peaks, providing evidence for successful synthesis. Moreover, the successful functionalization with a Schiff base was demonstrated by the presence of an azomethane peak in the FTIR spectra of the synthesized nanocatalyst. The fabricated nanocatalyst was adeptly utilized for the reduction of 4-NP, NB, and MO demonstrating a remarkably elevated rate of catalytic efficacy. Moreover, this catalyst was effortlessly retrievable through the application of an external magnet, and it maintained its catalytic prowess across at least six consecutive cycles. The utilization of water as an environmentally friendly solvent, coupled with the utilization of abundant and cost-effective nickel catalyst instead of the costly Pd or Pt catalysts, along with the successful recovery and scalability of the catalyst, render this method highly advantageous from both environmental and economic perspectives for the reduction of 4-NP, NB, and MO.

Immobilization of silver-loaded graphene oxide (Ag-GO) on canvas fabric support for catalytic conversion of 4 nitrophenol.

Due to the rising human population and industrialization, harmful chemical compounds such as 4-nitrophenol (4-NP) and various dyes are increasingly released into the environment, resulting in water pollution. It is essential to convert these harmful chemicals into harmless compounds to mitigate this pollution. This research focuses on synthesizing a novel heterogeneous catalyst using modified canvas fabric (CF) decorated with silver metal nanoparticles on graphene oxide nanosheets (Ag-GO/CF). The process involves coating the fabrics (CF) with graphene oxide (GO) nanosheets through sonication. Subsequently, silver nanoparticles are deposited in situ and reduced on the GO surface, resulting in the formation of the Ag-GO/CF composite. Various physicochemical characterizations were conducted to examine the interfacial interactions between CF, GO, and Ag nanoparticles. The catalytic activity of the nanocomposite was assessed by hydrogenating 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of sodium borohydride (NaBH4). The results showed that the 10%Ag-5%GO/CF with a surface of 6 cm2 (3 × 2 cm) exhibited the highest catalytic activity, achieving a reduction efficiency of over 96% in 5 min. The 4-NP reduction reaction rate was well-fitted with a pseudo-first-order kinetics model with an apparent reaction rate constant (Kapp) of 0.676 min-1. Furthermore, the Ag-GO/CF composite demonstrated remarkable stability over successive cycles, with no noticeable decrease in its catalytic activity, suggesting its promising application for long-term chemical catalytic processes. This synthesized composite can be easily added to and removed from the reaction solution while maintaining high catalytic performance in the reduction of 4-NP, and it could be beneficial in avoiding problems related to powder separation.

Deep learning artificial neural network framework to optimize the adsorption capacity of 3-nitrophenol using carbonaceous material obtained from biomass waste.

The presence of toxic chemicals in water, including heavy metals like mercury and lead, organic pollutants such as pesticides, and industrial chemicals from runoff and discharges, poses critical public health and environmental risks leading to severe health issues and ecosystem damage; education plays a crucial role in mitigating these effects by enhancing awareness, promoting sustainable practices, and integrating environmental science into curricula to empower individuals to address and advocate for effective solutions to water pollution. However, the educational transformation should be accompanied with a technical process which can be eventually transferred to society to empower environmental education. In this study, carbonaceous material derived from Haematoxylum campechianum (CM-HC) was utilized for removing 3-nitrophenol (3-Nph) from aqueous solutions. The novelty of this research utilizes Haematoxylum campechianum bark and coconut shell, abundant agricultural wastes in Campeche, Mexico, for toxin removal, enhancing the adsorption process through artificial neural networks and genetic algorithms to optimize conditions and maximize the absorption efficiency. CM-HC's surface morphology was analyzed using scanning electron microscopy (SEM/EDS), BET method, X-ray powder diffraction (XRD), and pHpzc. Kinetic models including pseudo-first-order (PFO), pseudo-second-order (PSO), and Elovich were applied to fit the data. Adsorption isotherms were determined at varying pH (3-8), adsorbent dosages (2-10 g/L), and temperatures (300.15-330.15 K), employing Langmuir, Freundlich, Temkin, and Redlich-Peterson models. PSO kinetics demonstrated a good fit (R2 > 0.98) for Ci = 50-100 mg/L, indicating a chemical adsorption mechanism. The Langmuir isotherm model exhibited the best fit, confirming chemical adsorption, with a maximum adsorption capacity (Qm) of 236.156 mg/g at T = 300.15 K, pH = 6, contact time = 3 h, and 2 g/L adsorbent dosage. Lower temperatures favored exothermic adsorption. Artificial neural networks (ANNs) were employed for deep learning, optimizing the predictive model for removal percentage. Correlation heat maps highlighted positive correlations between time, dosage, and removal percentage, emphasizing the impact of initial concentration on efficiency. ANN modeling, incorporating iterative optimization, yielded highly accurate predictions, aligned closely with experimental results. The study showcases the success of deep learning in optimizing adsorption processes, emphasizing the importance of diverse correlation algorithms for comprehensive insights into competitive adsorption dynamics. The 5-14-14-1 deep learning architecture, fine-tuned over 228 epochs, demonstrated strong performance with mean squared error (MSE) values of 4.07, 18.406, and 6.2122 for training, testing, and total datasets, respectively, and high R-squared values. Graphical analysis showed a solid linear correlation between experimental and simulated removal percentages, emphasizing the need to consider more than just testing data for optimization. Experimental validation confirmed a 98.77% removal efficiency, illustrating the effectiveness of combining deep learning with genetic algorithms, and highlighting the necessity of experimental trials to verify computational predictions. It is concluded that the carbonaceous material from Haematoxylum campechianum waste (CM-HC) is an effective, low-cost adsorbent for removing 3-nitrophenol from aqueous solutions, achieving optimal removal at pH 6 and 300.15 K with a maximum adsorption capacity of 236.156 mg/g, following Langmuir model and pseudo-second order kinetics. The validated ANN model offers a reliable tool for practical applications in environmental remediation, advancing both environmental science and educational innovation by integrating artificial neural networks and data science methodologies into student learning experiences.

Important yet Overlooked HONO Source from Aqueous-phase Photochemical Oxidation of Nitrophenols.

Nitrites (NO2-/HONO), as the primary source of hydroxyl radicals (•OH) in the atmosphere, play a key role in atmospheric chemistry. However, the current understanding of the source of NO2-/HONO is insufficient and therefore hinders the accurate quantification of atmospheric oxidation capacity. Herein, we highlighted an overlooked HONO source by the reaction between nitrophenols (NPs) and •OH in the aqueous phase and provided kinetic data to better evaluate the contribution of this process to atmospheric HONO. Three typical NPs, including 4-nitrophenol (4NP), 2-nitrophenol (2NP), and 4-nitrocatechol (4NC), underwent a denitration process to form aqueous NO2- and gaseous HONO through the •OH oxidation, with the yield of NO2-/HONO varied from 15.0 to 33.5%. According to chemical composition and structure analysis, the reaction pathway, where the ipso addition of •OH to the NO2 group on 4NP generated hydroquinone, can contribute to more than 61.9% of the NO2-/HONO formation. The aqueous photooxidation of NPs may account for HONO in the atmosphere, depending on the specific conditions. The results clearly suggest that the photooxidation of NPs should be considered in the field observation and calculation to better evaluate the HONO budget in the atmosphere.

A dual-signal triple-readout optical sensing platform for α-glucosidase and ß-glucosidase activity monitoring and inhibitor screening based on luminescent covalent organic framework.

BACKGROUND: As promising biomarkers of diabetes, α-glucosidase (α-Glu) and ß-glucosidase (ß-Glu) play a crucial role in the diagnosis and management of diseases. However, there is a scarcity of techniques available for simultaneously and sensitively detecting both enzymes. What's more, most of the approaches for detecting α-Glu and ß-Glu rely on a single-mode readout, which can be affected by multiple factors leading to inaccurate results. Hence, the simultaneous detection of the activity levels of both enzymes in a single sample utilizing multiple-readout sensing approaches is highly attractive. RESULTS: In this work, we constructed a facile sensing platform for the simultaneous determination of α-Glu and ß-Glu by utilizing a luminescent covalent organic framework (COF) as a fluorescent indicator. The enzymatic hydrolysis product common to both enzymes, p-nitrophenol (PNP), was found to affect the fluorometric signal through an inner filter effect on COF, enhance the colorimetric response by intensifying the absorption peak at 400 nm, and induce changes in RGB values when analyzed using a smartphone-based color recognition application. By combining fluorometric/colorimetric measurements with smartphone-assisted RGB mode, we achieved sensitive and accurate quantification of α-Glu and ß-Glu. The limits of detection for α-Glu were determined to be 0.8, 1.22, and 1.85 U/L, respectively. Similarly, the limits of detection for ß-Glu were 0.16, 0.42, and 0.53 U/L, respectively. SIGNIFICANCE: Application of the proposed sensing platform to clinical serum samples revealed significant differences in the two enzymes between healthy people and diabetic patients. Additionally, the proposed sensing method was successfully applied for the screening of α-Glu inhibitors and ß-Glu inhibitors, demonstrating its viability and prospective applications in the clinical management of diabetes as well as the discovery of antidiabetic medications.

Efficient degradation of p-nitrophenol from water by enhancing dielectric barrier discharge (DBD) plasma through ozone circulation: Optimization, kinetics and mechanism.

Non-thermal dielectric barrier discharge (DBD) plasma has received great attention for degradation of persistent organic pollutants such as p-nitrophenol (PNP). However, the feasibility of the DBD implementation is not clear due to its high energy consumption and relatively low degradation efficiency. In this research, a novel strategy was suggested based on re-circulation of the generated O3 in the DBD system to enhance the PNP degradation efficiency and energy yield. The potential mechanism and possible pathway of PNP degradation were studied by EPR, ESR, DFT and GS-MS analytical tests. According to the results, the PNP degradation efficiency and energy yield increased from 57.4% to 94.4% and from 0.52 to 1.18 g kW-1h-1, respectively through ozone circulation into the DBD reactor. This was due to the more release of long-lived and short-lived reactive species (ROS) in the DBD-O3 system by the O3 circulation. The variations in pH (4-10), initial concentration (50-90 mg L-1), and the presence of co-existing substances in the water matrix had minimal impact on the DBD-O3 system, in comparison to the conventional system. The biological toxicity evaluation revealed that the hybrid DBD-O3 system transform PNP to less toxic intermediates. This study proposes a promising strategy to improve the utilization of DBD for the degradation of PNP.

A bifunctional MoS2/SGCN nanocatalyst for the electrochemical detection and degradation of hazardous 4-nitrophenol.

Herein, we reported the dual functions of molybdenum disulfide/sulfur-doped graphitic carbon nitride (MoS2/SGCN) composite as a sensing material for electrochemical detection of 4-NP and a catalyst for 4-NP degradation. The MoS2 nanosheet, sulfur-doped graphitic carbon nitride (SGCN) and MoS2/SGCN were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of these materials with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 mM K4[Fe(CN)6]3-/4- show that the composite has the lowest charge transfer resistance and the best electrocatalytic activity. The limit of detection (LOD) and the linear range of 4-nitrophenol at MoS2/SGCN modified glassy carbon electrode (MoS2/SGCN/GCE) were computed as 12.8 nM and 0.1 - 2.6 µM, respectively. Also, the percentage recoveries of 4-NP in spiked tap water samples ranged from 97.8 - 99.1 %. The electroanalysis of 4-NP in the presence of notable interferons shows that the proposed electrochemical sensor features outstanding selectivity toward 4-NP. Additionally, the results of the catalytic degradation of 4-NP at MoS2/SGCN show that the nanocatalyst catalyzed the transformation of 4-NP to 4-aminophenol (4-AP) with a first-order rate constant (k) estimated to be 4.2 ×10-2 s-1. The results of this study confirm that the MoS2/SGCN nanocatalyst is a useful implement for electroanalytical monitoring and catalytic degradation of the hazardous 4-NP in water samples.

Construction of hierarchical NCMTs@MoO2/FeNi3 tubular heterostructures for enhanced performance in catalysis and protein adsorption.

A new type of hybrid material (NCMTs@MoO2/FeNi3) with a multi-layer heterostructure was designed and fabricated via a one-step pyrolysis process using FeOOH/NiMoO4@PDA as the precursor. FeOOH/NiMoO4@PDA was prepared by the solvothermal method, followed by the nickel-ion etching method coupled with the polymerization of dopamine (DA). The as-obtained material was made of nitrogen-doped carbon nanotubes embedded with FeNi3 and MoO2 nanoparticles (NPs). Notably, the FeNi3 NPs exhibited significantly improved performance in the reduction of 4-nitrophenol (4-NP) and adsorption of histidine-rich protein as well as provided appropriate magnetism resources. The MoO2 NPs imparted a metallic nature with excellent conductivity, and the N-doped mesoporous carbon microtubes also improved conductivity and facilitated mass transfer, thus leading to enhanced performance in catalysis. Benefiting from the 1D hierarchical porous structure and compositional features, the NCMTs@MoO2/FeNi3 composites exhibited excellent performance in 4-NP reduction and protein adsorption via specific metal affinity between the polyhistidine groups of proteins and the FeNi3 NPs. The result presented here indicates that the strategy of combining tailored components, heterostructuring, and carbon integration is a promising way to obtain high-performance composites for other energy-related applications.

A multifunctional sensor for detecting tetracycline, 4-nitrophenol, and pesticides.

In recent years, due to the abuse of antibiotics, nitro explosives and pesticides, which have caused great harm to the environment and human health, social concerns have prompted researchers to develop more sensitive detection platforms for these pollutants. In this paper, a novel two-dimensional Zn (II) coordination polymer, [Zn(L)0.5(1,2-bimb)]·DMF (1), [H4L=[1,1':4',1''-terphenyl]-2, 2'',4, 4'' -tetracarboxylic acid, 1,2-bimb = 1,2-bis(imidazol-1-ylmethyl)benzene] was synthesized using a hydro-solvothermal method. Among commonly used organic solvents, 1 exhibits significant stability. Fast and efficient fluorescence response can be achieved for tetracycline (TET), 4-nitrophenol (4-NP), fluazinam (FLU), and abamectin benzoate (AMB) with low detection limits. A binary intelligent logic gate device with FLU and AMB as chemical input signals is successfully constructed, which provides a new idea for biochemical detection. In addition, a portable visual test paper has been prepared, which has high sensitivity, good selectivity, and simple operation. It can be used for rapid detection of pollutants in daily life and has broad application prospects. Finally, a detailed discussion was conducted on the fluorescence sensing mechanism of 1 for detecting TET, 4-NP, AMB and FLU.

Enhanced detection of 4-nitrophenol in drinking water: ECL sensor utilizing velvet-like graphitic carbon nitride and molecular imprinting.

In this work, a molecularly imprinted electrochemiluminescence (ECL) sensor was developed for selective detection of 4-nitrophenol (4-NP) in drinking water for the first time. By synthesizing velvet-like graphitic carbon nitride (V-g-C3N4) via one-step thermal polycondensation and integrating it with a molecularly imprinted polymer (MIP), the ECL sensor was fabricated. The MIP-modified V-g-C3N4 composites (MIP/V-g-C3N4) were synthesized using a sol-gel method with 4-NP as the template molecule. Under optimal conditions, the ECL sensor exhibited a wide detection range (5 × 10-10-1 × 10-5 mol/L) and a low detection limit (1.8 × 10-10 mol/L). In testing with actual drinking water samples, it displayed high accuracy (recoveries for intraday and inter-day: 93.50-106.2% and 97.00-107.3%, separately) and precision (RSDs for intraday and inter-day: 1.54-4.59% and 1.53-4.28%, respectively). The developed MIP-based ECL sensor demonstrated excellent selectivity, stability, and reproducibility, offering a promising and reliable approach for highly sensitive and selective determination of 4-NP in drinking water.

Thermo-Switchable Enzyme@Metal-Organic Framework for Selective Biocatalysis and Biosensing.

The stimulus-responsive regulation of enzyme catalytic activity and selectivity provides a new opportunity to extend the functionality and efficiency of immobilized enzymes. This work aims to design and synthesize a thermo-switchable enzyme@MOF for size-selective biocatalysis and biosensing through the immobilization of Candida rugosa lipase (CRL) within ZIF-8 functionalized with thermally responsive polymer, poly(N-isopropylacrylamide) (PNIPAM) (CRL@ZIF-8-PNIPAM). Unlike free CRL, which does not demonstrate substrate selectivity, we can reversibly tune the pore size of the ZIF-8-PNIPAM nanostructures (open pores or blocked pores) through temperature stimulus and subsequently modulate the substrate selectivity of CRL@ZIF-8-PNIPAM. CRL@ZIF-8-PNIPAM had the highest hydrolytic activity for small molecules (12 mM p-nitrophenol/mg protein/min, 4-nitrophenyl butyrate (p-NP Be)) and the lowest hydrolytic activity for large molecules (0.16 mM p-nitrophenol/mg protein/min, 4-nitrophenyl palmitate (p-NP P)). In addition, CRL@ZIF-8-PNIPAM demonstrated thermo-switchable behavior for large molecules (p-NP P). The p-NP P hydrolytic activity of CRL@ZIF-8-PNIPAM was significantly lower at 40 °C (blocked pores) than at 27 °C (open pores). However, the transition of blocked pores and open pores is a gradual process that resulted in a delay in the "thermo-switchable" catalytic behavior of CRL@ZIF-8-PNIPAM during thermal cycling. CRL@ZIF-8-PNIPAM was also successfully used for the fabrication of electrochemical biosensors for the selective biosensing of pesticides with different molecular sizes.

Exploring the potential of surface-modified alginate beads for catalytic removal of environmental pollutants and hydrogen gas generation.

In this study, hydrogel beads were fabricated using alginate (Algt) polymer containing dispersed nickel phthalocyanine (NTC) nanomaterial. The viscous solution of Algt and NTC was poured dropwise into a divalent Ca2+ ions, resulting in the formation of hydrogel beads known as NTC@Algt-BDs. The surface of the NTC@Algt-BDs was further modified by coating them with different types of metal ions, yielding metal-coated M+/NTC@Algt-BDs. The adsorbed metal ions i.e., Cu+2, Ag+, Ni+2, Co+2, and Fe+3 were subsequently reduced to zero-valent metal nanoparticles (M0) by NaBH4. The prepared beads were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Initially, M0/NTC@Algt-BDs were examined for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Among them, Cu0/NTC@Algt-BDs catalyst exhibited the highest reduction rate and therefore, investigated for reduction of different nitrophenols (NPs) and dyes, including 2-nitrophenol (2-NP), 2,6-dinitrophenol (2,6-DNP), methyl orange (MO), potassium ferrocyanide (PFC), congo red (CR), and acridine orange (ArO). The highest reduction rates of 2.019 and 1.394 min-1 were observed for MO and 2-NP, respectively. Furthermore, the fabricated catalysts were employed for the efficient production of H2 gas by NaBH4 methanolysis. Among which the Ag0/NTC@Algt-BDs catalyst showed excellent catalytic production of H2 gas, exhibiting the lowest activation energy (Ea) of 25.169 kJ/mol at ambient temperature. Furthermore, the impact of NaBH4 amount, and catalyst dosage on the reduction of 2-NP and H2 gas production was conducted whereas the effect of temperature on methanolysis of NaBH4 for evolution of H2 gas was studied. The amount of H2 gas was confirmed by GC-TCD system. Additionally, the recyclability of the catalyst was investigated, as it garnered significant research interest.

Green synthesis of novel Zn0.5Ni0.5FeCrO4 spinel magnetic nanoparticles: Photodegradation of 4-nitrophenol and aniline under visible light irradiation.

This study explores novel nanoparticles used in environmental remediation of 4-nitrophenol and aniline from wastewater bodies. The Zn0.5Ni0.5FeCrO4 magnetic nanoparticles (MNPs) were synthesized using tragacanth gel as a green, low-cost, and easy sol-gel method. The MNPs were characterized by XRD, XPS, FT-IR, VSM, TEM, EDX, FESEM, BET, DRS, and elemental mapping. The analysis demonstrated that nanoparticles have a spinel cubic structure, spatial distribution of the elements, ferromagnetic activity, narrow bandgap, and uniform morphology. Furthermore, effectiveness of the developed MNPs to degrade recalcitrant organic pollutants such as 4-nitrophenol (4-NP) and aniline under visible light exposure were studied. The results indicated 95% aniline and 80% of 4-NP were successfully degraded in 180 and 150 min, respectively. The total organic carbon (TOC) analysis revealed 65% and 54% removal of aniline and 4-NP. LC-MS was employed to elucidate the photodegradation mechanism and to identify the degradation products, including small fragmented molecules.

Carboxymethyl ß-Cyclodextrin Assistance for the 4-Nitrophenol Reduction Using Cobalt-Based Layered Double Hydroxides.

Cobalt-aluminum-layered double hydroxides containing carboxymethyl ß-cyclodextrin (CMßCD) were synthesized by coprecipitation and evaluated as a cobalt source for the 4-nitrophenol reduction in an aqueous medium. Several physicochemical techniques (XRD, FTIR, TGA) indicated the intercalation of the anionic cyclodextrin without damages to the hydrotalcite-type structure. These lamellar cobalt-aluminum hybrid materials (CoAl_CMßCD) were evaluated in the 4-nitrophenol reduction and showed higher activities in comparison with the CMßCD-free standard material (CoAl_CO3). To rationalize these results, a set of experimental controls going from physical mixtures of CoAl_CO3 with different cyclodextrins to other cobalt-based materials were investigated, highlighting the beneficial effects of both the layered double hydroxide and CMßCD-based hybrid structures. CMßCD also showed a beneficial effect as an additive during the 4-nitrophenol reduction. CoAl_CO3, dispersed in a fresh CMßCD solution could be re-used for five successive cycles without the loss of activity.

Coupling Peptide-Based Encapsulation of Enzymes with Bacteria for Paraoxon Bioremediation.

The catalytic efficiency of enzymes can be harnessed as an environmentally friendly solution for decontaminating various xenobiotics and toxins. However, for some xenobiotics, several enzymatic steps are needed to obtain nontoxic products. Another challenge is the low durability and stability of many native enzymes in their purified form. Herein, we coupled peptide-based encapsulation of bacterial phosphotriesterase with soil-originated bacteria, Arthrobacter sp. 4Hß as an efficient system capable of biodegradation of paraoxon, a neurotoxin pesticide. Specifically, recombinantly expressed and purified methyl parathion hydrolase (MPH), with high hydrolytic activity toward paraoxon, was encapsulated within peptide nanofibrils, resulting in increased shelf life and retaining ∼50% activity after 132 days since purification. Next, the addition of Arthrobacter sp. 4Hß, capable of degrading para-nitrophenol (PNP), the hydrolysis product of paraoxon, which is still toxic, resulted in nondetectable levels of PNP. These results present an efficient one-pot system that can be further developed as an environmentally friendly solution, coupling purified enzymes and native bacteria, for pesticide bioremediation. We further suggest that this system can be tailored for different xenobiotics by encapsulating the rate-limiting key enzymes followed by their combination with environmental bacteria that can use the enzymatic step products for full degradation without the need to engineer synthetic bacteria.

Enhancing the microbial advanced oxidation of P-nitrophenol in sediment through accelerating extracellular respiration with electrical stimulation.

Microbial advanced oxidation, a fundamental process for pollutant degradation in nature, is limited in efficiency by the weak respiration of indigenous microorganisms. In this study, an electric field was employed to enhance microbial respiration and facilitate the microbial advanced oxidation of p-nitrophenol (PNP) in simulated wetlands with alternation of anaerobic and aerobic conditions. With intermittent air aeration, an electric field of 0.8 V promoted extracellular electron transfer to increase Fe2+ generation through dissimilatory iron reduction and the production of hydroxyl radicals (•OH) through Fenton-like reactions. As a result, the PNP removal rate of the electrically-stimulated group was higher than that of the control (72.15 % vs 46.88 %). Multiple lines of evidence demonstrated that the electrically-induced polarization of respiratory enzymes expedited proton-coupled electron transfer within the respiratory chain to accelerate microbial advanced oxidation of PNP. The polarization of respiratory enzymes with the electric field hastened proton outflow to increase cell membrane potential for adenosine triphosphate (ATP) generation, which enhanced intracellular electron transportation to benefit reactive oxygen species generation. This study provided a new method to enhance microelectrochemical remediation of the contaminant in wetlands via the combination of intermittent air aeration.

Enhanced denitrification and p-nitrophenol removal performance via hydrophilic sponge carriers fixed with dual-bacterial: Optimization, performance, and enhancement mechanism.

Effective treatment of industrial wastewater containing complex pollutants, such as nitrate (NO3--N) and organic pollutants, remains a significant challenge to date. Here, a strain Nocardioides sp. ZS2 with denitrification and degradation of p-nitrophenol (PNP) was isolated and its culture conditions were optimized by kinetic analysis. Hydrophilic sponge carriers were prepared using polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), and chitosan (CS) to construct bioreactors. Furthermore, to further enhance the PNP degradation and denitrification performance of bioreactors, Pseudomonas stutzeri GF2 with denitrification capability was introduced. The results revealed that the removal efficiencies of PNP and NO3--N reached 97.9 % and 91.9 %, respectively, when hydraulic retention time (HRT) of 6 h, C/N of 2.0, and pH of 6.5. The bioreactor exhibited stable denitrification performance even with fluctuations in the influent PNP concentration. The potential functional prediction results revealed that the abundance of amino acids, fatty acids, and carbohydrates increased as the influent C/N decreased, reflecting a tendency of the microbial community to adjust carbon source utilization to maintain cell growth, metabolic balance, and resist adverse C/N environments. This research provides new insights into the effective removal of organic pollutants and NO3--N in wastewater treatment.

Preparation of fluorescent polyurethane microspheres and their applications as reusable sensor for 4-nitrophenol detection and as microplastics model for visualizing polyurethane in cells and zebrafish.

Fluorescent microspheres are of significant interests due to their wide applications in biotechnology fields. However, their preparation presents several challenges, such as the need for dye labeling, the complexity of materials and often sophisticated preparation conditions. Here a simple process for hydrophilic and crosslinked polyurethane (CPU) microspheres, with carboxyl groups on the surface via one-step precipitation polymerization in 40 min, is presented. The microsphere size is easily adjusted by varying experimental conditions. CPU microspheres exhibit high thermal and pH stability with good redispersibility in water, and emit fluorescence without any modification or dye labeling. The emission mechanism is discussed. CPU microspheres are used as fluorescent probe to detect 4-nitrophenol (4-NP) based on their emission in UV light region, with excellent selectivity and sensitivity. In addition, they are reusable with detection limit unchanged after 7 cycles of reuses, a significant feature of this work. The mechanism of fluorescence detection is thoroughly explored and ascribed to the internal filtration effect. Based on the emission in visible light region, CPU microspheres are used as a model of PU microplastics (MPs) to visualize their biodistribution in HeLa and macrophage cells, as well as in zebrafish larvae, providing a reliable tracer for the visualization and tracking of PU MPs in organisms.

Preparation of GO/COFs composites by interlayer-confined strategy for the adsorption of nitro aromatic pollutants.

With the continuous development of industrialization, the excessive emission of nitro aromatic with strong toxicity, high carcinogenicity and non-degradability has attracted great attention. How to efficiently remove nitro aromatic pollutants is an important research topic. In this work, graphene oxide/covalent organic frameworks (GO/COFs) composites were successfully synthesized via interlayer confinement strategy selecting GO, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) and 1,3,5-tri(4-aminophenyl)benzene (TPB) as raw materials. Due to high specific surface area, hierarchical porous structure and good thermal stability, GO/COFs were utilized to adsorb and remove nitro aromatic hydrocarbons in the water environment. The adsorption behavior of GO/COFs for o-nitrophenol, 1,3-dinitrobenzene and 2,4,6-trinitrophenol were further investigated. The GO/COFs composites showed the strongest adsorption capacity for 2,4,6-trinitrophenol, and the maximum adsorption capacity for 2,4,6-trinitrophenol, o-nitrophenol, and 1,3-dinitrobenzene were 438, 317, and 173 mg g-1, respectively. The experimental results indicated that the GO/COFs composites provided great adsorption capability for nitro aromatic pollutants and can be reused, rendering it an extremely potential adsorbent for organic pollutants.

A composite of AgNPs and lignin porous microspheres via in-situ reduction of Ag+ and its catalytic performance.

Despite the widespread utilization of nano silver composites in the domain of catalytic hydrogenation of aromatic pollutants in wastewater, certain challenges persist, including the excessive consumption of chemical reagents during the preparation process and the difficulty in recycling. In this study, silver ions were reduced in-situ by taking advantage of the adsorptive and reducing capacities of hydroxyls and amino groups on lignin porous microspheres (LPMs) under mild ultrasonic conditions, and lignin porous microspheres loaded with silver nanoparticles (Ag@LPMs) were conveniently prepared. Ag@LPMs had excellent catalytic and cycling performances for p-nitrophenol (4-NP), methylene blue (MB) and methyl orange (MO). The 4-NP could be completely reduced to 4-AP within 155 s under the catalysis of Ag@LPMs, with a pseudo-first-order kinetic constant of 1.28 min-1. Furthermore, Ag@LPMs could still complete the catalytic reduction of 4-NP within 10 min after five cycles. Ag@LPMs with the particle size ranging from 100 to 200 µm conferred ease of recycling, and the porous structure effectively resolved the issue of sluggish mass transfer encountered during the catalytic process. At the same time, the binding force of nano silver and LPMs obtained by ultrasonic was stronger than that of heating, so the materials prepared by ultrasonic had better cycling performance. Silver ions concentration and pH value in the preparation process affected the catalytic performance of Ag@LPMs, 50 mmol/L Ag+ and pH value of 7 turned out to be the optimization conditions.