Microbial degradation mechanism and pathway of the insecticide thiamethoxam by isolated Bacillus Cereus from activated sludge.

The high water solubility and ecotoxicity of thiamethoxam (TMX) is a potential hazard to ecosystems and human health. Here, a strain of Bacillus cereus with high TMX degradation activity was isolated from the sediment of the A2O process in the wastewater treatment plant and was able to utilize TMX as its sole carbon source. Under different environmental conditions, the degradation efficiency of TMX by Bacillus cereus-S1 (strain S1) ranged from 41.0% to 68.9% after 216 h. The optimum degradation conditions were DO = 3.5 mg/L and pH 9.0. The addition of an appropriate carbon-to-nitrogen ratio could accelerate the degradation of TMX. A plausible biodegradation pathway has been proposed based on the identified metabolites and their corresponding degradation pathways. TMX can be directly converted into Clothianidin (CLO), TMX-dm-hydroxyl and TMX-Urea by a series of reactions such as demethylation, oxadiazine ring cleavage and C=N substitution by hydroxy group. The main products were TMX-dm-hydroxyl and TMX-Urea, the amount of CLO production is relatively small. This study aims to provide a new approach for efficient degradation of TMX; furthermore, strain S1 is a promising biological source for in situ remediation of TMX contamination.

Response mechanism of a highly efficient partial nitritation-anammox (PN/A) process under antibiotic stress: Extracellular polymers, microbial community, and functional genes.

The Partial nitritation-Anammox (PN/A) process can be restricted when treating high ammonia nitrogen wastewater containing antibiotics. This study aims to explore the response mechanism of the PN/A process under antibiotic stress. Results showed the PN/A process achieved a nitrogen removal rate higher than 1.01 ± 0.03 kg N/m3/d under long-term sulfamethazine stress. The increase of extracellular polymers from 22.52 to 43.96 mg/g VSS was conducive to resisting antibiotic inhibitory. The increase of Denitratisoma and SM1A02 abundance as well as functional genes nirS and nirK indicated denitrifiers should play an important role in the stability of the PN/A system under sulfamethazine stress. In addition, antibiotic-resistant genes (ARGs) sul1 and intI1 significantly increased by 8.78 and 5.12 times of the initial values to maintain the resistance of PN/A process to sulfamethazine stress. This study uncovers the response mechanism of the PN/A process under antibiotic stress, offering a scientific basis and guidance for further application in the future.

Highly Sensitive Pressure Sensor Based on Elastic Conductive Microspheres.

Elastic pressure sensors play a crucial role in the digital economy, such as in health care systems and human-machine interfacing. However, the low sensitivity of these sensors restricts their further development and wider application prospects. This issue can be resolved by introducing microstructures in flexible pressure-sensitive materials as a common method to improve their sensitivity. However, complex processes limit such strategies. Herein, a cost-effective and simple process was developed for manufacturing surface microstructures of flexible pressure-sensitive films. The strategy involved the combination of MXene-single-walled carbon nanotubes (SWCNT) with mass-produced Polydimethylsiloxane (PDMS) microspheres to form advanced microstructures. Next, the conductive silica gel films with pitted microstructures were obtained through a 3D-printed mold as flexible electrodes, and assembled into flexible resistive pressure sensors. The sensor exhibited a sensitivity reaching 2.6 kPa-1 with a short response time of 56 ms and a detection limit of 5.1 Pa. The sensor also displayed good cyclic stability and time stability, offering promising features for human health monitoring applications.

Thiamethoxam adsorption by ZnCl2 modified cow manure biochar: Mechanism and quantitative prediction.

The overuse of thiamethoxam (THM) has threatened the survival of living organisms and it is necessary to find an environmentally friendly material to remove THM frequently detected in water. Biochar prepared from cow manure modified with ZnCl2 (Zn-CBC) was used to remove THM. Compared to the unmodified cow manure biochar (CBC), the removal ratio of THM by Zn-CBC was enhanced 35 times. In the mechanistic analysis, SEM and BET showed that Zn-CBC had a good pore structure and its specific surface area (166.502 m2 g-1) increased to 17 times that of CBC, indicating that Zn-CBC had good pore adsorption properties. The adsorption kinetic and isotherm implied that the main mechanism was chemisorption including π-π interaction and H-bonding. Furthermore, the stable graphitized structure of Zn-CBC allowed for efficient adsorption and reusability. In addition, this study constructed an intelligent prediction model using batch experiment data, and the high R2 (0.978) and low RMSE (0.057) implied that the model could accurately and quantitatively predict the adsorption efficiency. This paper provides a novel perspective to simultaneously remove the neonicotinoid insecticides and realize the resource utilization of cow manure.

Free nitrous acid prediction in ANAMMOX process using hybrid deep neural network model.

Free nitrous acid (FNA) is a critical metric for stabilization of ANAMMOX but can not be directly and immediately measured by sensors or chemical measurement method, which hinders the effective management and operation for ANAMMOX. This study focuses on FNA prediction using hybrid model based on temporal convolutional network (TCN) combined with attention mechanism (AM) optimized by multiobjective tree-structured parzen estimator (MOTPE), called MOTPE-TCNA. A case study in an ANAMMOX reactor is carried out. Results show that nitrogen removal rate (NRR) is highly correlated with FNA concentration, indicating that it can forecast the operational status by predicting FNA. Then, MOTPE successfully optimizes the hyperparameters of TCN, helping TCN achieve a high prediction accuracy, and AM furtherly improves model accuracy. MOTPE-TCNA obtains the highest prediction accuracy, whose R2 value gets 0.992, increasing 1.71-11.80% compared to other models. As a deep neural network model, MOTPE-TCNA has more advantages than traditional machine learning methods in FNA prediction, which is beneficial to maintain the stable operation and easy control for ANAMMOX process.

Water quality prediction model using Gaussian process regression based on deep learning for carbon neutrality in papermaking wastewater treatment system.

Wastewater recycling is the measure with enormous potentiality to achieve carbon neutrality in wastewater treatment plants. High-precision online monitoring can improve the stability of wastewater treatment system and help wastewater recycling. A new water quality prediction CSWLSTM-GPR model, which fused the spatial feature of convolutional neural network (CNN), the temporal feature of sharing-weight long short-term memory (SWLSTM) and the probabilistic reliability of Gaussian process regression (GPR), was applied for monitoring papermaking wastewater treatment system with high-precision point prediction and interval prediction. Compared with SWLSTM-GPR and CLSTM-GPR, RMSE of CSWLSTM-GPR reduced by more than 48.9% on effluent chemical oxygen demand (CODeff), MAE reduced by more than 49.3%, R2 increased by more than 25.14%, R increased by more than 7.07%. And for the effluent suspended solids (SSeff), CSWLSTM-GPR had better predictive results than SWLSTM-GPR and CSWLSTM-GPR. Compared with SWLSTM-GPR, RMSE, MAE, R, R2 of CSWLSTM-GPR on effluent suspended solids (SSeff) were improved by 4.8%, 6.1%, 29.01% and 31.15%, respectively. Simulation results showed convincing comprehensive forecasting ability were obtained and the true values frequently stayed within the water quality range obtained by CSWLSTM-GPR model, which provided important insights for online monitoring, wastewater recycling and carbon neutrality of papermaking industry.

Photo-biodegradation of imidacloprid under blue light-emitting diodes with bacteria and co-metabolic regulation.

Imidacloprid (IMI) is existence in the soil environment with a half-life habitually more than hundred days. This study targets to determine, identify and characterize photo-biodegradation bacteria from neonicotinoids (NEOs) contaminated agricultural field soils. The sub-surface soil had a higher level contamination of NEOs, in specifically greater concentration of IMI (3445.2 ± 0.09 µg/g) and thiacloprid (4084.4 ± 0.09 µg/g) has been found. Three bacteria Ralstonia pickettii (PBMS-2), Bacillus cereus (PBMS-3) and Shinella zoogloeoides (PBMS-4) was identified from soil-free stable enrichment cultures. The biodegradability of IMI (50 mg L-1) by three bacteria under different colors of light-emitting diodes (LEDs) with a constant 12 V power supply was tested and found that the blue-LEDs had greatest efficiency in supporting biodegradation of IMI which is called photo-biodegradation. In specific, the rate of photo-biodegradation of IMI by Ralstonia pickettii (87%), Bacillus cereus (80%) and Shinella zoogloeoides (80%) was measured. Besides this study also tested the effect of aeration (rpm), pH, and temperature on photo-biodegradation of IMI. There were seven intermediate metabolites were measured as biodegradation products of IMI under photo-biodegradation conditions and they are; IMI-urea, IMI-desnitro, 6-chloronicotinic acid, 6-hydroxy nicotinic acid, IMI- aminoguanidine, IMI-nitrosoguanidine and 4,5-hydroxy IMI, these metabolites are may non-toxic to the environment.

Organic and hybrid resistive switching materials and devices.

The explosive increase in digital communications in the Big Data and internet of Things era spurs the development of universal memory that can run at high speed with high-density and nonvolatile storage capabilities, as well as demonstrating superior mechanical flexibility for wearable applications. Among various candidates for the next-generation information storage technology, resistive switching memories distinguish themselves with low power consumption, excellent downscaling potential, easy 3D stacking, and high CMOS compatibility, fulfilling key requirements for high-performance data storage. Employing organic and hybrid switching media in addition allows light weight and flexible integration of molecules with tunable device performance via molecular design-cum-synthesis strategy. In this review, we present a timely and comprehensive review of the recent advances in organic and hybrid resistive switching materials and devices, with particular attention on their design principles for electronic property tuning and flexible device performance. The current challenges posed with development of organic and hybrid resistive switching materials and flexible memory devices, together with their future perspectives, are also discussed.

Residue levels and spatial distribution of phthalate acid esters in water and sediment from urban lakes of Guangzhou, China.

The residue levels and composition profiles of phthalate acid esters (PAEs) in water and sediment samples were investigated in eight urban lakes of Guangzhou, China. A total of 23 water and 16 sediment samples were collected. Results showed that all target PAEs were detected with dimethyl phthalate and di(2-ethylhexyl) phthalate as the most abundant compounds. The total concentrations of PAEs from different urban lakes were in the range of 273-1173 ng/L for water and 16.5-242 ng/g for sediments, with the geometric mean of 515 ng/L and 75.0 ng/g, respectively. Zhongshan Park Lake and Liwan Lake were the most highly contaminated with PAEs in water and in sediment, respectively. The spatial distribution of PAEs exhibited that distribution coefficients of PAEs between sediment and water are consistent with hydrophilicity of PAEs, and pollution levels and characteristics of PAEs in different lakes had a close relationship with the geographical location of the lake, industrial and commercial types, population density, and the association between the lake and the Pearl River. According to Pearson correlation analysis, PAEs would be derived from similar or identical sources. Risk assessment suggested that the exposure of PAEs in Guangzhou has a moderate toxicity at the current level.

Low dark current broadband 360-1650 nm ITO/Ag/n-Si Schottky photodetectors.

This work designed an ITO/Ag/n-Si Schottky photodetector with broad wavelength detection and low dark current. The introduction of Ag interfacial layer and post rapid thermal annealing dramatically increase the barrier height of ITO/n-Si Schottky diode by 0.32 eV, leading to the 2300 × reduction of dark current. A well-behaved ITO/Ag (8 nm)/n-Si Schottky diode with a high rectification ratio ( ± 1 V) of 4 × 105 and low dark current (-1 V) of 9.2 nA was achieved. Such low dark current device spontaneously provides high sensitivity for visible/near infrared wavelength detection, in which substantial responsivity for wavelengths from 360 to 1650 nm was realized through both inter-band and internal photoemission. The design here provides an encouraging strategy for monolithically integrated pure Si photodetectors operating at long wavelength up to 1650 nm.

Rational Organization of Lanthanide-Based SMM Dimers into Three-Dimensional Networks.

Optimization of the reaction of [Ln(hfac)3]·2H2O and pyridine-N-oxide (PyNO), which is known to afford double-bridged dimers, leads to triple-bridged dimers of formula [(Ln(hfac)3)2(PyNO)3] (Ln = Gd (1), Dy (2)) from which the Dy derivative (2) behaves as a single-molecule magnet (SMM). The pseudo threefold axis symmetry of this zero-dimensional building block makes possible its extension into a tridimensional network. By changing PyNO for 4,4'-bipyridine N,N'-dioxide (4,4'BipyNO) a tridimensional compound of formula {[Ln(hfac)3]2(4,4'BipyNO)2]} (Ln = Eu (3), Gd (4), and Dy (5)) is then rationally obtained. This covalent three-dimensional (3D) network has a remarkably high cell volume (V = 24 419 A(3)) and is an arrangement of interpenetrated 3D subnetworks whose triple-bridged dimers still behave as SMMs.

A family of lanthanide-based coordination polymers with boronic Acid as ligand.

Reactions in water between the sodium salt of 4-carboxyphenylboronic acid (Hcpb) and lanthanide ions (Pr-Nd, Sm-Lu, and Y) led to a family of lanthanide-based coordination polymers with general chemical formula {[Ln(cpbOH)(H2O)2](cpb)}∞. Structural characterizations were ensured by single-crystal X-ray diffraction and solid-state NMR spectroscopy ((11)B, (13)C, and (89)Y). This family of compounds constitutes the first example of lanthanide-based coordination polymers involving 4-carboxyphenylboronic acid as ligand. To evaluate their potential usefulness, luminescent and magnetic properties of some of the compounds that constitute this family were explored. From a magnetic point of view, the Yb(III) compound is the more promising. On the other hand, upon UV irradiation (λexc = 303 nm) ligand phosphorescence is quite intense and offers a sizable blue component to emission spectra. This is quite unusual and can constitute an asset as far as white emission is targeted. Moreover, luminescence properties of these compounds are highly temperature-dependent, and some of them seem promising as molecular thermometers.

Unraveling the crystal structure of lanthanide-murexide complexes: use of an ancient complexometry indicator as a near-infrared-emitting single-ion magnet.

Herein, we provide some structural evidence of the complexation color-change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln = Sm to Lu and Y, the compounds crystallize as monomeric [Ln(Murex)3]⋅11 H2O with an N3O6 tricapped square-antiprism environment, which are stable up to 250 °C. Single-ion magnet (SIM) behavior is then observed on the Yb(III) derivative in an original nine-coordinated environment. In-field slow relaxation (Δ = (15.6±1) K; τ0 = 2.73×10(-6) s) is observed with a very narrow distribution of the relaxation time (αmax = 0.09). Magnetic and photophysical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic measurements permit to identify the nature of the MJ states involved in the (2)F5/2 → (2)F7/2 luminescence spectrum. The gap between the low-lying states is in agreement with the energy barrier obtained from magnetic slow-relaxation measurement.

U-shaped stereoscopic design strategy toward N-doped nanographene segment.

There have been scarce reports about stereoscopic design of N-heteroacenes (NHAs), especially for the electron-deficient π-building blocks. Herein, we report the design and synthesis of a U-shaped bis(pyrene-quinoxaline) (BPQ). Single crystal X-ray diffraction reveals the herringbone stacking pattern and the presence of regular and incompletely closed pores.

Enhanced biodegradation of thiamethoxam with a novel polyvinyl alcohol (PVA)/sodium alginate (SA)/biochar immobilized Chryseobacterium sp H5.

Long-term and extensive usage of thiamethoxam, the second-generation neonicotinoid insecticide, has caused a serious threat to non-target organisms and ecological security. Efficient immobilized microorganism techniques are a sustainable solution for bioremediation of thiamethoxam contamination. A Gram-negative aerobic bacterium Chryseobacterium sp H5 with high thiamethoxam-degrading efficiencies was isolated from activated sludge. Then we developed a novel polyvinyl alcohol (PVA)/sodium alginate (SA)/biochar bead with this functional microbe immobilization to enhance the biodegradation and removal of thiamethoxam. Results indicated that the total removal and biodegradation rate of thiamethoxam with PVA/SA/biochar (0.7 %) beads with Chryseobacterium sp H5 immobilization at 30 °C and pH of 7.0 within 7 d reached about 90.47 % and 68.03 %, respectively, much higher than that using PVA/SA immobilized microbes (75.06 %, 56.05 %) and free microbes (61.72 %). Moreover, the PVA/SA/biochar (0.7 %) immobilized microbes showed increased tolerance to extreme conditions. Biodegradation metabolites of thiamethoxam were identified and two intermediates were first reported. Based on the identified biodegradation intermediates, cleavage of C-N between the 2-chlorothiazole ring and oxadiazine, dichlorination, nitrate reduction and condensation reaction would be the major biodegradation routes of thiamethoxam. Results of this work suggested the novel PVA/SA/biochar beads with Chryseobacterium sp H5 immobilization would be helpful for the effective bioremediation of thiamethoxam contamination.

Novel hydrophilic straw biochar for the adsorption of neonicotinoids: kinetics, thermodynamics, influencing factors, and reuse performance.

Nitenpyram (NIT) is the most water-soluble neonicotinoid (NEO). It has been shown to pose a serious threat to human health and the environment but was always ignored due to its limited market share. There were few experts who studied NIT's transport behavior on biochar. In this study, two types of biochar were co-activated separately using zinc chloride combined with phosphoric acid and potassium hydroxide combined with acetic acid, marked as ZBC and KBC. Characterizations suggested that hydrophilic ZBC and KBC had more surface functional groups than unmodified biochar (BC), and specific surface areas of ZBC (456.406 m2·g-1) and KBC (750.588 m2·g-1) were significantly higher than of BC (67.181 m2·g-1). The pore structures of KBC and ZBC were hierarchical porous structures with different pore sizes and typical microporous structure, respectively. The adsorption performance of either NIT or IMI on KBC was better than that on ZBC. Only 0.4 g·L-1 of KBC can absorb 89.62% of NIT in just 5 min. The equilibrium adsorption amounts of NIT on ZBC and KBC were 17.995 mg·g-1 and 82.910 mg·g-1. Elovich and Langmuir models were used to evaluate the whole adsorption process, which was attributed to the chemisorption mechanism. In addition, removal rates of NIT were negatively correlated to NIT's initial concentration and positively correlated to the dose of biochar. pH had almost no effect on adsorption, but the presence of salt ions can inhibit the removal of NIT. Long-term stabilities of biochars were also acceptable. These findings will promote the development in the preparation of biochar fields and provide a positive reference value for NEO removal.

Design and 3D Printing of Stretchable Conductor with High Dynamic Stability.

As an indispensable part of wearable devices and mechanical arms, stretchable conductors have received extensive attention in recent years. The design of a high-dynamic-stability, stretchable conductor is the key technology to ensure the normal transmission of electrical signals and electrical energy of wearable devices under large mechanical deformation, which has always been an important research topic domestically and abroad. In this paper, a stretchable conductor with a linear bunch structure is designed and prepared by combining numerical modeling and simulation with 3D printing technology. The stretchable conductor consists of a 3D-printed bunch-structured equiwall elastic insulating resin tube and internally filled free-deformable liquid metal. This conductor has a very high conductivity exceeding 104 S cm-1, good stretchability with an elongation at break exceeding 50%, and great tensile stability, with a relative change in resistance of only about 1% at 50% tensile strain. Finally, this paper demonstrates it as a headphone cable (transmitting electrical signals) and a mobile phone charging wire (transmitting electrical energy), which proves its good mechanical and electrical properties and shows good application potential.

Targeting immunosuppressive Ly6C+ classical monocytes reverses anti-PD-1/CTLA-4 immunotherapy resistance.

Introduction: Despite significant clinical advancement with the use of immune checkpoint blockade (ICB) in non-small cell lung cancer (NSCLC) there are still a major subset of patients that develop adaptive/acquired resistance. Understanding resistance mechanisms to ICB is critical to developing new therapeutic strategies and improving patient survival. The dynamic nature of the tumor microenvironment and the mutational load driving tumor immunogenicity limit the efficacy to ICB. Recent studies indicate that myeloid cells are drivers of ICB resistance. In this study we sought to understand which immune cells were contributing to resistance and if we could modify them in a way to improve response to ICB therapy. Results: Our results show that combination anti-PD-1/CTLA-4 produces an initial antitumor effect with evidence of an activated immune response. Upon extended treatment with anti-PD-1/CTLA-4 acquired resistance developed with an increase of the immunosuppressive populations, including T-regulatory cells, neutrophils and monocytes. Addition of anti-Ly6C blocking antibody to anti-PD-1/CTLA-4 was capable of completely reversing treatment resistance and restoring CD8 T cell activity in multiple KP lung cancer models and in the autochthonous lung cancer KrasLSL-G12D/p53fl/fl model. We found that there were higher classical Ly6C+ monocytes in anti-PD-1/CTLA-4 combination resistant tumors. B7 blockade illustrated the importance of dendritic cells for treatment efficacy of anti-Ly6C/PD-1/CTLA-4. We further determined that classical Ly6C+ monocytes in anti-PD-1/CTLA-4 resistant tumors are trafficked into the tumor via IFN-γ and the CCL2-CCR2 axis. Mechanistically we found that classical monocytes from ICB resistant tumors were unable to differentiate into antigen presenting cells and instead differentiated into immunosuppressive M2 macrophages or myeloid-derived suppressor cells (MDSC). Classical Ly6C+ monocytes from ICB resistant tumors had a decrease in both Flt3 and PU.1 expression that prevented differentiation into dendritic cells/macrophages. Conclusions: Therapeutically we found that addition of anti-Ly6C to the combination of anti-PD-1/CTLA-4 was capable of complete tumor eradication. Classical Ly6C+ monocytes differentiate into immunosuppressive cells, while blockade of classical monocytes drives dendritic cell differentiation/maturation to reinvigorate the anti-tumor T cell response. These findings support that immunotherapy resistance is associated with infiltrating monocytes and that controlling the differentiation process of monocytes can enhance the therapeutic potential of ICB.

A luminescent and sublimable Dy(III)-based single-molecule magnet.

The reaction of [Ln(hfac)(3)]·2H(2)O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3)(PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4 K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0)=(5.62±0.4)×10(-11) s and Δ=(167±1) K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42 Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001) cm(-1)). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1%, respectively. The thermal investigation of [Dy(hfac)(3)(PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods.

Computational Analysis of the Related Factors of Deep Vein Thrombosis (DVT) Formation in Patients Undergoing Hip Fracture Surgery.

A retrospective study was conducted on 51 patients undergoing hip fracture surgery to investigate the factors associated with the formation of deep venous thrombosis (DVT). The independent sample t-test and correlation analysis were used to sort out and analyze the data. The findings are as follows. (1) Different gender samples showed significant differences in the Caprini score and thrombus location. Most DVTs in females are located in the posterior tibial vein and intermuscular veins. The Caprini score of females was significantly higher than that of males. (2) Age displays a positive correlation with DVT, coronary heart disease, hypertension, and different surgical types, respectively. (3) There is a correlation between age and operation duration. (4) Hyperlipidemia and cerebrovascular disease show a positive correlation with DVT. (5) There was a significant negative correlation between the Caprini score and the quantification of D-dimer. This indicates that in this sample, the higher the patients' Caprini score is, the lower the quantitation of D-dimer will be. (6) Hyperlipidemia and cardiac insufficiency show a positive correlation with cerebrovascular disease. Patients with hyperlipidemia and cardiac insufficiency may also suffer from cerebrovascular diseases.