Effects of rhamnolipid pretreatment on DOM dissolution characteristics and anaerobic fermentation acid production of waste activated sludge.

In this paper, the change characteristics of DOM (dissolved organic matter) and acid production characteristics of anaerobic fermentation in waste activated sludge(WAS) pretreated with rhamnolipid (RL) were studied. The results showed that RL at the dose of 80 mg/gTS could significantly promote the disintegrating of EPS (extracellular polymers) and cell wall in WAS, and a large number of proteins and carbohydrates were dissolved. Three dimensional fluorescence parallel factor analysis showed that the addition of RL enhanced the dissolution and biodegradability of humus-like substances. LC-OCD (Liquid chromatography - organic carbon detection) analysis showed that RL promotes the dissolution of biodegradable components such as Biopolymer, Building Blocks and LMW Neutrals, and ensures the increase of VFA (volatile fatty acids) production in the process of anaerobic fermentation. Under the RL dose of 80 mg/gTS, the maximum VFA production of WAS was obtained at 108 h of anaerobic fermentation, which was 2699.39 mg/L. Acetic acid and propionic acid were the main components in the WAS fermentation broth pretreated by RL. The concentration of butyric acid increased with the increase of RL dose. The RL dose can significantly affect the composition of VFA in WAS fermentation broth.

Defect-Rich Monolayer MoS2 as a Universally Enhanced Substrate for Surface-Enhanced Raman Scattering.

Monolayer 2H-MoS2 has been widely noticed as a typical transition metal dichalcogenides (TMDC) for surface-enhanced Raman scattering (SERS). However, monolayer MoS2 is limited to a narrow range of applications due to poor detection sensitivity caused by the combination of a lower density of states (DOS) near the Fermi energy level as well as a rich fluorescence background. Here, surfaced S and Mo atomic defects are fabricated on a monolayer MoS2 with a perfect lattice. Defects exhibit metallic properties. The presence of defects enhances the interaction between MoS2 and the detection molecule, and it increases the probability of photoinduced charge transfer (PICT), resulting in a significant improvement of Raman enhancement. Defect-containing monolayer MoS2 enables the fluorescence signal of many dyes to be effectively burst, making the SERS spectrum clearer and making the limits of detection (LODs) below 10-8 M. In conclusion, metallic defect-containing monolayer MoS2 becomes a promising and versatile substrate capable of detecting a wide range of dye molecules due to its abundant DOS and effective PICT resonance. In addition, the synergistic effect of surface defects and of the MoS2 main body presents a new perspective for plasma-free SERS based on the chemical mechanism (CM), which provides promising theoretical support for other TMDC studies.

Surface Charge Transfer Doping of MoS2 Monolayer by Molecules with Aggregation-Induced Emission Effect.

Surface charge transfer doping has attracted much attention in modulating the optical and electrical behavior of 2D transition metal dichalcogenides (TMDCs), where finding controllable and efficient dopants is crucial. Here, 1,1,2,2-tetraphenylethylene (TPE) derivative molecules with aggregation-induced emission (AIE) effect were selected as adjustable dopants. By designing nitro and methoxyl functional groups and surface coating, controlled p/n-type doping can be achieved on a chemical vapor deposition (CVD) grown monolayer, MoS2. We investigated the electron transfer behavior between these two dopants and MoS2 with fluorescence, Raman, X-ray photoelectron spectra and transient absorption spectra. 1,1,2,2-Tetrakis(4-nitrophenyl)ethane (TPE-4NO2) with a negative charge aggregation can be a donor to transfer electrons to MoS2, while 1,1,2,2-Tetrakis(4-methoxyphenyl)ethane (TPE-4OCH3) is the opposite and electron-accepting. Density functional theory calculations further explain and confirm these experimental results. This work shows a new way to select suitable dopants for TMDCs, which is beneficial for a wide range of applications in optoelectronic devices.

A 3D-QSAR model for the comprehensive bioenrichment and biodegradation effect of benzotriazole ultraviolet stabilisers and application of the model in molecular modification.

Ultraviolet (UV) absorber, a type of light stabiliser, has received considerable attention because of its high bioenrichment ability and low biodegradability. In this study, benzotriazole ultraviolet stabilisers (BUVSs) were used as the research object, and the bioenrichment and biodegradation data of 13 types of BUVS molecules were subjected to dimensionless processing through quartile data transformation. Additionally, a three-dimensional quantitative structure-activity relationship (3D-QSAR) model was constructed for the investigation of the comprehensive effect of molecular bioenrichment and biodegradation of BUVSs, and improved derivative molecules were designed. Furthermore, the validity of the model was predicted using EPI simulation software, and finally, the biodegradability of BUVSs and their bioenrichment and biological effect before and after modification in the food chain and in the aerobic and anaerobic bacteria in sewage were analysed through the molecular docking technology. A total of 10 derivatives with reduced enrichment ability and enhanced degradability were designed using the CoMFA model analysis (reduction: combined effect value, 0.32-20.55%; log BCF, 2.37-17.59%; and log HL, 0.47-16.94%). Molecular docking showed that the bioenrichment ability of two derivative molecules in the four organisms was decreased by 1.87-27.67%, and the biodegradation ability of four derivative molecules in the three sewage bacteria was enhanced by 1.60-33.38% compared with those before modification. The molecular modification method of UV absorbent developed in this study provides a new perspective for further studies on environment-friendly UV absorbent and helps reduce the risks of these emerging pollutants on the environment and human body.

Interfacially Super-Assembled Benzimidazole Derivative-Based Mesoporous Silica Nanoprobe for Sensitive Copper (II) Detection and Biosensing in Living Cells.

Mesoporous silica nanoparticles (MSNs) functionalized with benzimidazole-derived fluorescent molecules (DHBM) are fabricated via a feasible interfacial superassembly strategy for the highly sensitive and selective detection of Cu2+ . DHBM-MSN exhibits an obvious quenching effect on Cu2+ in aqueous solutions, and the detection limit can be as low as 7.69×10-8  M. The DHBM-MSN solid-state sensor has good recyclability, and the silica framework can simultaneously improve the photostability of DHBM. Two mesoporous silica nanoparticles with different morphologies were specially designed to verify that nanocarriers with different morphologies do not affect the specific detectionability. The detection mechanism of the fluorescent probe was systematically elucidated by combining experimental results and density function theory calculations. Moreover, the detection system was successfully applied to detect Cu2+ in bovine serum, juice, and live cells. These results indicate that the DHBM-MSN fluorescent sensor holds great potential in practical and biomedical applications.

An adjusted 3D-QSAR model for the combined activity of fluoroquinolones photodegradation and microbial degradation assisted by dynamic simulation and its application in molecular modification.

This study developed a comprehensive characterization method for the combined degradation effect of modified fluoroquinolones (FQs) photodegradation and microbial degradation. A combination of revised 3D-QSAR model, molecular docking, path simulation inference, pharmacokinetics, molecular dynamics (MD) simulation and toxicokinetics simulation was used to construct a systematic environment-friendly drug screening system. Five derivatives were screened with significantly improved combined degradation effect (over 20%) and functional characteristics and human health parameters through combined model verification, functional and human health risk assessment. The simulation path of photo- and microbial-degradation of gatifloxacin and new gatifloxacin molecules was derived, and the reaction energy barrier was also calculated. The ratio of the total rate-determining steps change rate of the decreased energy barrier (14.10%:26.30%) was consistent with the ratio of the increased degradation performance predicted by the model (22.87%:19.77%), demonstrating the reliability of revised 3D-QSAR model and it could be applied in molecular modification. MD and toxicokinetics simulation were used to predict the binding energy and aquatic toxicity between photo- and microbial-degradation products and the degradation enzymes, which further to screen the degradation pathways with low potential environmental risks. The findings will be helpful to screen environment-friendly drug and develop appropriate strategies for its risk management.

Application of a 2D-QSAR with a sine normalization method for the biodegradation of fluoroquinolones to poison cyanobacteria.

Cyanobacteria are photosynthetic autotrophic aquatic prokaryotes. One of the methods for controlling cyanobacterial blooms is to destroy the phycobiliproteins required for photosynthesis. In this study, to improve the biodegradation of the fluoroquinolones through inhibit cyanobacteria, the molecular docking scores of 32 fluoroquinolones (FQs) with four categories of phycobiliproteins from cyanobacteria were calculated after sine normalization to characterize the binding ability between them. A two-dimensional quantitative structure-activity relationship (2D-QSAR) model was constructed based on the comprehensive scores. Danofloxacin (DAN) with the highest comprehensive score was chosen for molecular modification. When docking with four categories of phycobiliproteins from cyanobacteria, the docking values of DAN-11 and DAN-16 were increased up to 35.75%. Moreover, their functional characteristics and environmentally friendly predictive values were improved. When the DAN-11 and DAN-16 molecules docked with the other cyanobacterial phycobiliproteins, indicating that the designed DAN derivatives had general applicability to poison cyanobacteria, the weak interaction forces might increase the binding ability between the DAN derivatives and the receptor phycobiliprotein compared with the target molecule.

Investigation of the Potential Environmental Risks of Phthalate Derivatives Designed To Be Environmentally Friendly.

Phthalate derivatives with low estrogenic activity, high infrared spectrum signals, high Raman characteristic vibration spectrum, high fluorescence intensity, and high ultraviolet sensitivity were selected as precursors from our previous studies, so that the changes in their toxicity and estrogenic activity during biological metabolism, ozone oxidation, photocatalytic degradation, photodegradation, and microbial degradation could be studied.The transformation pathways of these derivatives were simulated, and the reaction energy barriers were calculated. To determine the potential environmental risks of these phthalate derivatives, the pharmacophore models of biotoxicity and estrogen activity of phthalates were used to predict the biotoxicity and estrogen activity of the transformed products. The results showed an increase in the biotoxicity and estrogen activity of the biometabolites, ozonation products, photocatalytic degradation products, and microbial degradation products; the only products that did not follow this trend were the photodegradation products. Notably, the pathways that produced more potentially toxic compounds were the less favorable paths. Our results indicate that the transformation products of the designed environmentally friendly phthalate derivatives potentially pose environmental risks. To avoid such risks, the environmental transformation pathway of these derivatives should be simulated to screen for environmentally friendly phthalate molecules. Environ Toxicol Chem 2020;39:1138-1148. © 2020 SETAC.

Environmental Conversion Path Inference of New Designed Fluoroquinolones and Their Potential Environmental Risk.

Fluoroquinolone (FQ) derivatives with environmental friendliness regarding photodegradation, bioconcentration, and genotoxicity were selected from our previous works so that their transformation pathways of biological metabolism, photodegradation, microbial degradation, and chlorination disinfection could be studied. The pathways of these molecules and their derivatives were simulated to investigate the genotoxicity of their transformation products. The results showed that the genotoxicity of the biological metabolites, photodegradation products, and microbial degradation products of the maternal FQ derivatives partially increased, whereas the disinfection by-products exhibited lower genotoxicity than their precursors. Some designed FQ molecular derivatives still had potential environmental risks in biological metabolism, photodegradation, and microbial degradation. This study demonstrated that it is necessary to take into account the potential environmental risks of the transformed products of the modified FQs molecules during biometabolism, photodegradation, microbial degradation, and chlorination processes when designing novel FQ molecules. In future studies, assessing the potential environmental risks during various artificial or natural processes can be applied to screen environmentally friendly novel FQ molecules to avoid and or reduce their threat to environmental and human health.