Co-Mn-Fe spinel-carbon composite catalysts enhanced persulfate activation for degradation of neonicotinoid insecticides: (Non) radical path identification, degradation pathway and toxicity analysis.

The extensive utilization of neonicotinoid insecticides (NNIs) in agricultural practices ultimately poses a significant threat to both the environment and human health. This work focuses on the efficient degradation and detoxification of the representative NNI, thiamethoxam (THX), and explores the underlying mechanism using a Co-Fe-Mn mixed spinel doped carbon composite catalyst activated persulfate. The findings demonstrate that the composite effectively degrades THX, achieving a degradation rate of 95% in 30 mins, while requiring only a fraction (one-sixteenth) of the oxidant dosage compared to pure carbon. The study aimed to examine the negative impact of reactive halogens on reactive oxygen species within a saline environment. The degradation byproducts were linked to the presence of two common electron-withdrawing groups, namely halogens and nitro in the THX molecule. It was hypothesized that the degradation process was primarily influenced by C-N bond breaking and hydroxylation occurring between the diazine oxide and 2-chlorothiazole rings. Consequently, dehalogenation and carbonylation processes facilitated the elimination of halogenated components and pharmacophores from the THX, leading to detoxification. In addition to the identified free radical pathway including SO4•-, •OH and O2•- contributed to THX degradation, the participation of non-radical pathways (1O2 and electron transfer) were also confirmed. The efficacy of detoxification was further validated through toxicity assessment, employing quantitative conformation relationship prediction and microbial culture utilizing Bacillus subtilis.

Hierarchical CoMoS3.13/MoS2 hollow nanosheet arrays as bifunctional electrocatalysts for overall water splitting.

Hollow hetero-nanosheet arrays have attracted great attention due to their efficient catalytic abilities for water splitting. We successfully fabricated ZIF-67-derived hollow CoMoS3.13/MoS2 nanosheet arrays on carbon cloth in situ through a two-step heating-up hydrothermal method, in which the MoS2 nanosheets were suitably distributed on the surface of the hollow CoMoS3.13 nanosheet arrays. There was a distinct synergistic effect between CoMoS3.13 and MoS2, and a large number of defective and disordered interfaces were formed, which improved the charge transfer rate and provided abundant electrochemical active sites. CMM 0.5, with the optimal Mo doping concentration of 0.5 mmol, exhibited the best catalytic properties. The overpotential values of CMM 0.5 at 10 mA cm-2 were only 107 and 169 mV for the HER and OER, respectively, and it had nearly 100% faradaic efficiency. A dual-electrode electrolytic cell assembled with CMM 0.5 required a voltage of only 1.507 V at 10 mA cm-2 for overall water splitting, and it displayed remarkable long-term durable bifunctional stability.

Determinants of Users' Attitude and Intention to Intelligent Connected Vehicle Infotainment in the 5G-V2X Mobile Ecosystem.

With the accelerating industrialization of 5G-V2X and smart automobiles, the intelligent connected vehicle (ICV) integrated with sophisticated communication, caching, computing, and control techniques enhance the functionality of in-vehicle infotainment (IVI) and also provide more powerful telematic or entertainment choices in vehicular environment. The diverse needs of ICV users (e.g., drivers and passengers) can be satisfied during commuting and traveling. However, considering the limitations of transportation environment, the potential attitude and usage behavior for the upcoming ICV infotainment directly impacts on the traffic and road safety in sustainable cities. In this paper, we conduct an online and offline survey to investigate the key factors influencing the user attitude and intention of ICV infotainment, where the answers of a total of 502 valid respondents (i.e., IVI users) are collected in China. A conceptual technology acceptance model with the constructs of perceived usefulness (PU), perceived ease of use (PEOU), social influence (SI), consumer innovation (CI), and perceived risk (PR) is established, and then assessed via partial least square structural equation modeling. We find that the constructs of PU, PEOU, CI, and SI have a direct impact on attitude and usage intention, of which 46.8% and 73.4% of variance, respectively, are explained. The respondents show positive attitudes and higher usage intention towards the ICV infotainment. Although PR has insignificant path with attitude and intention, the driving experience moderation effect exists between PR and usage intention. We can see that ICV infotainment will become a trend in future transportation scenario. Through this survey, reference for traffic safety and usage norms will be provided to reduce the risky of public health issues (e.g., traffic accidents) in the context of ICV infotainment.

Hydrogen sulfide and calcium effects on cadmium removal and resistance in the white-rot fungus Phanerochaete chrysosporium.

Hydrogen sulfide (H2S), an emerging gas transmitter, has been shown to be involved in multiple intracellular physiological and biochemical processes. In this study, the effects of hydrogen sulfide coupled with calcium on cadmium removal and resistance in Phanerochaete chrysosporium were examined. The results revealed that H2S enhanced the uptake of calcium by P. chrysosporium to resist cadmium stress. The removal and accumulation of cadmium by the mycelium was reduced by H2S and Ca2+ pretreatment. Moreover, oxidative damage and membrane integrity were alleviated by H2S and Ca2+. Corresponding antioxidative enzyme activities and glutathione were also found to positively respond to H2S and Ca2+, which played an important role in the resistance to cadmium-induced oxidative stress. The effects of hydroxylamine (HA; a hydrogen sulfide inhibitor) and ethylene glycol-bis-(2-aminoethylether)-N,N,N',N'-tetraacetic acid (EGTA; a calcium chelator) toward H2S and Ca2+ and their cross-interactions confirmed the positive roles and the potential crosstalk of H2S and Ca2+ in cadmium stress resistance. These findings imply that the protective effects of H2S in P. chrysosporium under cadmium stress may occur through a reduction in the accumulation of cadmium and promotion of the antioxidant system, and the H2S-regulated pathway may be associated with the intracellular calcium signaling system.Key points• Altered monoterpenoid tolerance mainly related to altered activity of efflux pumps.• Increased tolerance to geranic acid surprisingly caused by decreased export activity.• Reduction of export activity can be beneficial for biotechnological conversions.

Biodegradation and detoxification of neonicotinoid insecticide thiamethoxam by white-rot fungus Phanerochaete chrysosporium.

The extensive use of neonicotinoid pesticides in the past two decades caused serious impacts on many kinds of living beings. Therefore, it has been strongly suggested to detoxify and eliminate neonicotinoids' residual levels in environment. Here, the degradation and detoxification of thiamethoxam (THX) by white-rot fungus Phanerochaete chrysosporium was conducted. Results shown that P. chrysosporium can tolerate THX and degraded 49% of THX after incubation for 15 days, and then 98% for 25 days at the initial concentration of 10 mg/L, which indicates the excellent degradation ability of this fungus to THX. Based on the by-products identified, THX underwent dechlorination, nitrate reduction, and C-N cleavage between the 2-chlorothiazole ring and oxadiazine. (Z)-N-(3-methyl-1,3,5-oxadiazinan-4-ylidene)nitramide and 3-methyl-1,3,5-oxadiazinan-4-imine were identified as the main metabolites. The impacts of THX and its corresponding degradation intermediates on the growth of E. coil and Microcystis aeruginosa as well as the germination of rape and cabbage demonstrated that P. chrysosporium effectively degrades THX into metabolites and reduces its biotoxicity. The present work demonstrates that P. chrysosporium can be effectively used for degradation and detoxification of THX.