Tungsten doped FeCoP2 nanoparticles embedded into carbon for highly efficient oxygen evolution reaction.

Designing active and stable electrocatalysts with economic efficiency for oxygen evolution reaction (OER) is essential for developing water splitting process at an industrial scale. Herein, we rationally designed a tungsten doped iron cobalt phosphide incorporated with carbon (Wx-FeCoP2/C), prepared by a mechanochemical approach. X-ray photoelectron spectroscopy (XPS) revealed that the doping of W led to an increasing of Co3+/Co2+ and Fe3+/Fe2+ molar ratios, which contributed to the enhanced OER performance. As a result, a current density of 10 mA cm-2 was achieved in 1 M KOH at an overpotential of 264 mV on the optimized W0.1-FeCoP2/C. Moreover, at high current density of 100 mA cm-2, the overpotential value was 310 mV, and the corresponding Tafel slope was measured to be 48.5 mV dec-1, placing it among the best phosphide-based catalysts for OER. This work is expected to enlighten the design strategy of highly efficient phosphide-based OER catalysts.

Two aquaporins, PIP1;1 and PIP2;1, mediate the uptake of neonicotinoid pesticides in plants.

Neonicotinoids (NEOs), a large class of organic compounds, are a type of commonly used pesticide for crop protection. Their uptake and accumulation in plants are prerequisites for their intra- and intercellular movements, transformation, and function. Understanding the molecular mechanisms that underpin NEO uptake by plants is crucial for effective application, which remains elusive. Here, we demonstrate that NEOs enter plant cells primarily through the transmembrane symplastic pathway and accumulate mainly in the cytosol. Two plasma membrane intrinsic proteins discovered in Brassica rapa, BraPIP1;1 and BraPIP2;1, were found to encode aquaporins (AQPs) that are highly permeable to NEOs in different plant species and facilitate NEO subcellular diffusion and accumulation. Their conserved transport function was further demonstrated in Xenopus laevis oocyte and yeast assays. BraPIP1;1 and BraPIP2;1 gene knockouts and interaction assays suggested that their proteins can form functional heterotetramers. Assessment of the potential of mean force indicated a negative correlation between NEO uptake and the energy barrier of BraPIP1;1 channels. This study shows that AQPs transport organic compounds with greater osmolarity than previously thought, providing new insight into the molecular mechanisms of organic compound uptake and facilitating innovations in systemic pesticides.

Insights into the volatile flavor and quality profiles of loquat (Eriobotrya japonica Lindl.) during shelf-life via HS-GC-IMS, E-nose, and E-tongue.

Loquat fruits are among the most popular Chinese fruits because of their unique taste and aroma. The quality profiles of these fruits during 18 days of shelf-life at 20 °C were elucidated by headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS), E-nose, and E-tongue. During shelf-life period, the properties and variations of 43 (20 aldehydes, 7 esters, 6 ketones, 1 alcohol, and 1 furan) volatile flavored compounds were determined by GC-IMS, which showed that the contents of methyl 3-methyl butanoate, ethyl acetate, and dimethyl ketone gradually decrease with prolonged shelf-life time, while (E)-2-heptenal, heptanal, (E)-2-pentenal, 1-penten-3-one 3-pentanone and 2-pentylfuran increase. The PCA based on the signal intensity of GC-IMS and E-nose, revealed that loquat fruits are well distinguished at different shelf-life times. The taste profile alternates as the storage time increases, along with higher pH, and lower amounts of total soluble solids, vitamin C, and total phenolics. The visual plots of GC-IMS, E-nose, and E-tongue had good consistency, and they characterized the aroma characteristics of loquat fruits well during different shelf-life periods. The findings of this research provide a useful understanding of the flavors of loquat fruits during their prolonged shelf-life, and a potential research basis for advancements in the loquat industry.

Visible-Light-Promoted Intermolecular ß-Acyl Difunctionalization of Alkenes via Oxidative Radical-Polar Crossover.

A visible-light-induced ß-acyl difunctionalization of alkenes with acyl oxime esters and various nucleophiles was developed to achieve molecular complexity from readily available raw materials via oxidative radical-polar crossover. A variety of nucleophiles, including NH-sulfoximines, indoles, indazole, and trimethoxybenzene, were all effectively applicable to the sustainable reaction system. The novel synthetic strategy features mild reaction conditions, a broad substrate scope (39 examples), easy scale-up, and excellent regioselectivity.

Visible-Light-Induced Decarboxylation of Dioxazolones to Phosphinimidic Amides and Ureas.

A visible-light-induced external catalyst-free decarboxylation of dioxazolones was realized for the bond formation of N=P and N-C bonds to access phosphinimidic amides and ureas. Various phosphinimidic amides and ureas (47 examples) were synthesized with high yields (up to 98%) by this practical strategy in the presence of the system's ppm Fe.

CuCl-photocatalyzed C-H amination of benzoxazoles.

The direct coupling of benzoxazoles and amines was realized by visible light irradiation and CuCl catalysis. Various aminated benzoxazoles were successfully synthesized under mild conditions with air as an oxidant.

Effects of tebuconazole application at different growth stages on rice grain quality of rice-based untargeted metabolomics.

Tebuconazole (TEB) is a pesticide widely used in crops and has a strong control effect on fungal pathogens. TEB abuse has caused many food safety problems. In this study, the TEB residue in rice and the effect of TEB on white rice quality were investigated. The results showed that under two spraying concentrations, the TEB residue in rice was 11.21-19.05 µg/kg and 24.45-31.12 µg/kg, and there was no food safety risk of pesticide residue. When applying TEB according to the instructions, no significant effect was found. However, when 3 times the recommended TEB concentration was used at the filling stage, the protein content of white rice decreased significantly from 106.52 mg/g to 80.72 mg/g. At the jointing，heading and filling stage, the amylose content of white rice decreased to 53.95 mg/g, 48.77 mg/g and 49.04 mg/g from the blank control group. Plant metabolic analysis using LC-QTOF/MS revealed that the amino acid-related metabolic pathways in white rice were significantly affected by TEB. This is closely related to the decrease in protein accumulation in white rice and the stress response of rice plants. The increase in pantothenic acid content in white rice indicated that the glycolysis pathway of white rice plants was affected, and the consumption of starch and sucrose increased, leading to the inhibition of amylose accumulation in white rice. The increase in soluble sugar content and decrease in phosphocholine content in white rice suggested that rice plants were affected by TEB exposure, which produced similar effects under drought stress.

Impact of substrate digestibility on microbial community stability in methanogenic digestors: The mechanism and solution.

This study investigated the temporal dynamics of digestion efficiency and community stability in digesters fed with waste activated sludge (WAS), straw (STR-AD), food waste (FW-AD) and mixture of straw-and-food waste (STR-FW-AD). Results showed that carbon removals of recalcitrant substrates (i.e., 48.2 ± 3.9% in WAS-AD and 57.8 ± 4.9% in STR-AD) were lower than that of labile substrates (i.e., 70.7 ± 4.0% in FW-AD). Nonetheless, carbon removal of recalcitrant substrates was largely improved through co-digestion (70.3 ± 3.2% in STR-FW-AD). In contrast to monopoly communities (e.g., the highly enriched Paludibacter) fed with the labile substrates, recalcitrant substrates supported highly diverse communities. Accordingly, the medians of negative/positive cohesions of communities in WAS-AD, STR-AD, STR-FW-AD and FW-AD decreased from 0.86 to 0.63, suggesting their decreasing community stability. Microbial source tracking analyses showed the major contribution of the STR-AD community to the co-digestion community. This study provided unprecedented mechanistic insight into stability improvement of substrate co-digestion on the methanogenic digestion microbiome.

Ce(III)/Photoassisted Synthesis of Amides from Carboxylic Acids and Isocyanates.

The Ce(III)-photocatalyzed synthesis of amides from carboxylic acids and aryl isocyanates was developed. The reaction includes the formation of alkyl radicals from carboxylic acids followed by radical addition to the electron-deficient carbon of isocyanate.

Uptake, translocation, and subcellular distribution of three triazole pesticides in rice.

Triazole pesticides are widely used for the control of pathogenic fungi in crops, which were frequently detected in edible parts. Its extensive use has caused many environmental pollution and food safety problems. In this study, the uptake, translocation, and subcellular distribution of three triazole pesticides (triadimefon, tebuconazole, and epoxiconazole) in rice were investigated. The results showed that the three triazole pesticides could be taken up by rice roots, but their distribution in plant tissues were different. The accumulation of the three pesticides in rice root followed the order of epoxiconazole (4.26 mg/kg, 24 h) > tebuconazole (2.63 mg/kg, 24 h) > triadimefon (1.37 mg/kg, 24 h), while a reversed order was observed in rice shoots, triadimefon (0.48 mg/kg, 24 h) > tebuconazole (0.40 mg/kg, 24 h) > epoxiconazole (0.21 mg/kg, 24 h). The translocation of triazole pesticides within rice tissues involved both symplast and apoplast pathways, with triadimefon preferentially through by the apoplast pathway and epoxiconazole through by the symplast pathway. The proportions of triadimefon, tebuconazole, and epoxiconazole in the symplast and apoplast of rice plants were 15-33%, 6-31%, 7-37%, and 67-85%, 69-94%, 63-93%, respectively. The subcellular distribution revealed that all pesticides have a higher proportion in cell walls than in cell organelles and soluble components. Epoxiconazole has the highest accumulated capacity in the cell wall (45-67%) and triadimefon was more concentrated in the soluble components (24-29%). However, there were no significant differences in the amount of three pesticides in cell organelles. The distribution of the three pesticides in aboveground and underground parts of rice plant, uptake and transportation in symplast and apoplast pathways, and distribution in the subcellular tissue are all related to their hydrophobicity.

Metal-Free Photosynthesis of Alkylated Benzimidazo[2,1-a]isoquinoline-6(5H)-ones and Indolo[2,1-a]isoquinolin-6(5H)-ones in PEG-200.

A visible-light-induced decarboxylation reaction was developed for the synthesis of alkylated benzimidazo[2,1-a]isoquinoline-6(5H)-ones and indolo[2,1-a]isoquinolin-6(5H)-ones under metal-free conditions. Impressively, metal catalysts and traditionally volatile organic solvents could be effectively avoided.

Acyl Radicals from α-Keto Acids: Metal-Free Visible-Light-Promoted Acylation of Heterocycles.

A general and metal-free visible-light-induced decarboxylative arylation procedure at room temperature was described for the construction of acylated heterocyclic derivatives, such as benzimidazo/indolo[2,1-a]isoquinolin-6(5H)-ones, aroylazaspiro[4.5]trienones, thioflavones, and so on. This practical arylation procedure was conducted by using 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) as a photocatalyst under mild conditions, which avoided the use of an additional base, traditional heating, and metal reagents.

Sludge pre-treatments change performance and microbiome in methanogenic sludge digesters by releasing different sludge organic matter.

In this study, temporal impacts of thermal, alkaline/acid and thermal-alkaline sludge pre-treatments on digestion performance and microbiome were investigated and compared in methanogenic sludge digesters. Results showed that thermal and alkaline/acid pre-treatments were efficient in releasing intracellular and EPS organic matter, respectively. The thermal-alkaline pre-treatment showed synergistic impacts of both thermal and alkaline/acid pre-treatments by releasing the major portion of sludge organic matter from solid- to liquid-phase, which result in 60-65% organic carbon removal in subsequent sludge digestion and further optimizing digestion temperature had negligible improvement. The 16S rRNA gene-based analyses suggested that organic matter released from sludge pre-treatments is a major deterministic parameter in shaping sludge microbiome. Pre-treatment specific lineages were identified in different sludge digesters, whereas several taxa were identified as common functionally active populations in sludge digestion. This study provided mechanistic insights into impacts of pre-treatments on digestion performance and microbiome in methanogenic sludge digesters.

Development of an alkaline/acid pre-treatment and anaerobic digestion (APAD) process for methane generation from waste activated sludge.

Anaerobic sludge digesters are biorefineries for energy recovery from waste activated sludge (WAS) via methane production, in which disintegration of floc structure and microbial cells is a major challenge in releasing extracellular polymeric substances (EPS) and cytoplasmic macromolecules for subsequent hydrolysis and fermentation. Here, we developed a new process combining alkaline/acid pre-treatments and anaerobic digestion (APAD) to improve sludge digestion. Both alkaline and acid pre-treatments effectively disintegrated the floc structure and microbial cells to release sludge organic contents. Under the optimized alkaline/acid pre-treatment condition, carbon removal achieved 52.8 ± 1.7% in APAD digesters, in contrast to 30.9 ± 2.2% and 42.4 ± 1.6% in anaerobic digesters fed with fresh WAS (control-AD) and thermal pre-treated sludge (thermal-AD), respectively. Both alkaline/acid and thermal pre-treatments largely shifted sludge community composition and function, but in distinct ways, possibly due to their different sludge constitutes (i.e., dissolved organic matter and NaCl). Correspondingly, microbial network analysis identified three modules with varied keystone taxa and interaction patterns in the three digesters. Life cycle assessment showed the comparable environmental impacts of APAD, thermal-AD and control-AD. In all, this study provided a new solution for WAS treatment and insights into impact of sludge pre-treatments on sludge digestion microbiome.

Effect of Imidacloprid Uptake from Contaminated Soils on Vegetable Growth.

In the present study, the effect of imidacloprid uptake from contaminated soils on the growth of leaf vegetable Shanghaiqing was investigated. The result showed that during 35-day exposure, the concentration of imidacloprid (IMI) was in the order of vegetable shoots > vegetable roots > soil, indicating that IMI was more readily concentrated in vegetable shoots than in roots. Moreover, the biomass of IMI-treated vegetable shoots was comparable to that of the controls with early exposure, but was higher than that of the controls after 7-day exposure, showing that the test concentration of IMI could stimulate vegetable growth. The plant metabolic analysis of vegetable shoots using LC-QTOF/MS revealed that IMI may cause oxidative stress to the plant shoots with early exposure; however, the stressful situation of IMI seems to be relieved with the increase of some substances (such as spermidine and phenylalanine) with late exposure. Moreover, the upregulation of N-rich amino acids (glutamine, aspartate, and arginine) suggested that the process of fixing inorganic nitrogen in the plant should be enhanced, possibly contributing to enhanced growth rates. Additionally, four IMI's metabolites were identified by using MS-FINDER software, and the distribution of three metabolites in vegetable tissues was compared.

Organic matter rather than salinity as a predominant feature changes performance and microbiome in methanogenic sludge digesters.

Due to low digestibility and long retention time of anaerobic sludge digestion, pre-treatment with alkaline/acid has been widely employed to enhance the rate and extent of sludge digestion. Nonetheless, effects of gradient concentrations of alkaline/acid pre-treatments and resulting salinity on digestion performance and sludge microbiome remain poorly understood. To elucidate these effects, both batch- and reactor-experiments were setup with varied feeding sludge. Significant digestion improvement and sludge microbiome changes were observed with alkaline/acid sludge pre-treatment, compared to non-pretreatment controls, e.g., ˜88% increase of carbon removal in sludge digesters. Surprisingly, with the same concentration of influent sludge, no notable change in digestion performance and sludge microbiome was observed in digesters when increasing alkaline/acid concentrations from 0.25 to 0.8 mol/L, and in batch serum bottles with or without NaCl amendment. Consequently, organic compounds dissolved in sludge pre-treatment could be a predominant selective pressure driving the performance and microbiome changes. By contrast, salinity as a consequence of the alkaline/acid pre-treatment could only enrich specific lineages, without altering the overall community profile and function. Together, this study provided insights into specific impacts of major factors on digester performance and sludge microbiome, and shed lights on optimization of sludge digestion.