Co-exposure of butyl benzyl phthalate and TiO2 nanomaterials (anatase) in Metaphire guillelmi: Gut health implications by transcriptomics.

During the COVID-19 pandemic, an abundance of plastic face masks has been consumed and disposed of in the environment. In addition, substantial amounts of plastic mulch film have been used in intensive agriculture with low recovery. Butyl benzyl phthalate (BBP) and TiO2 nanomaterials (nTiO2) are widely applied in plastic products, leading to the inevitable release of BBP and nTiO2 into the soil system. However, the impact of co-exposure of BBP and nTiO2 at low concentrations on earthworms remains understudied. In the present study, transcriptomics was applied to reveal the effects of individual BBP and nTiO2 exposures at a concentration of 1 mg kg-1, along with the combined exposure of BBP and nTiO2 (1 mg kg-1 BBP + 1 mg kg-1 nTiO2 (anatase)) on Metaphire guillelmi. The result showed that BBP and nTiO2 exposures have the potential to induce neurodegeneration through glutamate accumulation, tau protein, and oxidative stress in the endoplasmic reticulum and mitochondria, as well as metabolism dysfunction. The present study contributes to our understanding of the toxic mechanisms of emerging contaminants at environmentally relevant levels and prompts consideration of the management of BBP and nTiO2 within the soil ecosystems.

Butyl benzyl phthalate exposure impact on the gut health of Metaphire guillelmi.

Agricultural films are extensively utilized in high-intensity agriculture, with China's annual usage reaching 1.5 million tons. Unfortunately, the recovery rate is less than 60%, leading to an inevitable accumulation of plastic mulch in agricultural soils. This accumulation primarily introduces butyl benzyl phthalate (BBP) into soil ecosystems, whose specific effects remain largely unclear, thereby posing potential risks. The present study focuses on the exposure impact of BBP on earthworms, Metaphire guillelmi, a commonly found endogenic earthworm within real farmland, as it provides insight into the direct interaction between biota gut health and contaminants. Specifically, we studied the biomarkers related to oxidative stress, the digestive system, and neurotoxicity within the gut of Metaphire guillelmi, and the integrated biological response (IBR) index was utilized to track these markers at different timeframes after BBP exposures. Our findings indicate that BBP exposures lead to oxidative damage, digestive system inhibition, and neurotoxicity, with IBR indexes of 14.6 and 17.3 on the 14th and 28th days, respectively. Further, the underlying mechanisms at a molecular level through molecular docking were investigated. The results showed that the most unstable interaction was with the Na+K+-ATPase (binding energy: -2.25 kcal-1), while BBP displayed stable bonds with superoxide dismutase and 8-hydroxydeoxyguanosine via hydrogen bonds and hydrophobic interaction. These interactions resulted in changes in protein conformation and their normal physiological functions, offering new insights into the molecular mechanism underlying enzymatic activity changes. This study has significant implications for the prediction of toxicity, environmental risk assessment, and the establishment of regulations related to BBP.

Co-exposure effects of butyl benzyl phthalate and TiO2 nanomaterials (anatase) on Metaphire guillelmi gut health.

Phthalic acid esters (PAEs) and TiO2 nanomaterials (nTiO2) are commonly used as plastic additives, nano-fertilizers or nano-pesticides. Their excessive co-applications led to the co-occurrence, which can induce damage to soil organisms such as Metaphire guillelmi (an earthworm widespread in farmland). However, the co-exposure effects of butyl benzyl phthalate (BBP, a typical PAEs) and nTiO2 on Metaphire guillelmi at environmental-relevant concentrations remain unclear. In this study, 1 mg kg-1 BBP and 1 mg kg-1 nTiO2 (anatase) were added into the soil to assess: (1) their effects on oxidative damage, digestive system, and neurotoxicity in Metaphire guillelmi gut on days 14 and 28; and (2) whether BBP and nTiO2 affected Metaphire guillelmi gut health by disrupting intestinal microorganisms. The results demonstrated that BBP and nTiO2 had the potential to inhibit the activity of superoxide dismutase, cellulase, protease, Na+K+-ATPase, and Ca2+-ATPase, as well as cause oxidative damage by altering intestinal bacteria such as Marmoricola and Microvirga at genus levels after 28 d-exposure. However, the exposure did not cause disorders of the intestinal bacteria. The present study provides more evidence for the sustainable application and scientific management of BBP and nTiO2, thus providing better guidance for PAEs and engineered nanomaterials regulations in agroecosystems.

Rational Construction of Yolk-Shell Bimetal-Modified Quinonyl-Rich Covalent Organic Polymers with Ultralong Lithium-Storage Mechanism.

Covalent organic polymers are attracting more and more attention for energy storage devices due to their lightweight, molecular viable design, stable structure, and environmental benignity. However, low charge-carrier mobility of pristine covalent organic materials is the main drawback for their application in lithium-ion batteries. Herein, a yolk-shell bimetal-modified quinonyl-rich covalent organic material, Co@2AQ-MnO2, has been designed and synthesized by in situ loading of petal-like nanosized MnO2 and coordinating with Co centers, with the aim to improve the charge conductivity of the covalent organic polymer and activate its Li-storage sites. As investigated by in situ FT-IR, ex situ XPS, and electrochemical probing, the quinonyl-rich structure provides abundant redox sites (carbonyl groups and π electrons from the benzene ring) for lithium reaction, and the introduction of two types of metallic species promotes the charge transfer and facilitates more efficient usage of active energy-storage sites in Co@2AQ-MnO2. Thus, the Co@2AQ-MnO2 electrode exhibits good cycling performance with large reversible capacity and excellent rate performance (1534.4 mA h g-1 after 200 cycles at 100 mA g-1 and 596.0 mA h g-1 after 1000 cycles at 1000 mA g-1).

Boosted π-Li Cation Effect in the Stabilized Small Organic Molecule Electrode via Hydrogen Bonding with MXene.

The high solubility of the small organic molecule materials in organic electrolytes hinders their development in rechargeable batteries. Hence, this work designs an ultrarobust hydrogen-bonded organic-inorganic hybrid material: the small organic unit of the 1,3,6,8-tetrakis (p-benzoic acid) pyrene (TBAP) molecule connected with the hydroxylated Ti3C2Tx MXene through hydrogen bonds between the terminal groups of -COOH and -OH. The robust and elastic hydrogen bonds can empower the TBAP, despite being a low-molecule organic chemical, with unusually low solubility in organic electrolytes and thermal stability. The alkali-treated Ti3C2Tx MXene provides a hydroxyl-rich conductive network, and the small organic molecule of TBAP reduces the restacking of MXene layers. Therefore, the combination of these two materials complements each other well, and this organic-inorganic TBAP@D-Ti3C2Tx electrode delivers large reversible capacities and long cyclic life. Notably, with the assistance of the in situ FT-IR characterization of the electrode within the fully lithiated (0.005 V) and the delithiated (3.0 V) states, it is revealed that a powerful π-Li cation effect mainly governs the lithium-storage mechanism with the highly activated benzene ring and each C6 aromatic ring, which can reversibly accept six Li-ions to form a 1:1 Li/C complex.

Boosting storage properties of reduced graphene oxide fiber modified with MOFs-derived porous carbon through a wet-spinning fiber strategy.

Supercapacitors that are light weight and flexible, while occupying a low volume and demonstrating good mechanical properties are in demand for portable energy storage devices. Graphene composite fibers are supposed to be ideal electrodes for flexible fiber-shaped supercapacitors. Integration of MOFs-derived porous carbon into graphene fibers provides desirable electrochemical and mechanical properties. Herein, a general strategy is shown for the preparation of MOFs-derived porous carbon/reduced graphene oxide fibers. Close-packed and aligned graphene sheets along with porous MOFs-derived porous carbon can achieve outstanding mechanical properties through synergistic effects. Consequently, a large specific capacitance of 56.05 F cm-3, a good tensile property of 86.5 MPa and a high retention of 96.6% after 10 000 cycles can be achieved with the composite fibers. Moreover, a further deposition of polyaniline (PANI) and manganese dioxide (MnO2) by in situ growth on the fabricated composite fibers provide an improvement in specific capacitance with value of 74.21 F cm-3 and 65.08 F cm-3, respectively. The above results demonstrate the promising application of composite fibers as a flexible and stable electrode and substrate for energy storage devices.

Flexible all-solid-state supercapacitors of polyaniline nanowire arrays deposited on electrospun carbon nanofibers decorated with MOFs.

Porous carbons derived from metal-organic frameworks (MOFs) are promising materials for a number of energy- and environment-related applications. To integrate the powder MOFs-derived carbon into feasible engineered materials, a facile strategy to fabricate integrated flexible film is developed by growing MOFs nanoparticles on polyimide electrospun nanofibers, followed by calcination, to fabricate freestanding carbon nanofiber membranes decorated with porous carbon. Then vertically polyaniline nanowire arrays are uniformly deposited on the hierarchical porous carbon substrates by in situ polymerization. Thanks to the good distribution of MOFs-derived porous carbon on carbon nanofibers and the compact configuration interwoven by conducting polymers, the designed hybrid electrode could be used directly as a freestanding electrode for supercapacitors, which displayed a high specific capacitance of 1268 F g-1. The assembled flexible solid-state supercapacitor based on the integrated electrodes demonstrated a high volumetric capacitance of 1973 mF cm-3 and a good capacitance retention of 84.9% after 10 000 cycles, which could power a commercial light emitting diode. This strategy may shed light on the design of MOFs-based flexible materials for practical applications of supercapacitors and other electrochemical devices.