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To gather enough energy to respond to harmful stimuli, most immune cells quickly shift their metabolic profile. This process of immunometabolism plays a critical role in the regulation of immune cell function. Triclosan, a synthetic antibacterial component present in a wide range of consumer items, has been shown to cause immunotoxicity in a number of organisms. However, it is unclear whether and how triclosan impacts immunometabolism. Here, human macrophages were used as model cells to explore the modulatory effect of triclosan on immunometabolism. Untargeted metabolomics using integrated liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) revealed that triclosan changed the global metabolic profile of macrophages. Furthermore, Seahorse energy analysis and

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO 2 @Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N 4 active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO 5 - oxidation and SO 5 ·− desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating 1 O 2 . Subsequently, the h VB + can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly–enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).

Graphene oxide (GO, a popular 2D graphene-based nanomaterial) has developed quickly and has received considerable attention for its applications in environmental protection and pollutant removal. However, significant knowledge gaps still exist about the interaction characteristic and joint toxicity mechanism of GO and cadmium (Cd) on aquatic organisms. In this study, GO showed a high adsorption capacity (120. 6 mg/g) and strong adsorption affinity (K

Engineered nanomaterials (ENMs), especially transition metal dichalcogenide (TMDC), have received great attention in recent years due to their advantageous properties and applications in various fields and are inevitably released into the environment during their life cycle. However, the effect of natural nanocolloids, widely distributed in the aquatic environment, on the environmental transformation and ecotoxicity of ENMs remains largely unknown. In this study, the effects of natural nanocolloids were compared to humic acid on the environmental transformation and ecotoxicity of single-layer molybdenum disulfide (SLMoS2), a representative TMDC. SLMoS2 with nanocolloids or humic acid (HA) enhanced their dispersion and Mo ion release in deionized water. Nanocolloids induced growth inhibition, reactive oxygen species (ROS) elevation, and cell permeability. Low-toxicity SLMoS2 combined with nanocolloids will enhance the above adverse effects. SLMoS2-nanocolloids induced serious damage (cell distortion and deformation), SLMoS2 internalization, and metabolic perturbation on Chlorella vulgaris (C. vulgaris). In contrast, the addition of HA induced the growth promotion and lower ROS level, inhibited the internalization of SLMoS2, and mitigated metabolic perturbation on C. vulgaris. This work provides insights into the effect of natural nanocolloids on the behaviors and biological risks of ENMs in aquatic environments, deserving substantial future attention.

Nanocolloids (Ncs) are ubiquitous in natural surface waters. However, the effects of Ncs on the fate and ecotoxicity of graphene oxide (GO, a popular engineered nanomaterial (ENM)) remain largely unknown. Ncs exhibit strong adsorption affinity (KL = 1.93 L/mg) and high adsorption capacity (176.2 mg/g) for GO. After Ncs hybridization, GO nanosheets became scrolls, and the aggregation rate of GO decreased. The influence of humic acid and Ncs on GO toxicity was compared. Humic acid mitigated the phytotoxicity of GO. However, GO and GO-Ncs were found to have an envelopment effect on algal cells, and both could enter algal cells. GO-Ncs induced higher reactive oxygen species (ROS) generation, stronger DNA damage and plasmolysis, and more obvious inhibition of photosynthesis compared to GO. Proteomic analysis revealed that photosystem I- and II-related proteins (e.g., E1ZQR2 and E1ZPG5) were regulated more significantly in the GO-Ncs groups than in the GO groups. A combined proteomic and metabolomic analysis showed that inhibition of carbohydrate, fatty acid, and amino acid metabolism contributed to ROS generation. Given the high concentrations and activity of Ncs, the above results highlight the need for reconsideration of the Ncs-mediated environmental behaviors and risks of ENMs and other pollutants.

Nanocolloids (Ncs) are highly dispersed mixtures of nanoscale (1–100 nm) heterogeneous systems, which are ubiquitous in aquatic environments. Ncs are considered a vital pollutant carrier due to their special surface properties and unique hydrodynamic characteristics. They play an essential role in the process of promoting pollutant migration and transformation. In recent years, with the increase in chemicals in the environment and the complexity of environmental pollution, the health threats of Ncs in ecological systems are arousing great concerning. Therefore, recent work to characterize the ecotoxicity of Ncs has focused on the potential environmental health implications, including exploration of toxicity to aquatic organisms from a wide range of the ecosystem food webs. Herein, we summarize the formation, distribution, and characterization of natural Ncs in the marine environments. Moreover, we highlight the adverse impacts of Ncs on representatives of various trophic levels aquatic organisms (e.g., algae, bacteria, invertebrates, and fish). The mechanisms of Ncs ecotoxicity at the cellular level are reviewed, and the remaining unclear points on toxic tools such as oxidative damage and metabolic disorder are presented. We also discuss the research challenges and future developments within the field of ecotoxicity. This study will bridge our knowledge gap on the ecotoxicity of Ncs.

Lakes are critical for biogeochemical and ecological processes and are sensitive and vulnerable to anthropogenic disturbances, but how and to what extent human activities disturb the biodiversity in lakes remain unknown. Here, we showed the microbial diversity in 46 lakes and assessed the influence of 27 anthropogenic factors. We found that the economic level (e.g., per capita gross domestic product) was strongly negatively correlated (r = -0.97) with bacterial diversity but positively correlated (r = 0.17) with fungal diversity in lakes. The composition of the microbial community significantly changed with increasing economic level. Bacteria are more sensitive than fungi to anthropogenic impacts. Expanding the population size and increasing the economic level may promote the development of fungal diversity but inhibit bacterial diversity. Air quality, urbanization and ozone were negatively correlated with bacterial diversity, and fisheries had a negative correlation with fungal diversity. The anti-interference ability of lake microorganisms in the middle economic level zones (45,000-90,000 yuan/person) was stronger than that in high-level (90,000 yuan/person) and low-level (45,000 yuan/person) economic zones. Overall, our investigation provides national-scale evidence that changes in the microbial diversity in lakes were related to economic levels.

Applications of graphene-based nanomaterials in agriculture have attracted much attention, but their potential risks to crop quality and food safety are largely unknown. The present study found that graphene oxide (GO), GO quantum dots (GOQDs) and reduced GO (rGO) translocated from wheat stems to grains and formed large nanomaterial aggregates. The nanomaterials also reduced the globulin, prolamin, amylose and amylopectin contents by 8–28%, 11–25%, 5–34%, and 23–37%, respectively, decreased the levels of mineral elements and upregulated the soluble sugar content by 19–36% in wheat grains, while rGO downregulated the levels of proteins with nutrient reservoir activity to a greater extent than GO. The downregulation of alpha-amylase inhibitor was responsible for the observed decrease in starch content in grains. The decrease in the mineral element contents obtained with rGO and GOQD was greater than that observed with GO, and this effect was linked to the upregulation of calmodulin mediated by ABC transporters. GOQD and rGO changed the proteomic and metabolomic profiles more strongly than GO, suggesting that graphene materials with a small size and a low oxidation content are clearly more detrimental to grain quality. The above results provide an important basis for further nanomaterial design and agricultural applications.

Nanocolloids are widespread in natural water systems, but their characterization and ecological risks are largely unknown. Herein, tangential flow ultrafiltration (TFU) was used to separate and concentrate nanocolloids from surface waters. Unexpectedly, nanocolloids were present in high concentrations ranging from 3.7 to 7.2 mg/L in the surface waters of the Harihe River in Tianjin City, China. Most of the nanocolloids were 10-40 nm in size, contained various trace metals and polycyclic aromatic hydrocarbons, and exhibited fluorescence properties. Envelopment effects and aggregation of Chlorella vulgaris in the presence of nanocolloids were observed. Nanocolloids entered cells and nanocolloid-exposed cells exhibited stronger plasmolysis, chloroplast damage and more starch grains than the control cells. Moreover, nanocolloids inhibited the cell growth, promoted reactive oxygen species (ROS), reduce the chlorophyll a content and increased the cell permeability. The genotoxicity of nanocolloids was also observed. The metabolomics analysis revealed a significant ( p0.05) downregulation of amino acids and upregulation of fatty acids contributing to ROS increase, chlorophyll a decrease and plasmolysis. The present work reveals that nanocolloids, which are different from specific, engineered nanoparticles (e.g., Ag nanoparticles), are present at high concentrations, exhibit an obvious toxicity in environments, and deserve more attention in the future.

The environmental behaviors and risks associated with graphene oxide (GO, a popular 2D nanomaterial) have attracted considerable attention. GO released to aquatic systems will most likely interact with ubiquitous nanocolloids (Nc) in surface water. However, the effects of Nc on the fate and risk of GO remain largely unknown in water. Herein, the binding of Nc onto GO was investigated via electron microscopy, electron paramagnetic resonance, 2D correlation spectroscopy and biolayer interferometry. The results revealed that electron charge transfers, hydrophilic effects and π-π stacking contributed to a strong affinity (KD = 5.6 nM) and high adsorption capacity (159.8 mg/g) of Nc onto the GO surface. Moreover, GO nanosheets transformed to a scroll morphology or multiple GO particles bridging by Nc, which remarkably reduced the aggregation and sedimentation rates after binding with Nc. Interestingly, co-exposure with Nc greatly alleviated the toxicity (e.g., tail malformation, yolk sac edema and oxidative stress) of GO to zebrafish embryos. Morphological and structural alterations of GO after binding to Nc contributed to the mechanisms for the antagonistic effects on the zebrafish embryos toxicity. The present work provides insights into the environmental fate and risk of GO by ubiquitous Nc in natural water.

The interactions between nanoparticles and humic acid (HA) are critical to understanding the environmental risks and applications of nanoparticles. However, the interactions between HA fractions and graphene oxide (GO, a popular carbon nanosheet) at the molecular level remain largely unclear. Four HA fractions with molecular weights ranging from 4.6 to 23.8 kDa were separated, and the large HA fractions presented low oxygen contents and many aromatic structures. The binding constants of the large HA fractions on GO were 2.6- to 3551-fold higher than those of the small HA fractions, while the maximum adsorption capacities of the larger HA fractions onto GO were much higher. Atomic force microscopy (AFM) found that the small and large HA fractions were spread over the center and the edge of the GO nanosheets, respectively. Density functional theory (DFT) simulation and nuclear magnetic resonance spectroscopy confirmed the above phenomena (three adsorption patterns, "vs", "ps", and "pea") and revealed that HA bonded to the GO nanosheets mainly through van der Waals force and π-π interactions. The integrating analysis of binding affinity, AFM, and DFT provides new insights into the environmental behavior of GO and the applications of GO in pollutant removal under exposure from HA.

Graphene oxide (GO), a novel two-dimension carbon nanomaterial, has showed tremendous potential for utilization in intelligent manufacturing and environmental protection. In parallel, tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) is widely distributed in the water environment and represents a great threat to ecosystem health. However, the related knowledge remained absent regarding the impact of GO on the biological risks of TDCIPP. Herein, GO significantly reduced the mortality and malformation rates of zebrafish induced by TDCIPP maximumly by 28.6% and 41.8%, respectively. Decreased mitochondrial respiratory chain (MRC) enzyme and ATP activity induced by TDCIPP were mitigated by GO. Integrating proteomics and metabolomics revealed TDCIPP obviously induced the downregulation of the proteins and metabolites involved in the cytoskeleton, mitochondrial function, carbohydrate and amino acid metabolism, and the TCA cycle, but the alterations were attenuated by GO. GO primarily promoted MRC activity, carbohydrate metabolism, and fatty acid β-oxidation, thus activating the energy metabolism of zebrafish and leading to antagonistic effects on the developmental toxicity of TDCIPP. These results provide a novel view on the co-exposure of GO with other pollutants and promote the reconsideration of the environmental risks of GO.

Nanomaterial oxides are common formations of nanomaterials in the natural environment. Herein, the nanotoxicology of typical graphene oxide (GO) and carboxyl single-walled carbon nanotubes (C-SWCNT) was compared. The results showed that cell division of Chlorella vulgaris was promoted at 24 h and then inhibited at 96 h after nanomaterial exposure. At 96 h, GO and C-SWCNT inhibited the rates of cell division by 0.08-15% and 0.8-28.3%, respectively. Both GO and C-SWCNT covered the cell surface, but the uptake percentage of C-SWCNT was 2-fold higher than that of GO. C-SWCNT induced stronger plasmolysis and mitochondrial membrane potential loss and decreased the cell viability to a greater extent than GO. Moreover, C-SWCNT-exposed cells exhibited more starch grains and lysosome formation and higher reactive oxygen species (ROS) levels than GO-exposed cells. Metabolomics analysis revealed significant differences in the metabolic profiles among the control, C-SWCNT and GO groups. The metabolisms of alkanes, lysine, octadecadienoic acid and valine was associated with ROS and could be considered as new biomarkers of ROS. The nanotoxicological mechanisms involved the inhibition of fatty acid, amino acid and small molecule acid metabolisms. These findings provide new insights into the effects of GO and C-SWCNT on cellular responses.

The interactions between nanomaterials and cells are fundamental in biological responses to nanomaterials. However, the size-dependent synergistic effects of envelopment and internalization as well as the metabolic mechanisms of nanomaterials have remained unknown. The nanomaterials tested here were larger graphene oxide nanosheets (GONS) and small graphene oxide quantum dots (GOQD). GONS intensively entrapped single-celled Chlorella vulgaris, and envelopment by GONS reduced the cell permeability. In contrast, GOQD-induced remarkable shrinkage of the plasma membrane and then enhanced cell permeability through strong internalization effects such as plasmolysis, uptake of nanomaterials, an oxidative stress increase, and inhibition of cell division and chlorophyll biosynthesis. Metabolomics analysis showed that amino acid metabolism was sensitive to nanomaterial exposure. Shrinkage of the plasma membrane is proposed to be linked to increases in the isoleucine levels. The inhibition of cell division and chlorophyll a biosynthesis was associated with decreases in aspartic acid and serine, the precursors of chlorophyll a. The increases in mitochondrial membrane potential loss and oxidative stress were correlated with an increase in linolenic acid. The above metabolites can be used as indicators of the corresponding biological responses. These results enhance our systemic understanding of the size-dependent biological effects of nanomaterials.

In the present work, we identified root exudates that were stimulated by pristine graphene oxide (PGO), including small-molecule acids, alcoholates, alkanes, amino acids and secondary metabolites. These exudates acted as ligands and became immobilized on the PGO to form ligand-GO complexes (LGO). Compared with PGO, LGO exhibited increased thickness, a higher C : O ratio, and reduced transparency and size. Nitrogen- and sulfur-containing groups were observed in LGO. LGO, with its decreased negative charges, was less stable than PGO. In addition, LGO exhibited more unpaired electrons and disordered structures and greater UV absorption compared with PGO. The above alterations in the properties of PGO that occurred after modification of the PGO by exudates induced significant malformations (abnormal tail flexure and pericardial edema) and the loss of mitochondrial membrane polarization in zebrafish as a model organism. This work revealed that root exudates act as natural ligands and significantly alter the properties of PGO.