High sensitivity in quantitative analysis of mixed-size polystyrene micro/nanoplastics in one step.

As emerging environmental pollutants, microplastics (MPs) and nanoplastics (NPs) pose a serious threat to human health. Owing to the lack of feasible and reliable analytical methods, the separation and identification of MPs and NPs of different sizes remains a challenge. In this study, a hyphenated method involving filtration and surface-enhanced Raman spectroscopy (SERS) for the separation and identification of MPs and NPs is reported. This method not only avoids the loss of MPs and NPs during the transfer process but also provides an excellent SERS substrate. The SERS substrate was fabricated by electrochemically depositing silver particles onto the reduced graphene oxide layer coated on stainless steel mesh. Results show that polystyrene (PS) MPs and NPs are efficiently separated on the SERS substrate via vacuum filtration, resulting in high retention rates (74.26 % ± 1.58 % for 100 nm, 81.06 % ± 1.49 % for 500 nm, and 97.73 % ±0.11 % for 5 µm) and low limit of detection (LOD). The LOD values of 100 nm, 500 nm, and 5 µm PS are 8.89 × 10-5, 3.39 × 10-5, and 1.57 × 10-4 µg/mL, respectively. More importantly, a linear relationship for uniform quantification of 100 nm, 500 nm, 3 µm and 5 µm PS was established, and the relationship is Y = 225.61 lgX + 1076.36 with R2 = 0.980. The method was validated for the quantitative analysis of a mixture of 100 nm, 500 nm PS NPs, 3 µm and 5 µm PS MPs in a ratio of 1:1:1:1, which successfully approaches the evaluation of evaluated PS NPs in the range of 10-4-10 µg/mL with an LOD value of approximately 7.82 × 10-5 µg/mL. Moreover, this method successfully detected (3.87 ± 0.06) × 10-5 µg MPs and NPs per gram of oyster tissue.

Differences in toxicity induced by the various polymer types of nanoplastics on HepG2 cells.

The problem of microplastics (MPs) contamination in food has gradually come to the fore. MPs can be transmitted through the food chain and accumulate within various organisms, ultimately posing a threat to human health. The concentration of nanoplastics (NPs) exposed to humans may be higher than that of MPs. For the first time, we studied the differences in toxicity, and potential toxic effects of different polymer types of NPs, namely, polyethylene terephthalate (PET), polyvinyl chloride (PVC), and polystyrene (PS) on HepG2 cells. In this study, PET-NPs, PVC-NPs, and PS-NPs, which had similar particle size, surface charge, and shape, were prepared using nanoprecipitation and emulsion polymerization. The results of the CCK-8 assay showed that the PET-NPs and PVC-NPs induced a decrease in cell viability in a concentration-dependent manner, and their lowest concentrations causing significant cytotoxicity were 100 and 150 µg/mL, respectively. Moreover, the major cytotoxic effects of PET-NPs and PVC-NPs at high concentrations may be to induce an increase in intracellular ROS, which in turn induces cellular damage and other toxic effects. Notably, our study suggested that PET-NPs and PVC-NPs may induce apoptosis in HepG2 cells through the mitochondrial apoptotic pathway. However, no relevant cytotoxicity, oxidative damage, and apoptotic toxic effects were detected in HepG2 cells with exposure to PS-NPs. Furthermore, the analysis of transcriptomics data suggested that PET-NPs and PVC-NPs could significantly inhibit the expression of DNA repair-related genes in the p53 signaling pathway. Compared to PS-NPs, the expression levels of lipid metabolism-related genes were down-regulated to a greater extent by PET-NPs and PVC-NPs. In conclusion, PET-NPs and PVC-NPs were able to induce higher cytotoxic effects than PS-NPs, in which the density and chemical structure of NPs of different polymer types may be the key factors causing the differences in toxicity.

The effect of polystyrene nanoplastics on arsenic-induced apoptosis in HepG2 cells.

Microplastics are detrimental to the environment. However, the combined effects of microplastics and arsenic (As) remain unclear. In this study, we investigated the combined effects of polystyrene (PS) microplastics and As on HepG2 cells. The results showed that PS microplastics 20, 50, 200, and 500 nm in size were taken up by HepG2 cells, causing a decrease in cellular mitochondrial membrane potential. The results of lactate dehydrogenase release and flow cytometry showed that PS microplastics, especially those of 50 nm, enhanced As-induced apoptosis. In addition, transcriptome analysis revealed that TP53, AKT1, CASP3, ACTB, BCL2L1, CASP8, XIAP, MCL1, NFKBIA, and CASP7 were the top 10 hub genes for PS that enhanced the role of As in HepG2 cell apoptosis. Our results suggest that nano-PS enhances As-induced apoptosis. Furthermore, this study is important for a better understanding of the role of microplastics in As-induced hepatotoxicity.

Purification and characterization of a novel immunoregulatory peptide from Sipunculus nudus L. protein.

This study aimed to purify and characterize immunoregulatory peptides from Sipunculus nudus L. and to explore the underlying mechanisms. Ultrafiltration, gel filtration chromatography, and reverse phase high-performance liquid chromatography (RP-HPLC) were used to purify the peptide following enzymatic hydrolysis. Rates of lymphocyte proliferation and phagocytosis as well as nitric oxide (NO) production levels were used as indicators of immunoregulatory activity to screen the fractions. The amino acid sequence of the peptide, designated as SNLP, was identified as Arg-Val-Lys-Gly-Lys-Ile-Leu-Ala-Lys-Arg-Leu-Asn (RVKGKILAKRLN) by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Treatment with the synthetic SNLP increased the proliferation and phagocytosis of RAW 264.7 macrophages and promoted the secretion of tumor necrosis factor-ɑ (TNF-α), interleukin-6 (IL-6), interleukin-1ß (IL-1ß), and NO levels. The mRNA levels of these cytokines and iNOS were also increased by SNLP. Our results provide preliminary evidence suggesting that SNLP acts as a dual immunomodulatory peptide with immunostimulatory and anti-inflammatory activities. In summary, SNLP derived from Sipunculus nudus L. is a potent immunoregulatory peptide and represents a potential functional food or immunoregulatory drug.

Plastic wastes and surface antibiotic resistance genes pollution in mangrove environments.

Mangroves are located at the intersection of land and sea and are also heavily affected by plastic wastes. Biofilms of plastic wastes in mangroves are reservoirs for antibiotic resistance genes (ARGs). In this study, plastic wastes and ARG pollution were investigated from three typical mangrove areas in Zhanjiang, South China. Transparent was the dominant colors of plastic wastes in three mangroves. Fragment and film shape accounted for 57.73-88.23% of plastic waste samples in mangroves. In addition, 39.50% of plastic wastes in protected area mangroves are PS. The metagenomic results shows that the 175 ARGs were found on plastic wastes of the three mangroves, the abundance accounting for 91.11% of the total ARGs. The abundance of Vibrio accounted for 2.31% of the total bacteria genera in aquaculture pond area mangrove. Correlation analysis shows that a microbe can carry multiple ARGs that may improve resistance to antibiotics. Microbes are the potential hosts of most ARGs, suggesting that ARGs can be transmitted by microbes. Because the mangroves are closely related to human activities and the high abundance of ARGs on plastic increases the ecological risks, people should improve plastic waste management and prevent the spread of ARGs by reducing plastic pollution.

Distribution and risk assessment of microplastics in typical ecosystems in the South China Sea.

Microplastic pollution in the marine environment has attracted worldwide attention. The South China Sea is considered a hotspot for microplastic pollution due to the developed industries and high population density around the South China Sea. The accumulation of microplastics in ecosystems can adversely affect the health of the environment and organisms. This paper reviews the recent microplastic studies conducted in the South China Sea, which novelty summarizes the abundance, types, and potential hazards of microplastics in coral reef ecosystems, mangrove ecosystems, seagrass bed ecosystems, and macroalgal ecosystems. A summary of the microplastic pollution status of four ecosystems and a risk assessment provides a more comprehensive understanding of the impact of microplastic pollution on marine ecosystems in the South China Sea. Microplastic abundances of up to 45,200 items/m3 were reported in coral reef surface waters, 5738.3 items/kg in mangrove sediments, and 927.3 items/kg in seagrass bed sediments. There are few studies of microplastics in the South China Sea macroalgae ecosystems. However, studies from other areas indicate that macroalgae can accumulate microplastics and are more likely to enter the food chain or be consumed by humans. Finally, this paper compared the current risk levels of microplastics in the coral reef, mangrove, and seagrass bed ecosystems based on available studies. Pollution load index (PLI) ranges from 3 to 31 in mangrove ecosystems, 5.7 to 11.9 in seagrass bed ecosystems, and 6.1 to 10.2 in coral reef ecosystems, respectively. The PLI index varies considerably between mangroves depending on the intensity of anthropogenic activity around the mangrove. Further studies on seagrass beds and macroalgal ecosystems are required to extend our understanding of microplastic pollution in marine environments. Recent microplastic detection in fish muscle tissue in mangroves requires more research to further the biological impact of microplastic ingestion and the potential food safety risks.

Molecular Mechanism of the Debye Relaxation in Monohydroxy Alcohols Revealed from Rheo-Dielectric Spectroscopy.

Rheo-dielectric spectroscopy is employed to investigate the effect of external shear on Debye-like relaxation of a model monohydroxy alcohol, i.e., the 2-ethyl-1-hexanol (2E1H). Shear deformation leads to strong acceleration in the structural relaxation, the Debye relaxation, and the terminal relaxation of 2E1H. Moreover, the shear-induced reduction in structural relaxation time, τ_{α}, scales quadratically with that of Debye time, τ_{D}, and the terminal flow time, τ_{f}, suggesting a relationship of τ_{D}^{2}∼τ_{α}. Further analyses reveal τ_{D}^{2}/τ_{α} of 2E1H follows Arrhenius temperature dependence that applies remarkably well to many other monohydroxy alcohols with different molecular sizes, architectures, and alcohol types. These results cannot be understood by the prevailing transient chain model, and suggest a H-bonding breakage facilitated sub-supramolecular reorientation as the origin of Debye relaxation of monohydroxy alcohols, akin to the molecular mechanism for the terminal relaxation of unentangled "living" polymers.

Occurrence of antibiotic resistance genes carried by plastic waste from mangrove wetlands of the South China Sea.

Plastic waste can carry organisms such as bacterial pathogens and antibiotic resistance genes (ARGs) over long distances. However, only few studies have been conducted on the occurrence of ARGs in plastic waste from mangrove wetlands. This study evaluated the distribution characteristics and ecological risks of plastic waste from mangroves in the coastal areas of the South China Sea. The correlation between anthropogenic activity levels and abundance of ARGs in mangroves was evaluated. Transparent and white were the common colors of plastic waste in mangroves. The main shapes of plastic waste were foam and film. The predominant types of plastic waste order were as follows: polyethylene (30.18 %) > polypropylene (27.51 %) > polystyrene (23.59 %). The living area (LA) mangroves had the highest polymer hazard and pollution load indices of 329.09 and 10.03, respectively. The abundance of ARGs (5.08 × 108 copies/g) on the plastic surface in LA mangroves was significantly higher than that of the other mangrove areas. Furthermore, there was a significant correlation between ARGs and intI1 on the plastic surface in mangroves. Correlation analysis between the ARGs and intI1 showed that most of the ARGs were correlated with intI1 except for msbA. In LA mangroves, sociometric and environmental factors showed significant correlations with the absolute abundances of the four ARGs and intI1, indicating that anthropogenic activities may lead to changes in the amount of ARGs on plastic surfaces. Furthermore, the ARG storage of plastic waste from different mangroves was as follows: protected areas (3.12 × 1017 copies) > living areas (2.99 × 1017 copies) > aquaculture pond areas (2.88 × 1017 copies). The higher ARG storage of LA mangroves, with the smallest area, greatly increased its ecological risk. The results of this study can provide basic data for processes that influence the distribution of plastic waste and ARGs in mangroves.

Relaxation dynamics of deformed polymer nanocomposites as revealed by small-angle scattering and rheology.

The relaxation dynamics of polystyrene (PS)/silica nanocomposites after a large step deformation are studied by a combination of small-angle scattering techniques and rheology. Small-angle X-ray scattering measurements and rheology show clear signatures of nanoparticle aggregation that enhances the mechanical properties of the polymer nanocomposites (PNCs) in the linear viscoelastic regime and during the initial phase of stress relaxation along with accelerated relaxation dynamics. Small-angle neutron scattering experiments under the zero-average-contrast condition reveal, however, smaller structural anisotropy in the PNCs than that in the neat polymer matrix, as well as accelerated anisotropy relaxation. In addition, the degrees of anisotropy reduction and relaxation dynamics acceleration increase with increasing nanoparticle loading. These results are in sharp contrast to the prevailing viewpoint of enhanced molecular deformation as the main mechanism for the mechanical enhancement in PNCs. Furthermore, the observed acceleration of stress relaxation and reduction in structural anisotropy point to two types of nonlinear effects in the relaxation dynamics of PNCs at large deformation.

Separation of false-positive microplastics and analysis of microplastics via a two-phase system combined with confocal Raman spectroscopy.

In the field of microplastics research, more accurate standardised methods and analytical techniques still need to be explored. In this study, a new method for the microplastics quantitatively and qualitatively analysis by two-phase (ethyl acetate-water) system combined with confocal Raman spectroscopy was developed. Microplastics can be separated from false-positive microplastics in beach sand and marine sediment, attributing to the hydrophobic-lipophilic interaction (HLI) of the two-phase system. Results show that the recovery rates of complex environment microplastics (polypropylene (PP), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide 66 (PA 66), polycarbonate (PC) and polyethylene (PE)) are higher than 92.98%. Moreover, the new technique can also be used to detect hydrophobic and lipophilic antibiotics, such as sulfamethoxazole (SMX), erythromycin (EM), madimycin (MD), and josamycin (JOS), which adsorbed on microplastics and are extracted based on the dissolving-precipitating mechanism. This innovative research strategy provides a new scope for further detection of marine environment microplastics and toxic compounds adsorbed on its surface.

Impact of the surrounding environment on antibiotic resistance genes carried by microplastics in mangroves.

The pollution of antibiotic resistance genes (ARGs) carried by microplastics (MPs) is a growing concern. Mangroves are located at the intersection of land and sea and are seriously affected by MP pollution. However, few studies have systematic research evaluating the transmission risk of ARGs carried by MPs in mangroves. We conducted in situ experiments by burying five different MPs (polypropylene, high-density polyethylene, polystyrene, polyethylene glycol terephthalate, and polycaprolactone particles) in mangroves with different surrounding environments. A total of 10 genes in the MPs of mangroves were detected using quantitative real-time polymerase chain reactions, including eight ARGs and two mobile genetic elements (MGEs). The abundance of ARGs in Guanhai park mangroves in living areas (GH) was higher than that of Gaoqiao mangroves in protected areas (GQ) and Beiyue dike mangroves in aquaculture pond areas (BY). Pathogenic bacteria, such as Acinetobacter, Bacillus, and Vibrio were found on the MP surfaces of the mangroves. The number of ARGs carried by multiple drug-resistant bacteria in the GH mangroves was greater than that in the GQ and BY mangroves. Moreover, the ARGs carried by MPs in GH mangroves had the highest potential transmission risk by horizontal gene transfer. Sociometric and environmental factors were the main drivers shaping the distribution characteristics of ARGs and MGEs. Polypropylene and high-density polyethylene particles are preferred substrates for obtaining diffuse ARGs. This study investigated the drivers of ARGs in the MPs of mangroves and provided essential guidance on the use and handling of plastics.

Molecular View on Mechanical Reinforcement in Polymer Nanocomposites.

The microscopic origin of mechanical enhancement in polymer nanocomposite (PNC) melts is investigated through the combination of rheology and small-angle neutron scattering. It is shown that in the absence of an extensive particle network, the molecular deformation of polymer chains dominates the stress response on intermediate time scales. Quantitative analyses of small-angle neutron scattering spectra, however, reveal no enhanced structural anisotropy in the PNCs, compared with the pristine polymers under the same deformation conditions. These results demonstrate that the mechanical reinforcement of PNCs is not due to molecular overstraining, but instead a redistribution of strain field in the polymer matrix, akin to the classical picture of hydrodynamic effect of nanoparticles.

AtMAD: Arabidopsis thaliana multi-omics association database.

Integration analysis of multi-omics data provides a comprehensive landscape for understanding biological systems and mechanisms. The abundance of high-quality multi-omics data (genomics, transcriptomics, methylomics and phenomics) for the model organism Arabidopsis thaliana enables scientists to study the genetic mechanism of many biological processes. However, no resource is available to provide comprehensive and systematic multi-omics associations for Arabidopsis. Here, we developed an Arabidopsis thaliana Multi-omics Association Database (AtMAD, http://www.megabionet.org/atmad), a public repository for large-scale measurements of associations between genome, transcriptome, methylome, pathway and phenotype in Arabidopsis, designed for facilitating identification of eQTL, emQTL, Pathway-mQTL, Phenotype-pathway, GWAS, TWAS and EWAS. Candidate variants/methylations/genes were identified in AtMAD for specific phenotypes or biological processes, many of them are supported by experimental evidence. Based on the multi-omics association strategy, we have identified 11 796 cis-eQTLs and 10 119 trans-eQTLs. Among them, 68 837 environment-eQTL associations and 149 622 GWAS-eQTL associations were identified and stored in AtMAD. For expression-methylation quantitative trait loci (emQTL), we identified 265 776 emQTLs and 122 344 pathway-mQTLs. For TWAS and EWAS, we obtained 62 754 significant phenotype-gene associations and 3 993 379 significant phenotype-methylation associations, respectively. Overall, the multi-omics associated network in AtMAD will provide new insights into exploring biological mechanisms of plants at multi-omics levels.

Hydrophobic Magnetic Porous Material of Eichhornia crassipes for Highly Efficient Oil Adsorption and Separation.

Many oil adsorption materials are composed of nonrenewable raw materials, and their disposal can increase resource consumption and cause new environmental pollution. In this paper, the carbonized Eichhornia crassipes (CEC) were immobilized with Fe3O4 magnetic nanoparticles and modified with 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (PFOS) to prepare an oil adsorption material, referred to here as CEC/Fe3O4/PFOS. The magnetic and mechanical strength of the CEC was enhanced by adding Fe3O4 magnetic particles, which enable it efficient to dispose the oil/water solution. CEC/Fe3O4/PFOS shows high porosity (83.53%), low skeletal density (0.487 g/cm3), excellent magnetism, ultrahigh oil absorption capacity (49.94-140.90 g/g), hydrophobic performances with a water contact angle of 150.1 ± 2.3°, and a sliding angle of 10.5°. It is worth noting that the material can be recycled, and the absorbed oil is obtained by distillation. Therefore, this work may provide a candidate for solving the problem of oil pollution using E. crassipes.

In Situ Growth Visualization Nanochannel Membrane for Ultrasensitive Copper Ion Detection under the Electric Field Enrichment.

The transport of ionic species through nanochannels plays an important role in the basic research and practical application of nanofluidic devices. Here, a visualized CdSe@ZIF-8/PAA nanochannel membrane was created by employing in situ growth of zeolite imidazole skeleton (ZIF-8) and CdSe quantum dots (CdSe QDs) on a porous anodized aluminum oxide (PAA) membrane surface using CdSe QDs, 2-methylimidazole, and zinc nitrate as the precursor solvents. ZIF-8 is a kind of metal-organic framework, a microporous material that possesses strong metal adsorption capacity. In addition, CdSe quantum dots have fluorescent properties. The nanochannel membrane detects copper ions (Cu2+) by quenching the fluorescence intensity by the interaction between Cu2+ and Se and S atoms. The direct potential of 5 V was applied to achieve Cu2+ enrichment at the nanochannel interface, and the fluorescence change was observed. The CdSe@ZIF-8/PAA nanochannel membrane has a good linear range of concentration (0.01 pM-1 µM) for Cu2+ detection. With the help of nanochannel enrichment, its detection limit reaches 4 fM. In addition, this nanochannel membrane has good selectivity for Cu2+.

Nonmonotonic Strain Rate Dependence on the Strain Hardening of Polymer Nanocomposites.

This Letter investigates the external deformation on modifying the polymer-nanoparticle (NP) and NP-NP interactions as well as their influences on the macroscopic properties of polymer nanocomposites (PNCs). Specifically, the applied uniaxial extension brings together the NPs along the transverse stretching direction and catalyzes the percolation transition from the initially well-dispersed NPs in the PNCs. The percolated NP network thus increases the strength of PNCs and leads to a strong surge in the elongation viscosity at very low strain rates, exhibiting the unexpected nonmonotonic strain rate dependence on the strain hardening. These results reveal explicitly the unconventional roles of the external deformation on modulating the relative strength of the polymer-NP and the NP-NP interactions, enabling advanced structures and properties control of PNCs.