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1.
Mikrochim Acta ; 191(6): 362, 2024 06 01.
Article En | MEDLINE | ID: mdl-38822867

Rapid and accurate in situ determination of dopamine is of great significance in the study of neurological diseases. In this work, poly (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS)/graphene oxide (GO) fibers were fabricated by an effective method based on microfluidic wet spinning technology. The composite microfibers with stratified and dense arrangement were continuously prepared by injecting PEDOT: PSS and GO dispersion solutions into a microfluidic chip. PEDOT: PSS/GO fiber microelectrodes with high electrochemical activity and enhanced electrochemical oxidation activity of dopamine were constructed by controlling the structure composition of the microfibers with varying flow rate. The fabricated fiber microelectrode had a low detection limit (4.56 nM) and wide detection range (0.01-8.0 µM) for dopamine detection with excellent stability, repeatability, and reproducibility. In addition, the PEDOT: PSS/GO fiber microelectrode prepared was successfully used for the detection of dopamine in human serum and PC12 cells. The strategy for the fabrication of multi-component fiber microelectrodes is a new and effective approach for monitoring the intercellular neurotransmitter dopamine and has high potential as an implantable neural microelectrode.


Dopamine , Graphite , Microelectrodes , Polystyrenes , PC12 Cells , Dopamine/blood , Humans , Rats , Animals , Polystyrenes/chemistry , Graphite/chemistry , Limit of Detection , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Microfluidic Analytical Techniques/instrumentation , Microfluidic Analytical Techniques/methods , Bridged Bicyclo Compounds, Heterocyclic/chemistry , Thiophenes/chemistry , Lab-On-A-Chip Devices , Polymers
2.
Environ Geochem Health ; 46(6): 185, 2024 May 02.
Article En | MEDLINE | ID: mdl-38695908

Microplastics (MPs), as emerging contaminants, usually experience aging processes in natural environments and further affect their interactions with coexisted contaminants, resulting in unpredictable ecological risks. Herein, the effect of MPs aging on their adsorption for coexisting antibiotics and their joint biotoxicity have been investigated. Results showed that the adsorption capacity of aged polystyrene (PS, 100 d and 50 d) for ciprofloxacin (CIP) was 1.10-4.09 times higher than virgin PS due to the larger BET surface area and increased oxygen-containing functional groups of aged PS. Following the increased adsorption capacity of aged PS, the joint toxicity of aged PS and CIP to Shewanella Oneidensis MR-1 (MR-1) was 1.03-1.34 times higher than virgin PS and CIP. Combined with the adsorption process, CIP posed higher toxicity to MR-1 compared to aged PS due to the rapid adsorption of aged PS for CIP in the first 12 h. After that, the adsorption process tended to be gentle and hence the joint toxicity to MR-1 was gradually dominated by aged PS. A similar transformation between the adsorption rate and the joint toxicity of PS and CIP was observed under different conditions. This study supplied a novel perception of the synergistic effects of PS aging and CIP on ecological health.


Ciprofloxacin , Polystyrenes , Shewanella , Ciprofloxacin/chemistry , Ciprofloxacin/toxicity , Polystyrenes/toxicity , Polystyrenes/chemistry , Adsorption , Shewanella/drug effects , Microplastics/toxicity , Microplastics/chemistry , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/toxicity , Water Pollutants, Chemical/toxicity , Water Pollutants, Chemical/chemistry
3.
Biosens Bioelectron ; 258: 116327, 2024 Aug 15.
Article En | MEDLINE | ID: mdl-38703496

Proper customization in size and shape is essential in implantable bioelectronics for stable bio-signal recording. Over the past decades, many researchers have heavily relied on conventional photolithography processes to fabricate implantable bioelectronics. Therefore, they could not avoid the critical limitation of high cost and complex processing steps to optimize bioelectronic devices for target organs with various sizes and shapes. Here, we propose rapid prototyping using all laser processes to fabricate customized bioelectronics. PEDOT:PSS is selectively irradiated by an ultraviolet (UV) pulse laser to form wet-stable conductive hydrogels that can softly interact with biological tissues (50 µm line width). The encapsulation layer is selectively patterned using the same laser source by UV-curing polymer networks (110 µm line width). For high stretchability (over 100%), mesh structures are made by the selective laser cutting process. Our rapid prototyping strategy minimizes the use of high-cost equipment, using only a single UV laser source to process the electrodes, encapsulation, and substrates that constitute bioelectronics without a photomask, enabling the prototyping stretchable microelectrode array with an area of 1 cm2 less than 10 min. We fabricated an optimized stretchable microelectrode array with low impedances (∼1.1 kΩ at 1 kHz) that can effectively record rat's cardiac signals with various health states.


Biosensing Techniques , Electric Conductivity , Hydrogels , Lasers , Hydrogels/chemistry , Animals , Biosensing Techniques/instrumentation , Rats , Polymers/chemistry , Equipment Design , Polystyrenes/chemistry , Thiophenes
4.
Aquat Toxicol ; 271: 106934, 2024 Jun.
Article En | MEDLINE | ID: mdl-38728926

Microplastics (MP) and antibiotics coexist in the environment and their combined exposure represents a source of increasing concern. MP may act as carriers of antibiotics because of their sorption capacity. Knowledge of the interactions between them may help improve understanding of their migration and transformation. In this work, the adsorption behaviour of a group of sulfonamides and their acetylated metabolites on different sizes of polyamide (PA) and polystyrene (PS) MP were investigated and compared. Sulfonamides were adsorbed on both MP (qmax up to 0.699 and 0.184 mg/g, for PA and PS, respectively) fitting to a linear isotherm model (R2 > 0.835). A low particle size and an acidic and salinity medium significantly enhances the adsorption capacity of sulfonamides (i.e. removal of sulfamethoxazole increased from 8 % onto 3 mm PA pellets to 80 % onto 50 mm of PA pellets). According to characterization results, adsorption mechanism is explained by pore filling and hydrogen bonds (for PA) and hydrophobic interactions (for PS). After adsorption, surface area was increased in both MP as result of a potential ageing of the particles and the intensity of XRD peaks was higher denoting a MP structure more amorphized. Metabolites were adsorbed more efficiently than their parent compounds on PS while the opposite effect was observed on PA explained by the acetylation of the amine group and, subsequently the reduction of hydrogen bond interactions. Although the dissolved organic matter inhibits sulfonamides adsorption, removal up to 65.2 % in effluent wastewater and up to 72.1 % in surface water were observed in experiments using real matrices denoting the role of MP as vectors of sulfonamide antibiotics in aquatic media.


Anti-Bacterial Agents , Microplastics , Nylons , Polystyrenes , Sulfonamides , Water Pollutants, Chemical , Water Pollutants, Chemical/chemistry , Polystyrenes/chemistry , Adsorption , Anti-Bacterial Agents/chemistry , Sulfonamides/chemistry , Nylons/chemistry , Microplastics/chemistry , Particle Size
5.
Bioelectrochemistry ; 158: 108725, 2024 Aug.
Article En | MEDLINE | ID: mdl-38714062

An enzymatic amperometric uric acid (UA) biosensor was successfully developed by modifying a screen-printed carbon electrode (SPCE) with Prussian blue-poly(3,4-ethylene dioxythiophene) polystyrene sulfonate composite (PB-PEDOT:PSS). The modified SPCE was coated with gold nanoparticles-graphene oxide-chitosan composite cryogel (AuNPs-GO-CS cry). Uricase (UOx) was directly immobilized via chemisorption on AuNPs. The nanocomposite was characterized by scanning electron microscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and Fourier transform infrared spectroscopy. The electrochemical characterization of the modified electrode was performed by cyclic voltammetry and electrochemical impedance spectroscopy. UA was determined using amperometric detection based on the reduction current of PB which was correlated with the amount of H2O2 produced during the enzymatic reaction. Under optimal conditions, the fabricated UA biosensor in a flow injection analysis (FIA) system produced a linear range from 5.0 to 300 µmol L-1 with a detection limit of 1.88 µmol L-1. The proposed sensor was stable for up to 221 cycles of detection and analysis was rapid (2 min), with good reproducibility (RSDs < 2.90 %, n = 6), negligible interferences, and recoveries from 94.0 ± 3.9 to 101.1 ± 2.6 %. The results of UA detection in blood plasma were in agreement with the enzymatic colorimetric method (P > 0.05).


Biosensing Techniques , Cryogels , Electrodes , Gold , Graphite , Limit of Detection , Metal Nanoparticles , Uric Acid , Biosensing Techniques/methods , Uric Acid/blood , Uric Acid/analysis , Gold/chemistry , Graphite/chemistry , Cryogels/chemistry , Metal Nanoparticles/chemistry , Carbon/chemistry , Polymers/chemistry , Porosity , Flow Injection Analysis , Bridged Bicyclo Compounds, Heterocyclic/chemistry , Chitosan/chemistry , Polystyrenes/chemistry , Enzymes, Immobilized/chemistry , Enzymes, Immobilized/metabolism , Humans , Urate Oxidase/chemistry , Electrochemical Techniques/methods , Nanocomposites/chemistry , Ferrocyanides/chemistry
6.
Sci Adv ; 10(22): eadj4370, 2024 May 31.
Article En | MEDLINE | ID: mdl-38809990

Tumor heterogeneity is a primary factor that contributes to treatment failure. Predictive tools, capable of classifying cancer cells based on their functions, may substantially enhance therapy and extend patient life span. The connection between cell biomechanics and cancer cell functions is used here to classify cells through mechanical measurements, via particle uptake. Machine learning (ML) was used to classify cells based on single-cell patterns of uptake of particles with diverse sizes. Three pairs of human cancer cell subpopulations, varied in their level of drug resistance or malignancy, were studied. Cells were allowed to interact with fluorescently labeled polystyrene particles ranging in size from 0.04 to 3.36 µm and analyzed for their uptake patterns using flow cytometry. ML algorithms accurately classified cancer cell subtypes with accuracy rates exceeding 95%. The uptake data were especially advantageous for morphologically similar cell subpopulations. Moreover, the uptake data were found to serve as a form of "normalization" that could reduce variation in repeated experiments.


Drug Resistance, Neoplasm , Machine Learning , Neoplasms , Humans , Neoplasms/metabolism , Neoplasms/pathology , Neoplasms/drug therapy , Cell Line, Tumor , Particle Size , Algorithms , Polystyrenes/chemistry , Flow Cytometry
7.
Sci Rep ; 14(1): 12302, 2024 05 29.
Article En | MEDLINE | ID: mdl-38811698

The correlation between altered extracellular pH and various pathological conditions, including cancer, inflammation and metabolic disorders, is well known. Bulk pH measurements cannot report the extracellular pH value at the cell surface. However, there is a limited number of suitable tools for measuring the extracellular pH of cells with high spatial resolution, and none of them are commonly used in laboratories around the world. In this study, a versatile ratiometric nanosensor for the measurement of extracellular pH was developed. The nanosensor consists of biocompatible polystyrene nanoparticles loaded with the pH-inert reference dye Nile red and is surface functionalized with a pH-responsive fluorescein dye. Equipped with a targeting moiety, the nanosensor can adhere to cell membranes, allowing direct measurement of extracellular pH at the cell surface. The nanosensor exhibits a sensitive ratiometric pH response within the range of 5.5-9.0, with a calculated pKa of 7.47. This range optimally covers the extracellular pH (pHe) of most healthy cells and cells in which the pHe is abnormal, such as cancer cells. In combination with the nanosensors ability to target cell membranes, its high robustness, reversibility and its biocompatibility, the pHe nanosensor proves to be well suited for in-situ measurement of extracellular pH, even over extended time periods. This pH nanosensor has the potential to advance biomedical research by improving our understanding of cellular microenvironments, where extracellular pH plays an important role.


Fluorescent Dyes , Nanoparticles , Hydrogen-Ion Concentration , Humans , Fluorescent Dyes/chemistry , Nanoparticles/chemistry , Cell Membrane/metabolism , Biosensing Techniques/methods , Biosensing Techniques/instrumentation , Oxazines/chemistry , Polystyrenes/chemistry
8.
Int J Mol Sci ; 25(10)2024 May 07.
Article En | MEDLINE | ID: mdl-38791107

The present study employs X-ray photoelectron spectroscopy (XPS) to analyze plastic samples subjected to degradation processes with the aim to gain insight on the relevant chemical processes and disclose fragmentation mechanisms. Two model plastics, namely polystyrene (PS) and polyethylene (PE), are selected and analyzed before and after artificial UV radiation-triggered weathering, under simulated environmental hydrodynamic conditions, in fresh and marine water for different time intervals. The object of the study is to identify and quantify chemical groups possibly evidencing the occurrence of hydrolysis and oxidation reactions, which are the basis of degradation processes in the environment, determining macroplastic fragmentation. Artificially weathered plastic samples are analyzed also by Raman and FT-IR spectroscopy. Changes in surface chemistry with weathering are revealed by XPS, involving the increase in chemical moieties (hydroxyl, carbonyl, and carboxyl functionalities) which can be correlated with the degradation processes responsible for macroplastic fragmentation. On the other hand, the absence of significant modifications upon plastics weathering evidenced by Raman and FT-IR spectroscopy confirms the importance of investigating plastics surface, which represents the very first part of the materials exposed to degradation agents, thus revealing the power of XPS studies for this purpose. The XPS data on experimentally weathered particles are compared with ones obtained on microplastics collected from real marine environment for investigating the occurring degradation processes.


Photoelectron Spectroscopy , Plastics , Polyethylene , Photoelectron Spectroscopy/methods , Plastics/chemistry , Polyethylene/chemistry , Spectroscopy, Fourier Transform Infrared/methods , Spectrum Analysis, Raman/methods , Polystyrenes/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/analysis , Seawater/chemistry , Microplastics/chemistry , Oxidation-Reduction
9.
ACS Appl Mater Interfaces ; 16(20): 25740-25756, 2024 May 22.
Article En | MEDLINE | ID: mdl-38722759

Micro- and nano-plastics (NPs) are found in human milk, blood, tissues, and organs and associate with aberrant health outcomes including inflammation, genotoxicity, developmental disorders, onset of chronic diseases, and autoimmune disorders. Yet, interfacial interactions between plastics and biomolecular systems remain underexplored. Here, we have examined experimentally, in vitro, in vivo, and by computation, the impact of polystyrene (PS) NPs on a host of biomolecular systems and assemblies. Our results reveal that PS NPs essentially abolished the helix-content of the milk protein ß-lactoglobulin (BLG) in a dose-dependent manner. Helix loss is corelated with the near stoichiometric formation of ß-sheet elements in the protein. Structural alterations in BLG are also likely responsible for the nanoparticle-dependent attrition in binding affinity and weaker on-rate constant of retinol, its physiological ligand (compromising its nutritional role). PS NP-driven helix-to-sheet conversion was also observed in the amyloid-forming trajectory of hen egg-white lysozyme (accelerated fibril formation and reduced helical content in fibrils). Caenorhabditis elegans exposed to PS NPs exhibited a decrease in the fluorescence of green fluorescent protein-tagged dopaminergic neurons and locomotory deficits (akin to the neurotoxin paraquat exposure). Finally, in silico analyses revealed that the most favorable PS/BLG docking score and binding energies corresponded to a pose near the hydrophobic ligand binding pocket (calyx) of the protein where the NP fragment was found to make nonpolar contacts with side-chain residues via the hydrophobic effect and van der Waals forces, compromising side chain/retinol contacts. Binding energetics indicate that PS/BLG interactions destabilize the binding of retinol to the protein and can potentially displace retinol from the calyx region of BLG, thereby impairing its biological function. Collectively, the experimental and high-resolution in silico data provide new insights into the mechanism(s) by which PS NPs corrupt the bimolecular structure and function, induce amyloidosis and onset neuronal injury, and drive aberrant physiological and behavioral outcomes.


Caenorhabditis elegans , Lactoglobulins , Muramidase , Animals , Muramidase/chemistry , Muramidase/metabolism , Lactoglobulins/chemistry , Lactoglobulins/metabolism , Caenorhabditis elegans/metabolism , Polystyrenes/chemistry , Nanoparticles/chemistry , Vitamin A/chemistry , Vitamin A/metabolism , Humans , Homeostasis/drug effects , Plastics/chemistry
10.
ACS Appl Mater Interfaces ; 16(20): 25977-25993, 2024 May 22.
Article En | MEDLINE | ID: mdl-38741563

Environmental pollution with plastic polymers has become a global problem, leaving no continent and habitat unaffected. Plastic waste is broken down into smaller parts by environmental factors, which generate micro- and nanoplastic particles (MNPPs), ultimately ending up in the human food chain. Before entering the human body, MNPPs make their first contact with saliva in the human mouth. However, it is unknown what proteins attach to plastic particles and whether such protein corona formation is affected by the particle's biophysical properties. To this end, we employed polystyrene MNPPs of two different sizes and three different charges and incubated them individually with saliva donated by healthy human volunteers. Particle zeta potential and size analyses were performed using dynamic light scattering complemented by nanoliquid chromatography high-resolution mass spectrometry (nLC/HRMS) to qualitatively and quantitatively reveal the protein soft and hard corona for each particle type. Notably, protein profiles and relative quantities were dictated by plastic particle size and charge, which in turn affected their hydrodynamic size, polydispersity, and zeta potential. Strikingly, we provide evidence of the latter to be dynamic processes depending on exposure times. Smaller particles seemed to be more reactive with the surrounding proteins, and cultures of the particles with five different cell lines (HeLa, HEK293, A549, HepG2, and HaCaT) indicated protein corona effects on cellular metabolic activity and genotoxicity. In summary, our data suggest nanoplastic size and surface chemistry dictate the decoration by human saliva proteins, with important implications for MNPP uptake in humans.


Particle Size , Polystyrenes , Saliva , Salivary Proteins and Peptides , Surface Properties , Humans , Saliva/chemistry , Saliva/metabolism , Salivary Proteins and Peptides/chemistry , Salivary Proteins and Peptides/metabolism , Polystyrenes/chemistry , Protein Corona/chemistry , Protein Corona/metabolism , Nanoparticles/chemistry , Microplastics/chemistry
11.
Chemosphere ; 358: 142215, 2024 Jun.
Article En | MEDLINE | ID: mdl-38701865

The existence of microplastics (MPs) in water is a significant global concern since they have the potential to pose a threat to human health. Therefore, there is a need to develop a sustainable treatment technology for MPs removal, as the conventional methods are inadequate to address this problem. Coagulation is a typical process in treatment plants that can capture MPs before releasing them into the environment. In this work, the removal behaviors of polyamide (PA), polystyrene (PS), and polyethylene (PE) MPs were systematically investigated through coagulation processes using aluminum sulfate (Al2(SO4)3) and Moringa oleifera (MO) seeds extract. Subsequently, the coagulation performance of Al2(SO4)3 was improved by the separate addition of anionic polyacrylamide (APAM) and naturally derived MO. Results showed that Al2(SO4)3 in combination with APAM had better performance than Al2(SO4)3 or MO alone. In the Al2(SO4)3+APAM system, the removal efficiencies were 93.47%, 81.25%, and 29.48% for PA, PS, and PE MPs, respectively. Furthermore, the effectiveness of the Al2(SO4)3 and MO blended system was approximately similar to the Al2(SO4)3+APAM system. However, the required amount of Al2(SO4)3 was decreased to 50% in the Al2(SO4)3+MO system compared to the optimal dosage in the Al2(SO4)3 system alone. The combination of 40 mg/L of Al2(SO4)3 and 60 mg/L of MO resulted in removal efficiencies of 92.99%, 80.48%, and 28.94% for PA, PS, and PE MPs, respectively. The high efficacy of these enhanced methods was due to the synergic effects of charge neutralization and agglomeration adsorption, which were validated through zeta potential assessments and visual analysis using scanning electron microscopy (SEM) images. In the case of experimental conditions, initial pH had little impact on removal efficiency, while NaCl salinity and stirring speed directly affected MPs removal. Consequently, this research took a step toward finding a green strategy to remove MPs from water systems.


Acrylic Resins , Microplastics , Water Pollutants, Chemical , Water Purification , Water Pollutants, Chemical/chemistry , Acrylic Resins/chemistry , Water Purification/methods , Moringa oleifera/chemistry , Anions/chemistry , Adsorption , Polystyrenes/chemistry
12.
Chemosphere ; 358: 142165, 2024 Jun.
Article En | MEDLINE | ID: mdl-38704048

Expanded polystyrene (EPS) plastic is widely used because of its low density and lightweight properties, enabling it to float on water and increase its exposure to sunlight. In this study, we simulated the photoaging process of flame retardant-added EPS (FR-EPS) and common original EPS (OR-EPS) microplastic (MP) particles with and without methyl octabromoether flame retardant (MOBE) in the laboratory to explore the effect of MOBE on the photodegradation of EPS. Results showed that MOBE accelerated size reduction and surface hole formation on the particles, hastening the shedding and replacement of particle surfaces. FR-EPS particles exhibited a weight loss exceeding that of OR-EPS, reaching 40.85 ± 3.72% after 36 days of irradiation. Moreover, rapid physical peeling of the FR-EPS surface was accompanied by continuous chemical oxidation and fluctuations of the carbonyl index and O/C ratio. A diffusion model based on Fick's second law fitted well for the concentration of MOBE remaining in FR-EPS particles. MOBE's sensitivity to direct photochemical reactions inhibited the early-stage photoaging of EPS MP particles by competing for photons. However, MOBE as chromophores could absorb photons and produce •OH to promote the aging of EPS. Moreover, the capacity of EPS to absorb light energy also accelerated MOBE degradation. These findings suggested that the photoaging behavior of commercial EPS products containing flame retardants in the environment is quite different from that of pure EPS, indicating that additive-plastic interactions significantly alter MP fate and environmental risks.


Flame Retardants , Microplastics , Polystyrenes , Polystyrenes/chemistry , Microplastics/chemistry , Photolysis , Plastics/chemistry
13.
Chemosphere ; 358: 142220, 2024 Jun.
Article En | MEDLINE | ID: mdl-38710410

Microplastics have become a prevalent environmental pollutant due to widespread release and production. Algae, as primary producers, play a crucial role in maintaining the ecological balance of freshwater environments. Despite reports on the inhibition of microalgae by microplastics, the size-dependent effects on microalgae and associated molecular mechanism remain poorly understood. This study investigates the impacts of three polystyrene micro/nano-plastics (PS-MNPs) with different sizes (100 nm, 350 nm, and 6 µm) and concentrations (25-200 mg/L) on Chlamydomonas reinhardtii (C. reinhardtii) throughout its growth period. Results reveal size- and concentration-dependent growth inhibition and induction of oxidative stress by PS-MNPs, with microalgae exhibiting increased vulnerability to smaller-sized and higher-concentration PS-MNPs. Proteomics analysis elucidates the size-dependent suppression of proteins involved in the photosynthesis process by PS-MNPs. Photosynthetic activity assays demonstrate that smaller PS-MNPs more significantly reduce chlorophyll content and the maximal photochemical efficiency of photosystem II. Finally, electron microscope and Western blot assays collectively confirm the size effect of PS-MNPs on microalgae growth is attributable to suppressed protein expression rather than shading effects. This study contributes to advancing our understanding of the intricate interactions between micro/nano-plastics and algae at the molecular level, emphasizing the efficacy of proteomics in dissecting the mechanistic aspects of microplastics-induced biological effects on environmental indicator organisms.


Chlamydomonas reinhardtii , Microplastics , Photosynthesis , Polystyrenes , Proteomics , Chlamydomonas reinhardtii/drug effects , Chlamydomonas reinhardtii/metabolism , Chlamydomonas reinhardtii/growth & development , Polystyrenes/toxicity , Polystyrenes/chemistry , Microplastics/toxicity , Photosynthesis/drug effects , Oxidative Stress/drug effects , Chlorophyll/metabolism , Water Pollutants, Chemical/toxicity , Microalgae/drug effects , Plastics/toxicity , Particle Size , Photosystem II Protein Complex/metabolism
14.
Environ Sci Technol ; 58(20): 8878-8888, 2024 May 21.
Article En | MEDLINE | ID: mdl-38733558

Particulate contaminants, such as microplastics (1 µm to 5 mm) and nanoplastics (<1 µm), are disseminated in many terrestrial environments. However, it is still unclear how particles' properties drive their mobility through soils and aquifers due to (i) poor environmental relevance of the model particles that are studied (e.g., spherical and monodisperse) and (ii) the use of packed bed experiments which do not allow a direct observation of deposition dynamics. Using transparent 2D porous media, this study analyzes deposition dynamics of rough polystyrene fragments with irregular shapes and with a size continuum (≈10 nm to 5 µm). Using in situ and ex situ measurements, particle deposition as a function of size was monitored over time under repulsive conditions. In the absence of natural organic matter (NOM), micrometric particles rapidly deposit and promote the physical interception of smaller nanoparticles by creating local porous roughness or obstacles. In the presence of NOM, differences according to particle size were no longer observed, and all fragments were more prone to being re-entrained, thereby limiting the growth of deposits. This work demonstrates the importance of pore surface roughness and porosity of the pore surface for the deposition of colloidal particles, such as microplastics and nanoplastics, under repulsive conditions.


Microplastics , Particle Size , Nanoparticles/chemistry , Porosity , Polystyrenes/chemistry
15.
Environ Sci Process Impacts ; 26(5): 882-890, 2024 May 22.
Article En | MEDLINE | ID: mdl-38693902

Microplastics can function as carriers in the environment, absorbing various toxins and spreading to diverse ecosystems. Toxins accumulated in microplastics have the potential to be re-released, posing a threat. In this study, two typical plastics, namely polyethylene (PE) and polystyrene (PS), along with the degradable plastic poly(butylene adipate-co-terephthalate) (PBAT), were subjected to a long-term ultraviolet alternating weathering experiment. The study investigated the variations in the weathering process and pollutant adsorption of microplastics of different particle sizes. Furthermore, the adsorption capacity of microplastics for various pollutants was assessed. The findings indicate that particle size significantly influences weathering, leading to variations in adsorption capacity. The weathered PE displays a higher adsorption capacity for azo dyes. Additionally, the adsorption capacity of PBAT for neutral red is double that of antibiotics. Importantly, the maximum adsorption capacity of PBAT for pollutants after aging is approximately 10 times greater than that of PE. Consequently, degradable plastics undergoing weathering in the natural environment may pose a higher ecological risk than traditional plastics.


Microplastics , Water Pollutants, Chemical , Microplastics/chemistry , Adsorption , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Polyethylene/chemistry , Environmental Monitoring , Plastics/chemistry , Models, Chemical , Polystyrenes/chemistry , Weather
16.
Chem Biol Interact ; 396: 111043, 2024 Jun 01.
Article En | MEDLINE | ID: mdl-38735450

Microplastics have emerged as environmental hazards in recent years. This study was intended to prove the toxic effects of microplastics on the male reproductive system and further elucidate its mechanism. C57bl/6 mice were exposed to ultrapure water or different doses (0.25, 0.5 and 1 mg/d) of 5 µm polystyrene microplastics (PS-MPs) for 4 weeks, and the GC-1 mouse spermatogonium was treated with different concentrations of PS-MPs. The results showed that sperm count and motility were decreased, and sperm deformity rate was increased after exposure to PS-MPs. The morphology of testes in PS-MPs groups exhibited pathological changes, such as abnormal development of spermatogenic tubules, and inhibited spermatogonium function. Furthermore, the fluorescence intensity of TUNEL staining and the BAX/BCL2 ratio were increased. Exposure to PS-MPs resulted in impaired mitochondrial morphology of spermatogonium, decreased activity of GSH-px and SOD, and increased the MDA level. In vitro, after treatment with PS-MPs, the cell apoptosis rate of spermatogonium was significantly increased, mitochondrial membrane potential was decreased, mitochondrial morphology was damaged, and exposure to PS-MPs increased mitochondrial reactive oxygen species, inducing an oxidative stress state in spermatogonia. In summary, PS-MPs induced a decrease in sperm quality by activating spermatogonium mitochondrial oxidative stress and apoptosis, offering novel insights into mitigating the reproductive toxicity of microplastics.


Apoptosis , Membrane Potential, Mitochondrial , Mice, Inbred C57BL , Microplastics , Mitochondria , Oxidative Stress , Polystyrenes , Sperm Motility , Spermatogonia , Testis , Animals , Male , Apoptosis/drug effects , Oxidative Stress/drug effects , Microplastics/toxicity , Polystyrenes/toxicity , Polystyrenes/chemistry , Mice , Mitochondria/drug effects , Mitochondria/metabolism , Testis/drug effects , Testis/pathology , Testis/metabolism , Spermatogonia/drug effects , Spermatogonia/metabolism , Spermatogonia/pathology , Membrane Potential, Mitochondrial/drug effects , Sperm Motility/drug effects , Reactive Oxygen Species/metabolism , Spermatozoa/drug effects , Spermatozoa/pathology , Sperm Count , Superoxide Dismutase/metabolism
17.
Sci Total Environ ; 934: 173314, 2024 Jul 15.
Article En | MEDLINE | ID: mdl-38761937

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.


Microplastics , Polystyrenes , Spectrum Analysis, Raman , Polystyrenes/chemistry , Microplastics/analysis , Spectrum Analysis, Raman/methods , Environmental Monitoring/methods , Limit of Detection , Silver/analysis , Silver/chemistry , Graphite/chemistry , Water Pollutants, Chemical/analysis
18.
J Phys Chem Lett ; 15(20): 5428-5435, 2024 May 23.
Article En | MEDLINE | ID: mdl-38743920

Nanoplastic-lipid interaction is vital to understanding the nanoscale mechanism of plastic adsorption and aggregation on a lipid membrane surface. However, a single-particle mechanistic picture of the nanoplastic transport process on a lipid surface remains unclear. Here, we report a salt-dependent non-Gaussian transport mechanism of polystyrene particles on a supported 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) lipid bilayer surface. Particle stickiness on the POPC surface increases with salt concentration, where the particles stay longer at the surface and diffuse to shorter distances. Additionally, a non-Gaussian diffusion state dominates the transport process at high salt concentrations. Our current study provides insight into the transport mechanism of polystyrene (PS) particles on supported lipid membranes, which is essential to understanding fundamental questions regarding the adsorption mechanisms of nanoplastics on lipid surfaces.


Lipid Bilayers , Phosphatidylcholines , Polystyrenes , Sodium Chloride , Lipid Bilayers/chemistry , Phosphatidylcholines/chemistry , Polystyrenes/chemistry , Sodium Chloride/chemistry , Surface Properties , Adsorption , Diffusion
19.
J Am Chem Soc ; 146(21): 14391-14396, 2024 May 29.
Article En | MEDLINE | ID: mdl-38748513

Model membranes interfaced with bioelectronics allow for the exploration of fundamental cell processes and the design of biomimetic sensors. Organic conducting polymers are an attractive surface on which to study the electrical properties of membranes because of their low impedance, high biocompatibility, and hygroscopic nature. However, establishing supported lipid bilayers (SLBs) on conducting polymers has lagged significantly behind other substrate materials, namely, for challenges in membrane electrical sealing and stability. Unlike SLBs that are highly dependent on surface interactions, droplet interface bilayers (DIBs) and droplet hydrogel bilayers (DHBs) leverage the energetically favorable organization of phospholipids at atomically smooth liquid interfaces to build high-integrity membranes. For the first time, we report the formation of droplet polymer bilayers (DPBs) between a lipid-coated aqueous droplet and the high-performing conducting polymer poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS). The resulting bilayers can be produced from a range of lipid compositions and demonstrate strong electrical sealing that outcompetes SLBs. DPBs are subsequently translated to patterned and planar microelectrode arrays to ease barriers to implementation and improve the reliability of membrane formation. This platform enables more reproducible and robust membranes on conducting polymers to further the mission of merging bioelectronics and synthetic, natural, or hybrid bilayer membranes.


Lipid Bilayers , Lipid Bilayers/chemistry , Polymers/chemistry , Polystyrenes/chemistry , Surface Properties
20.
Nano Lett ; 24(21): 6218-6224, 2024 May 29.
Article En | MEDLINE | ID: mdl-38757765

Nanopore sensing is a popular biosensing strategy that is being explored for the quantitative analysis of biomarkers. With low concentrations of analytes, nanopore sensors face challenges related to slow response times and selectivity. Here, we demonstrate an approach to rapidly detect species at ultralow concentrations using an optical nanopore blockade sensor for quantitative detection of the protein vascular endothelial growth factor (VEGF). This sensor relies on monitoring fluorescent polystyrene nanoparticles blocking nanopores in a nanopore array of 676 nanopores. The fluorescent signal is read out using a wide-field fluorescence microscope. Nonspecific blockade events are then distinguished from specific blockade events based on the ability to pull the particles out of the pore using an applied electric field. This allows the detection of VEGF at sub-picomolar concentration in less than 15 min.


Biosensing Techniques , Nanopores , Polystyrenes , Vascular Endothelial Growth Factor A , Biosensing Techniques/methods , Biosensing Techniques/instrumentation , Vascular Endothelial Growth Factor A/analysis , Vascular Endothelial Growth Factor A/antagonists & inhibitors , Polystyrenes/chemistry , Nanoparticles/chemistry , Humans , Microscopy, Fluorescence/methods
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