Effect of Mass Fraction on Leaching Kinetics of Hydrophobic Ultraviolet Stabilizers in Low-Density Polyethylene.

The leaching kinetics of five hydrophobic ultraviolet (UV) stabilizers from low-density polyethylene (LDPE) (micro)fibers into water was evaluated in this study, with variation of the mass fraction (ω = 0.1-2.0 wt %) of the stabilizers. A one-dimensional convection-diffusion model for a cylindrical geometry, requiring partitioning between the LDPE fibers and water (KLDPEw) and the internal diffusion coefficients (DLDPE), was used to evaluate the leaching process and the leaching half-life of the target UV stabilizers at ω < 0.5 wt % (Case I). Diffusion through the aqueous boundary layer is the rate-determining step, and the leaching half-life is predicted to be very long (a few months to years) under unaffected conditions. When the UV stabilizers are supersaturated within LDPE fibers (i.e., ω > 0.5 wt %, Case II), the possible formation of a surficial crystal layer of the additives on the LDPE fiber extends the time scale for leaching compared to that in Case I due to the requirement of overcoming the crystallization energy. This study provides a fundamental understanding of the leaching profiles of plastic additives for assessing their potential chemical risks in aquatic environments; further studies under the relevant environmental conditions are required.

Effect of sp3/sp2 carbon ratio and hydrodynamic size on the biodistribution kinetics of nanodiamonds in mice via intravenous injection.

BACKGROUND: Nanodiamonds (NDs) have gained a rapidly growing interest in biomedical applications; however, little is known regarding their biokinetics owing to difficulties in measurements and limited synthesis/purification technologies. In this study, we investigated the distribution kinetics of detonation-synthesized NDs in mice via intravenous injection to evaluate the parameters that determine the behavior of the particles. We prepared two distinctive NDs that controlled the sp3/sp2 carbon ratio and particle size by coating them with serum proteins. The four control samples were intravenously injected into mice, and tissue distribution and clearance were evaluated at 30 min and 1, 7, and 28 days post-injection. RESULTS: The sp3/sp2 carbon ratio showed no correlation with the organ distribution of the NDs. However, hydrodynamic size showed an excellent correlation with organ distribution levels: a negative correlation in the liver and positive correlations in the spleen and lungs. Furthermore, the deposition levels of NDs in the lung suggest that particles smaller than 300 nm could avoid lung deposition. Finally, a similar organ distribution pattern was observed in mice injected with carbon black nanoparticles controlled hydrodynamic size. CONCLUSIONS: In conclusion, the tissue distribution of NDs is modulated not by the sp3/sp2 carbon ratio but by the hydrodynamic size, which can provide helpful information for targeting the tissue of NDs. Furthermore, the organ distribution pattern of the NDs may not be specific to NDs but also can apply to other nanoparticles, such as carbon black.

Development of a personal passive air sampler for estimating exposure to effective chlorine while using chlorine-based disinfectants.

With an increasing use of indoor disinfectants such as chlorine (Cl2 ) and hypochlorous acid, a convenient sampler for estimating exposure to oxidants, such as effective chlorine, is necessary. Here, we developed a personal passive air sampler (PPAS) composed of a redox dye, o-dianisidine, in a polydimethylsiloxane (PDMS) sheet. o-Dianisidine readily reacts with gaseous oxidants generated by bleach usage, and its color changes as the reaction progresses; hence, personal exposure to effective chlorine could be easily detected by the naked eye, while cumulative exposure could be determined by measuring concentrations of o-dianisidine reacting with it. The PPAS was calibrated, and a sampling rate of 0.00253 m3 /h was obtained using a small test chamber. The PPAS was tested with the help of ten volunteers whose personal exposure to Cl2 -equivalent gas was estimated after bathrooms were cleaned using spray and liquid-type household disinfection products, and the accumulated exposure-gas concentrations ranged from 69 to 408 ppbv and 148 to 435 ppbv, respectively. These PPAS-derived exposure concentrations were approximately two orders lower than those estimated using ConsExpo, suggesting a significant overestimation by prevailing screening models, possibly due to the ignorance of transformation reactions.

Bioavailability of Fullerene under Environmentally Relevant Conditions: Effects of Humic Acid and Fetal Bovine Serum on Accumulation in Lipid Bilayers and Cellular Uptake.

Carbon fullerene (C60) has emerged at the forefront of nanoscale research and application due to its unique properties. As the production of this nanoparticle rapidly increases, it can be released into natural aquatic environments and can accumulate in biological systems. This research examined the effects of humic acid and fetal bovine serum (FBS), which are ubiquitous in aquatic environments and representative of blood plasma in living organisms, respectively, on bioavailability of fullerene. Bioavailability was investigated using in vitro methods for lipid membrane accumulation and cellular uptake studies. Humic acid and FBS significantly changed the characteristics of fullerene including its particle size and surface charge. The effects of humic acid on lipid accumulation of fullerene depended on the lipid head charge. FBS also significantly decreased the lipid accumulation when positively charged and zwitterionic head groups were present on the lipids, possibly due to the higher steric repulsion of the protein coated nanoparticles. In addition, both humic acid and FBS protein effectively lowered the amounts of fullerene taken up by Caco-2 cells, which are derived from a human colorectal adenocarcinoma and have similar functions to the small intestinal epithelium. Results of this study suggest that surface modification of fullerene by environmentally relevant matrices can significantly affect the biological transport, as well as the possible toxicity of this nanomaterial.

Distribution of Fullerene Nanoparticles between Water and Solid Supported Lipid Membranes: Thermodynamics and Effects of Membrane Composition on Distribution.

The distribution coefficient (Klipw) of fullerene between solid supported lipid membranes (SSLMs) and water was examined using different lipid membrane compositions. Klipw of fullerene was significantly higher with a cationic lipid membrane compared to that with a zwitterionic or anionic lipid membrane, potentially due to the strong interactions between negative fullerene dispersions and positive lipid head groups. The higher Klipw for fullerene distribution to ternary lipid mixture membranes was attributed to an increase in the interfacial surface area of the lipid membrane resulting from phase separation. These results imply that lipid composition can be a critical factor that affects bioconcentration of fullerene. Distribution of fullerene into zwitterionic unsaturated lipid membranes was dominated by the entropy contribution (ΔS) and the process was endothermic (ΔH > 0). This result contrasts the partitioning thermodynamics of highly and moderately hydrophobic chemicals indicating that the lipid-water distribution mechanism of fullerene may be different from that of molecular level chemicals. Potential mechanisms for the distribution of fullerene that may explain these differences include adsorption on the lipid membrane surfaces and partitioning into the center of lipid membranes (i.e., absorption).

Effects of lipid composition on partitioning of fullerene between water and lipid membranes.

Fullerene partition coefficients (Klipw) between water and solid supported lipid membranes were determined for membranes of various lipid types and composition over a range of temperatures. The log Klipw (L/kg) values for fullerene, which range from 3.1 to 5.3, depend on the lipid type in the lipid membranes. Partition coefficients increased with increasing temperature, increasing acyl chain length of unsaturated lipids. The results indicate that lipid composition is a critical factor for bioconcentration of fullerene.

Exploiting the Potential of Magnetic Nanoparticles for Rapid Diagnosis Tests (RDTs): Nanoparticle-Antibody Conjugates and Color Development Strategies.

Magnetic nanoparticles (MNPs) have emerged as a promising material in disease diagnostics due to their potential to enhance detection sensitivity, facilitate concentration and purification of target substances in diverse samples, and enable favorable color-based detection. In this study, antibody-conjugated MNPs were successfully synthesized and validated through two appropriate methods: the measurement of MNPs' size and the use of phosphatase methods. Additionally, three methods were suggested and implemented for developing color in MNPs-based immunoassay, including the formation of MNP aggregations, utilization of MNPs' peroxidase-like activity, and synthesis of dually-conjugated MNPs with both enzyme and antibody. In particular, color development utilizing nanoparticle aggregations was demonstrated to result in a more yellowish color as virus concentration increased, while the peroxidase activity of MNPs exhibited a proportional increase in color intensity as the MNP concentration increased. This observation suggests the potential applicability of quantitative analysis using these methods. Furthermore, effective concentration and purification of target substances were demonstrated through the collection of MNPs using an external magnetic field, irrespective of factors such as antibody conjugation, dispersion medium, or virus binding. Finally, based on the key findings of this study, a design proposal for MNPs-based immunoassay is presented. Overall, MNPs-based immunoassays hold significant potential for advancing disease diagnostics.

Recent Developments in Innovative Magnetic Nanoparticles-Based Immunoassays: From Improvement of Conventional Immunoassays to Diagnosis of COVID-19.

During the ongoing COVID-19 pandemic, the development of point-of-care (POC) detection with high sensitivity and rapid detection time is urgently needed to prevent transmission of infectious diseases. Magnetic nanoparticles (MNPs) have been considered attractive materials for enhancing sensitivity and reducing the detection time of conventional immunoassays due to their unique properties including magnetic behavior, high surface area, excellent stability, and easy biocompatibility. In addition, detecting target analytes through color development is necessary for user-friendly POC detection. In this review, recent advances in different types of MNPs-based immunoassays such as improvement of the conventional enzyme-linked immunosorbent assay (ELISA), immunoassays based on the peroxidase-like activity of MNPs and based on the dually labeled MNPs, filtration method, and lateral-flow immunoassay are described and we analyze the advantages and strategies of each method. Furthermore, immunoassays incorporating MNPs for COVID-19 diagnosis through color development are also introduced, demonstrating that MNPs can become common tools for on-site diagnosis.

Leaching of microplastic-associated additives in aquatic environments: A critical review.

Microplastic pollution has attracted significant attention as an emerging global environmental problem. One of the most important issues with microplastics is the leaching of harmful additives. This review summarizes the recent advances in the understanding of the leaching phenomena in the context of the phase equilibrium between microplastics and water, and the release kinetics. Organic additives, which are widely used in plastic products, have been introduced because they have diverse physicochemical properties and mass fractions in plastics. Many theoretical and empirical models have been utilized in laboratory and field studies. However, the partition or distribution constant between microplastics and water (Kp) and the diffusivity of an additive in microplastics (D) are the two key properties explaining the leaching equilibrium and kinetics of hydrophobic organic additives. Because microplastics in aquatic environments undergo dynamic weathering, leaching of organic additives with high Kp and/or low D cannot be described by a leaching model that only considers microplastic and water phases with a fixed boundary. Surface modifications of microplastics as well as biofilms colonizing microplastic surfaces can alter the leaching equilibrium and kinetics and transform additives. Further studies on the release of hydrophobic organic additives and their transformation products under various conditions are required to extend our understanding of the environmental fate and transport of these additives in aquatic environments.

Estimating the Bioaccumulation Potential of Hydrophobic Ultraviolet Stabilizers Using Experimental Partitioning Properties.

Although hydrophobic ultraviolet (UV) stabilizers are an emerging environmental concern because of their widespread occurrence, persistence, and bioaccumulation potential, experimental values of their partitioning properties required for risk assessment are scarce. In this study, n-octanol-water partition (Kow) and lipid-water partition constants (Klipw), which are key parameters for environmental risk assessment, were experimentally determined for five selected hydrophobic UV stabilizers (UV326, UV327, UV328, UV329, and UV531) based on third-phase partitioning among polydimethylsiloxane (PDMS), water, and n-octanol/lipid. The partition constants between PDMS and water (KPDMSw), obtained using the dynamic permeation method were used to derive Kow and Klipw. The obtained log Kow and log Klipw values were in the ranges of 7.08-7.94 and 7.50-8.34, respectively, indicating that the UV stabilizers exhibited a high bioaccumulation potential in aquatic environments. The experimental Kow and Klipw values obtained in this study provide valuable information for the evaluation of the fate, distribution, bioavailability, and toxicity of the UV stabilizers in aquatic environments.

Equilibrium leaching of selected ultraviolet stabilizers from plastic products.

Despite the importance of (micro)plastics in the release of plastic additives, the leaching mechanism of organic plastic additives from various plastic materials is poorly understood. In this study, the equilibrium leaching of five highly hydrophobic ultraviolet (UV) stabilizers (UV326, UV327, UV328, UV329, and UV531) from three plastics (low-density polyethylene (LDPE), polyethylene terephthalate (PET), and polystyrene (PS)), was investigated employing acetonitrile-water cosolvent systems. Their extrapolated water solubilities were in the 0.15-0.54 µg L-1 range, limiting their transport as "dissolved" in water and (micro)plastics are likely those particulate carriers. The equilibrium leaching of UV stabilizers from plastics was better explained by the Flory-Huggins model incorporating the nonideal behavior caused by the size disparity between UV stabilizers and polymer materials and their compatibility. Specifically, leaching of UV stabilizers from LDPE showed a positive deviation from Raoult's law, whereas slight negative deviations were observed in PET and PS. In addition, the equilibrium concentration of the benzotriazoles in LDPE increased linearly with the volume fraction up to only 0.4%. These observations could be explained by the unfavorable interactions of UV stabilizers with polyethylene, indicating that polymer type should be also important when evaluating the fate of hydrophobic additives. Because equilibrium distribution of additives between (micro)plastics and water is crucial for evaluating the fate and transport of hydrophobic plastic additives, further studies on the leaching equilibrium of various additives from different plastic materials are necessary.

Personal Passive Air Samplers for Chlorinated Gases Generated from the Use of Consumer Products.

Various chlorine-based disinfectants are being used during the COVID-19 pandemic; however, only a few studies on exposure to harmful gases resulting from the use of these disinfectants exist. Previously, we developed a personal passive air sampler (PPAS) to estimate the exposure level to chlorine gas while using chlorinated disinfectants. Herein, we investigated the color development of the passive sampler corresponding to chlorine exposure concentration and time, which allows the general population to easily estimate their gas exposure levels. The uptake and reaction rate of PPAS are also explained, and the maximum capacity of the sampler was determined as 1.8 mol of chlorine per unit volume (m3) of the passive sampler. Additionally, the effects of disinfectant types on the gas exposure level were successfully assessed using passive samplers deployed in a closed chamber. It is noteworthy that the same level of chlorine gas is generated from liquid household bleach regardless of dilution ratios, and we confirmed that the chlorine gas can diffuse out from a gel-type disinfectant. Considering that this PPAS reflects reactive gas removal, individual working patterns, and environmental conditions, this sampler can be successfully used to estimate personal exposure levels of chlorinated gases generated from disinfectants.

Liposome leakage and increased cellular permeability induced by guanidine-based oligomers: effects of liposome composition on liposome leakage and human lung epithelial barrier permeability.

Over the decades, guanidine-based oligomer groups have been one of the most widely used antimicrobial agents. Reportedly, these cationic oligomers cause serious damage to microorganisms but have low toxicity to humans. However, public concerns regarding the guanidine group have rapidly grown after the fatal misuse of these oligomers as humidifier disinfectants, which resulted in thousands of fatalities in South Korea. Herein, we investigated liposome leakage and cellular permeability changes caused by polyhexamethylene guanidine (PHMG) and polyhexamethylene biguanide (PHMB), both representative guanidine-based oligomers. The leakage of zwitterionic liposomes, induced by cationic oligomers, was more extensive than that of negative liposomes, indicating that oligomer adsorption onto lipid head groups via electrostatic interaction cannot fully explain the induced lipid membrane damage. Furthermore, lipid packing parameters, including intrinsic curvature, cholesterol content, and lipid phases, affected liposome leakage, particularly for PHMG. Cellular permeability tests were performed using an A549 cell monolayer model and a respiratory 3D tissue model, revealing that PHMG and PHMB damaged cell membranes and reduced cell barrier function. Furthermore, liposome leakage induced by PHMG and PHMB was higher in human lung surfactant-mimicking liposomes than that observed in Escherichia coli-mimicking liposomes. These results indicated that human cells are susceptible to guanidine-based oligomers. Considering that the interaction of oligomers and cell membranes is a major mechanism of toxicity initiation, this study provides crucial insights into the action of these disinfectants on mammalian cells.

Effects of lipid membrane composition on the distribution of biocidal guanidine oligomer with solid supported lipid membranes.

Polyhexamethylene guanidine (PHMG) is a cationic antimicrobial oligomer that has been used prevalently over the past few decades. However, due to the lack of inhalation toxicity assessment of PHMG, it has caused severe health damage, including fatal lung fibrosis, after being used as one of the major active ingredients of humidifier disinfectants in Korea. Because the first step of the entry of PHMG into airway is its association with cell membranes, the distribution of PHMG between lipid membranes and water is very important to know the depositional flux in the respiratory systems and related toxic mechanisms. We developed a quantitative method to determine the distribution constant (K lipw) of PHMG between solid supported lipid membranes and water and evaluated the effects of lipid membrane compositions on the K lipw of PHMG. PHMG accumulated into anionic lipid membranes rapidly compared to into cationic or zwitterionic lipid membranes, suggesting fast adsorption of PHMG onto anionic lipid head groups. K lipw values with anionic/zwitterionic lipid mixtures were higher than K lipw values with anionic lipids only, potentially due to the later phase separation after preferential interaction between PHMG and anionic lipids in lipid mixtures. In addition, K lipw values increased with increasing single acyl chain lipid content in unsaturated lipids and decreasing cholesterol content. These results imply that changes in lipid spontaneous curvature and lipid bilayer packing density also affect the membrane distribution of PHMG.

Recent Advances Incorporating Superparamagnetic Nanoparticles into Immunoassays.

Superparamagnetic nanoparticles (SPMNPs) have attracted interest for various biomedical applications due to their unique magnetic behavior, excellent biocompatibility, easy surface modification, and low cost. Their unique magnetic properties, superparamagnetism, and magnetophoretic mobility have led to their inclusion in immunoassays to enhance biosensor sensitivity and allow for rapid detection of various analytes. In this review, we describe SPMNP characteristics valuable for incorporation into biosensors, including the use of SPMNPs to increase detection capabilities of surface plasmon resonance and giant magneto-resistive biosensors. The current status of SPMNP-based immunoassays to improve the sensitivity of rapid diagnostic tests is reviewed, and suggested strategies for the successful adoption of SPMNPs for immunoassays are presented.

Determination of 1-octanol-air partition coefficient using gaseous diffusion in the air boundary layer.

Exact determination of the partition coefficient between 1-octanol and air (K(OA)) is very important because it is a key descriptor for describing the thermodynamic partitioning between the air and organic phases. In spite of its importance, the number and quality of experimental K(OA) values for hydrophobic organic chemicals are limited because of experimental difficulties. Thus, to measure K(OA) values, a high-throughput method was developed that used liquid-phase extraction with 1-octanol drop at the tip of a microsyringe needle. The concentration in the headspace surrounding the 1 muL octanol drop was equilibrated with liquid octanol containing polycyclic aromatic hydrocarbons (PAHs). The change in concentrations of PAHs in the octanol drop was measured to obtain mass transfer rate constants, and these rate constants were then converted into K(OA) values using a film diffusion model. Thirteen polycyclic aromatic hydrocarbons with log K(OA) between 5 and 12 were chosen for the proof of the principle. Experimental determination of log K(OA) was accomplished in 30 h for PAHs with their log K(OA) less than 11. The measured log K(OA) values were very close to those obtained by various experimental and estimation methods in the literature, suggesting that this new method can provide a fast and easy determination of log K(OA) values for many chemicals of environmental interests. In addition, the applicability of the method can be extended to determine Henry's law constant for compounds with low vapor pressure and to estimate gaseous transfer rate of semivolatile compounds for environmental fate modeling.