Assessment of potential environmental and human risks for Bisphenol AF contaminant.

Bisphenol AF (BPAF) is found in high concentrations in aquatic environments due to the increased use of thermal paper and food packaging. However, there have been relatively few toxicological studies and potential risk assessments of BPAF. In this study, the risk quotient (RQ) and hazard quotient (HQ) of BPAF were derived to present the safety standards for environmental risk management and protection in lakes, rivers, bays, and Italian regions. We applied the species sensitivity distribution (SSD) method based on the previous ecotoxicological data and the results of supplementary toxicity tests on BPAF. From the SSD curves, the hazardous concentration for 5 % of the species (HC5) values for the acute and chronic toxicity data were 464.75 µg/L and 3.59 µg/L, respectively, and the acute- and chronic-based predicted no-effect concentration were derived as 154.92 µg/L and 1.20 µg/L, respectively. The acute-based RQ (RQA)values of BPAF in all regions were negligible (RQ < 0.1). The chronic-based RQ (RQC) in the Xitang River (XR) and the Central Italy (CI) showed a considerably high ecological risk (12.77 and 1.29) and the Hangzhou Bay (0.21), the South and North Italy (0.79 and 0.27), and the Tamagawa River (0.13) had a medium ecological risk (0.1 < RQ < 1.0). However, the HQ values based on the tolerable daily intake for BPAF over all age groups in these regions was < 0.1, indicating the low health risk. Nonetheless, the result of this study indicates that BPAF contamination is serious in XR and CI, and their use and emissions require continuous monitoring.

Assessment of potential ecological risk for polycyclic aromatic hydrocarbons in urban soils with high level of atmospheric particulate matter concentration.

Polycyclic aromatic hydrocarbons (PAHs) are known to be representative carcinogenic environmental pollutants with high toxicity. However, information on the potential ecological and environmental risks of PAH contamination in soil remains scarce. Thus, this study was evaluated the potential ecological risks of PAHs in soils of five Korean areas (Gunsan (GS), Gwangju, Yeongnam, Busan, and Gangwon) using organic carbon (OC)-normalized analysis, mean effect range-median quotient (M-ERM-Q), toxic equivalent quantity (TEQ) analysis, and risk quotient (RQ) derived by the species sensitivity distribution model. In this study, atmospheric particulate matter has a significant effect on soil pollution in GS through the presence of hopanes and the similar pattern of PAHs in soil and atmospheric PAHs. From analysis of source identification, combustion sources in soils of GS were important PAH sources. For PAHs in soils of GS, the OC-normalized analysis, M-ERM-Q, and TEQ analysis have 26.78 × 105 ng/g-OC, 0.218, and 49.72, respectively. Therefore, the potential ecological risk assessment results showed that GS had moderate-high ecological risk and moderate-high carcinogenic risk, whereas the other regions had low ecological risk and low-moderate carcinogenic risk. The risk level (M-ERM-Q) of PAH contamination in GS was similar to that in Changchun and Xiangxi Bay in China. The Port Harcourt City in Nigeria for PAH has the highest risk (M-ERM-Q = 4.02 and TEQ = 7923). Especially, compared to China (RQPhe =0.025 and 0.05), and Nigeria (0.059), phenanthrene showed the highest ecological risk in Korea (0.001-0.18). Korea should focus on controlling the release of PAHs originating from the PM in GS.

Identification of aquatic ecological risk of bisphenol S in four Asian countries based on the SSD and alternative toxicity data of model species Danio rerio.

Bisphenol S (BPS), an organic compound and bisphenol analog, is commonly used as a substitute for bisphenol A. BPS is widely used in epoxy glues, can coatings, and thermal receipt papers; however, its risks have not been fully determined and the probability of its toxicity has been continuously suggested. In this study, we conducted BPS toxicity tests on aquatic plants (acute), cladocerans (acute and chronic), and fish (chronic) to determine its adverse effects, and calculated the toxicity values. Additionally, we conducted an ecological risk assessment of BPS in freshwater ecosystems with toxicity data from previous studies using the species sensitivity distribution method and BPS exposure data from 14 rivers in four countries in Asia (China, Japan, India, and South Korea). The chronic-based risk quotient (RQ) values of BPS in one river in China and two rivers in India were > 1, indicating a high ecological risk of BPS to aquatic organisms. The other four rivers in China showed medium ecological risk (0.1 < RQ < 1) and those in Japan and South Korea showed negligible chronic risk (RQ < 0.1) to aquatic organisms. We also suggest sensitive indicators in the model organism Danio rerio and highlighted the importance of the development of new method of ecological risk assessment. This study could provide new information that will assist in managing BPS and bisphenol analogs in freshwater ecosystems.

Diesel vehicles-derived PM2.5 induces lung and cardiovascular injury attenuates by Securiniga suffruticosa: Involvement of NF-κB-mediated NLRP3 inflammasome activation pathway.

Respiratory exposure to Particulate matter (PM), including Diesel exhaust particulate (DEP), causes oxidative stress-induced lung inflammation. Especially, fine particulate matter with an aerodynamic diameter less than 2.5 µm (PM2.5) is a serious air pollutant associated with various health problems including cardiovascular diseases. The present study aimed to examine the inhibitory effect of Securiniga suffruticosa (S. suffruiticosa) on DEP and PM-induced lung and cardiovascular diseases. Mice inhaled DEP by using nebulizer chamber for two weeks. Treatment with S. suffruiticosa reduced the expression of C-X-C motif ligand 1/2 in bronchoalveolar lavage fluid and Muc5ac, ICAM-1, TNF-⍺, IL-6 mRNA in lung were also attenuated by S. suffruiticosa. In thoracic aorta, DEP increased CAMs, TNF-⍺ and inflammasome markers such as NLRP3, Caspase-1, and ASC. However, S. suffruiticosa suppressed these levels. S. suffruiticosa inhibited PM2.5 induced production of intracellular reactive oxygen species (ROS); and inhibited the translocation of NF-κB p65 to the nucleus in human umbilical vein endothelial cells. Taken together, this study proved that exposure to PM2.5 induced both lung and vascular inflammation, however, S. suffruiticosa attenuated this injury via the downregulation of the NLRP3 signaling pathway. These findings suggest that S. suffruiticosa may have potential therapeutic benefit against air pollution-mediated lung and cardiovascular diseases.

Coconut Oil Alleviates the Oxidative Stress-Mediated Inflammatory Response via Regulating the MAPK Pathway in Particulate Matter-Stimulated Alveolar Macrophages.

Exposure to particulate matter (PM) is related to various respiratory diseases, and this affects the respiratory immune system. Alveolar macrophages (AMs), which are defenders against pathogens, play a key role in respiratory inflammation through cytokine production and cellular interactions. Coconut oil demonstrates antioxidant and anti-inflammatory properties, and it is consumed worldwide for improved health. However, reports on the protective effects of coconut oil on the PM-induced respiratory immune system, especially in AMs, are limited. In this study, we generated artificial PM (APM) with a diameter approximately of 30 nm by controlling the temperature, and compared its cytotoxicity with diesel exhaust particles (DEP). We also investigated the antioxidant and anti-inflammatory effects of coconut oil in APM− and DEP−stimulated AMs, and the underlying molecular mechanisms. Our results showed that APM and DEP had high cytotoxicity in a dose-dependent manner in AMs. In particular, APM or DEP at 100 µg/mL significantly decreased cell viability (p < 0.05) and significantly increased oxidative stress markers such as reactive oxygen species (p < 0.01); the GSSH/GSH ratio (p < 0.01); and cytokine production, such as tumor necrosis factor-α (p < 0.001), interleukin (IL)-1ß (p < 0.001), and IL-6 (p < 0.001). The expression of the genes for chemokine (C-X-C motif) ligand-1 (p < 0.05) and monocyte chemoattractant protein-1 (p < 0.001); and the proteins toll-like receptor (TLR) 4 (p < 0.01), mitogen-activated protein kinase (MAPK), and c-Jun N-terminal kinase (p < 0.001), p38 (p < 0.001); and extracellular receptor-activated kinase (p < 0.001), were also upregulated by PM. These parameters were reversed upon treatment with coconut oil in APM− or DEP−stimulated AMs. In conclusion, coconut oil can reduce APM− or DEP−induced inflammation by regulating the TLR4/MAPK pathway in AMs, and it may protect against adverse respiratory effects caused by PM exposure.

Identification of Chemical Vapor Mixture Assisted by Artificially Extended Database for Environmental Monitoring.

A fully integrated sensor array assisted by pattern recognition algorithm has been a primary candidate for the assessment of complex vapor mixtures based on their chemical fingerprints. Diverse prototypes of electronic nose systems consisting of a multisensory device and a post processing engine have been developed. However, their precision and validity in recognizing chemical vapors are often limited by the collected database and applied classifiers. Here, we present a novel way of preparing the database and distinguishing chemical vapor mixtures with small data acquisition for chemical vapors and their mixtures of interest. The database for individual vapor analytes is expanded and the one for their mixtures is prepared in the first-order approximation. Recognition of individual target vapors of NO2, HCHO, and NH3 and their mixtures was evaluated by applying the support vector machine (SVM) classifier in different conditions of temperature and humidity. The suggested method demonstrated the recognition accuracy of 95.24%. The suggested method can pave a way to analyze gas mixtures in a variety of industrial and safety applications.

Relationship between Cytotoxicity and Surface Oxidation of Artificial Black Carbon.

The lacking of laboratory black carbon (BC) samples have long challenged the corresponding toxicological research; furthermore, the toxicity tests of engineered carbon nanoparticles were unable to reflect atmospheric BC. As a simplified approach, we have synthesized artificial BC (aBC) for the purpose of representing atmospheric BC. Surface chemical properties of aBC were controlled by thermal treatment, without transforming its physical characteristics; thus, we were able to examine the toxicological effects on A549 human lung cells arising from aBC with varying oxidation surface properties. X-ray photoelectron spectroscopy, as well as Raman and Fourier transform infrared spectroscopy, verified the presence of increased amounts of oxygenated functional groups on the surface of thermally-treated aBC, indicating aBC oxidization at elevated temperatures; aBC with increased oxygen functional group content displayed increased toxicity to A549 cells, specifically by decreasing cell viability to 45% and elevating reactive oxygen species levels up to 294% for samples treated at 800 °C.

On-Chip Chemiresistive Sensor Array for On-Road NO x Monitoring with Quantification.

The adverse effects of air pollution on respiratory health make air quality monitoring with high spatial and temporal resolutions essential especially in cities. Despite considerable interest and efforts, the application of various types of sensors is considered immature owing to insufficient sensitivity and cross-interference under ambient conditions. Here, a fully integrated chemiresistive sensor array (CSA) with parts-per-trillion sensitivity is demonstrated with its application for on-road NO x monitoring. An analytical model is suggested to describe the kinetics of the sensor responses and quantify molecular binding affinities. Finally, the full characterization of the system is connected to implement on-road measurements on NO x vapor with quantification as its ultimate field application. The obtained results suggest that the CSA shows potential as an essential unit to realize an air-quality monitoring network with high spatial and temporal resolutions.

Efficient and stable radiolabeling of polycyclic aromatic hydrocarbon assemblies: in vivo imaging of diesel exhaust particulates in mice.

As a robust radioanalytical method for tracking carbonaceous particulates in vivo, polycyclic aromatic hydrocarbons from diesel exhaust were labeled with a radioactive-iodine-tagged pyrene analogue. Single-photon emission computed tomography and biodistribution studies showed high uptake and slow clearance of this matter in the respiratory system, which may underlie its severe toxicity.

Measuring Bone Biomarker Alkaline Phosphatase with Wafer-Scale Nanowell Array Electrodes.

Biosensors that can analyze a single drop of biological fluid can overcome limitations such as extraction volume from humans or animals, ethical problems, time, and cost. In this work, we have developed a highly sensitive electrochemical (EC) biosensor based on a nanowell array (NWA) for the detection of alkaline phosphatase (ALP), a serum indicator of bone formation. The size of the electrode is 2 × 1 mm2 and has over 10 million nanowells (400 nm diameter) arranged uniformly on the electrode surface. For detecting ALP, anti-ALP was immobilized and oriented on the NWA surface using a self-assembled monolayer and protein G. EC impedance spectroscopy (EIS) was used to determine the amount of ALP in 10 µL of sample. The impedance was calibrated with ALP concentration. The NWA has a linear dynamic range from 1 pg/mL to 100 ng/mL with a limit of detection (LOD) at 12 pg/mL. We used the sensor to measure the ALP in real mouse serum from 4, 10, and 20 weeks old mice and compared the results to the standard photometric assay. This work demonstrates the potential of EC NWA sensors to analyze a single drop of a real body fluid sample and to be developed for broad applications.

Hollow Pt-Functionalized SnO2 Hemipill Network Formation Using a Bacterial Skeleton for the Noninvasive Diagnosis of Diabetes.

Hollow-structured nanomaterials are presented as an outstanding sensing platform because of their unique combination of high porosity in both the micro- and nanoscale, their biocompatibility, and flexible template applicability. Herein, we introduce a bacterial skeleton method allowing for cost-effective fabrication with nanoscale precision. As a proof-of-concept, we fabricated a hollow SnO2 hemipill network (HSHN) and a hollow Pt-functionalized SnO2 hemipill network (HPN). A superior detecting capability of HPN toward acetone, a diabetes biomarker, was demonstrated at low concentration (200 ppb) under high humidity (RH 80%). The detection limit reaches 3.6 ppb, a level satisfying the minimum requirement for diabetes breath diagnosis. High selectivity of the HPN sensor against C6H6, C7H8, CO, and NO vapors is demonstrated using principal component analysis (PCA), suggesting new applications of HPN for human-activity monitoring and a personal healthcare tool for diagnosing diabetes. The skeleton method can be further employed to mimic nanostructures of biomaterials with unique functionality for broad applications.

Chemiresistive Electronic Nose toward Detection of Biomarkers in Exhaled Breath.

Detection of gas-phase chemicals finds a wide variety of applications, including food and beverages, fragrances, environmental monitoring, chemical and biochemical processing, medical diagnostics, and transportation. One approach for these tasks is to use arrays of highly sensitive and selective sensors as an electronic nose. Here, we present a high performance chemiresistive electronic nose (CEN) based on an array of metal oxide thin films, metal-catalyzed thin films, and nanostructured thin films. The gas sensing properties of the CEN show enhanced sensitive detection of H2S, NH3, and NO in an 80% relative humidity (RH) atmosphere similar to the composition of exhaled breath. The detection limits of the sensor elements we fabricated are in the following ranges: 534 ppt to 2.87 ppb for H2S, 4.45 to 42.29 ppb for NH3, and 206 ppt to 2.06 ppb for NO. The enhanced sensitivity is attributed to the spillover effect by Au nanoparticles and the high porosity of villi-like nanostructures, providing a large surface-to-volume ratio. The remarkable selectivity based on the collection of sensor responses manifests itself in the principal component analysis (PCA). The excellent sensing performance indicates that the CEN can detect the biomarkers of H2S, NH3, and NO in exhaled breath and even distinguish them clearly in the PCA. Our results show high potential of the CEN as an inexpensive and noninvasive diagnostic tool for halitosis, kidney disorder, and asthma.

Highly Sensitive H2S Sensor Based on the Metal-Catalyzed SnO2 Nanocolumns Fabricated by Glancing Angle Deposition.

As highly sensitive H2S gas sensors, Au- and Ag-catalyzed SnO2 thin films with morphology-controlled nanostructures were fabricated by using e-beam evaporation in combination with the glancing angle deposition (GAD) technique. After annealing at 500 °C for 40 h, the sensors showed a polycrystalline phase with a porous, tilted columnar nanostructure. The gas sensitivities (S = Rgas/Rair) of Au and Ag-catalyzed SnO2 sensors fabricated by the GAD process were 0.009 and 0.015, respectively, under 5 ppm H2S at 300 °C, and the 90% response time was approximately 5 s. These sensors showed excellent sensitivities compared with the SnO2 thin film sensors that were deposited normally (glancing angle = 0°, S = 0.48).

Enhanced piezoelectric properties of vertically aligned single-crystalline NKN nano-rod arrays.

Piezoelectric materials capable of converting between mechanical and electrical energy have a great range of potential applications in micro- and nano-scale smart devices; however, their performance tends to be greatly degraded when reduced to a thin film due to the large clamping force by the substrate and surrounding materials. Herein, we report an effective method for synthesizing isolated piezoelectric nano-materials as means to relax the clamping force and recover original piezoelectric properties of the materials. Using this, environmentally friendly single-crystalline NaxK1-xNbO3 (NKN) piezoelectric nano-rod arrays were successfully synthesized by conventional pulsed-laser deposition and demonstrated to have a remarkably enhanced piezoelectric performance. The shape of the nano-structure was also found to be easily manipulated by varying the energy conditions of the physical vapor. We anticipate that this work will provide a way to produce piezoelectric micro- and nano-devices suitable for practical application, and in doing so, open a new path for the development of complex metal-oxide nano-structures.

High output piezo/triboelectric hybrid generator.

Recently, piezoelectric and triboelectric energy harvesting devices have been developed to convert mechanical energy into electrical energy. Especially, it is well known that triboelectric nanogenerators have a simple structure and a high output voltage. However, whereas nanostructures improve the output of triboelectric generators, its fabrication process is still complicated and unfavorable in term of the large scale and long-time durability of the device. Here, we demonstrate a hybrid generator which does not use nanostructure but generates much higher output power by a small mechanical force and integrates piezoelectric generator into triboelectric generator, derived from the simultaneous use of piezoelectric and triboelectric mechanisms in one press-and-release cycle. This hybrid generator combines high piezoelectric output current and triboelectric output voltage, which produces peak output voltage of ~370 V, current density of ~12 µA · cm(-2), and average power density of ~4.44 mW · cm(-2). The output power successfully lit up 600 LED bulbs by the application of a 0.2 N mechanical force and it charged a 10 µF capacitor to 10 V in 25 s. Beyond energy harvesting, this work will provide new opportunities for developing a small, built-in power source in self-powered electronics such as mobile electronics.

Extremely sensitive and selective NO probe based on villi-like WO3 nanostructures for application to exhaled breath analyzers.

Self-assembled WO3 thin film nanostructures with 1-dimensional villi-like nanofingers (VLNF) have been synthesized on the SiO2/Si substrate with Pt interdigitated electrodes using glancing angle deposition (GAD). Room-temperature deposition of WO3 by GAD resulted in anisotropic nanostructures with large aspect ratio and porosity having a relative surface area, which is about 32 times larger than that of a plain WO3 film. A WO3 VLNF sensor shows extremely high response to nitric oxide (NO) at 200 °C in 80% of relative humidity atmosphere, while responses of the sensor to ethanol, acetone, ammonia, and carbon monoxide are negligible. Such high sensitivity and selectivity to NO are attributed to the highly efficient modualtion of potential barriers at narrow necks between individual WO3 VLNF and the intrinsically high sensitivity of WO3 to NO. The theoretical detection limit of the sensor for NO is expected to be as low as 88 parts per trillion (ppt). Since NO is an approved biomarker of chronic airway inflammation in asthma, unprecedentedly high response and selectivity, and ppt-level detection limit to NO under highly humid environment demonstrate the great potential of the WO3 VLNF for use in high performance breath analyzers.

Sensitivity enhancement of nanostructured SnO2 gas sensors fabricated using the glancing angle deposition method.

0.5 wt.% Pd-catalyzed SnO2 thin-film gas sensors with microstructures controlled on a nanometer scale were fabricated by an e-beam evaporator using the glancing angle deposition (GAD) method. After annealing at 500 degrees C for 1 h, the sensors produced were polycrystalline with a nanoporous, tilted columnar microstructure. The gas-sensing properties of these SnO2 sensors were measured in the concentration range of 1 to 5 ppm NO2 at 250 degrees C and of 10 to 50 ppm C2H5OH at 400 degrees C, respectively. The sensors fabricated by e-beam evaporation in combination with the GAD method showed much higher sensitivities than normally prepared sensors and exhibited rapid response times. The gas sensitivity (S = R(gas)/R(air)) of the SnO2 sensor using the GAD method was 43.4 for 5 ppm NO2 and 0.08 for 10 ppm C2H5OH, respectively. These sensors showed excellent sensitivities compared to the normal thin film sensors (S = 2 for 5 ppm NO2 and 0.92 for 10 ppm C2H5OH). We consider that the nanostructured sensors produced using the GAD process could be used to detect various gases emitted by automobiles and industrial installations.

Highly ordered large-area colloid templates for nanostructured TiO2 thin film gas sensors.

We report a novel process that uses highly ordered colloidal templating to fabricate nanostructured TiO2 thin film gas sensors. An O2 plasma treatment is used to decrease the contact angle of a water droplet on a SiO2/Si substrate from 46 degrees to 3 degrees. The formation of this hydrophilic surface enhances the adhesion of polystyrene microspheres to the substrate during the spin coating of the colloidal solution, leading to a large-area colloid template of closely packed monolayer microspheres on the substrates. Embossed TiO2 thin film gas sensors fabricated through highly ordered colloidal templating using O2 plasma exhibit substantially enhanced gas sensing performance as compared to those without surface treatments prior to colloidal templating.

Self-activated ultrahigh chemosensitivity of oxide thin film nanostructures for transparent sensors.

One of the top design priorities for semiconductor chemical sensors is developing simple, low-cost, sensitive and reliable sensors to be built in handheld devices. However, the need to implement heating elements in sensor devices, and the resulting high power consumption, remains a major obstacle for the realization of miniaturized and integrated chemoresistive thin film sensors based on metal oxides. Here we demonstrate structurally simple but extremely efficient all oxide chemoresistive sensors with ~90% transmittance at visible wavelengths. Highly effective self-activation in anisotropically self-assembled nanocolumnar tungsten oxide thin films on glass substrate with indium-tin oxide electrodes enables ultrahigh response to nitrogen dioxide and volatile organic compounds with detection limits down to parts per trillion levels and power consumption less than 0.2 microwatts. Beyond the sensing performance, high transparency at visible wavelengths creates opportunities for their use in transparent electronic circuitry and optoelectronic devices with avenues for further functional convergence.