Rational design of hybrid sensor arrays combined synergistically with machine learning for rapid response to a hazardous gas leak environment in chemical plants.

Combinations of semiconductor metal oxide (SMO) sensors, electrochemical (EC) sensors, and photoionization detection (PID) sensors were used to discriminate chemical hazards on the basis of machine learning. Sensing data inputs were exploited in the form of either numerical or image data formats, and the classification of chemical hazards with high accuracy was achieved in both cases. Even a small amount of gas sensing or purging data (input for ∼30 s) input can be exploited in machine-learning-based gas discrimination. SMO sensors exhibit high performance even in a single-sensor mode, presumably because of the intrinsic cross-sensitivity of metal oxides, which is otherwise considered a major disadvantage of SMO sensors. EC sensors were enhanced through synergistic integration of sensor combinations with machine learning. For precision detection of multiple target analytes, a minimum number of sensors can be proposed for gas detection/discrimination by combining sensors with dissimilar operating principles. The Type I hybrid sensor combines one SMO sensor, one EC sensor, and one PID sensor and is used to identify NH3 gas mixed with sulfur compounds in simulations of NH3 gas leak accidents in chemical plants. The portable remote sensing module made with a Type I hybrid sensor and LTE module can identify mixed NH3 gas with a detection time of 60 s, demonstrating the potential of the proposed system to quickly respond to hazardous gas leak accidents and prevent additional damage to the environment.

Anisotropically Conductive Hydrogels with Directionally Aligned PEDOT:PSS in a PVA Matrix.

Electrical anisotropy, which is characterized by the efficient transmission of electrical signals in specific directions, is prevalent in both natural and engineered systems. However, traditional anisotropically conductive materials are often rigid and dry, thus limiting their utility in applications aiming for the seamless integration of various technologies with biological tissues. In the present study, we introduce a method for precisely controlling the microstructures of conductive and insulating polymers to create highly anisotropically conductive composite hydrogels. Our methodology involves combining aligned poly(vinyl alcohol) microfibrils, infused poly(3,4-ethylenedioxythiophene) polystyrenesulfonate, and sodium citrate precipitation to form dense, aligned conductive paths. This significantly enhances the electrical conductivity anisotropy (σ∥/σ⊥ ≈ 60.8) within these composite hydrogels.

Impact of peripheral alkyl chain length on mesocrystal assemblies of G2 dendrons.

Unique sphere-packing mesophases such as Frank-Kasper (FK) phases have emerged from the viable design of intermolecular interactions in supramolecular assemblies. Herein, a series of Cn-G2-CONH2 dendrons possessing an identical core wedge are investigated to elucidate the impact of peripheral alkyl chain lengths (Cn) on the formation of the close-packed structures. The C18 and C14 dendrons, of which the contour lengths of the periphery Lp are longer than the wedge length Lw, assemble into a uniform sphere-packing phase such as body-centred cubic (BCC), whereas the C8 dendron with short (Lp < Lw) corona environment forms the FK A15 phase. Particularly in the intermediate C12 and C10 dendrons (Lp ≈ Lw), cooling the samples from an isotropic state leads to cooling-rate-dependent phase behaviours. The C12 dendron produces two structures of hexagonal columnar and sphere-packing phases (BCC and A15), while the C10 dendron generates the A15 and σ phases by the fast- and slow-cooling processes, respectively. Our results show the impact of peripheral alkyl chain lengths on the formation of mesocrystal phases, where the energy landscape of the dendrons at Lp/Lw ≈ 1 must be more complex and delicate than those with either longer or shorter peripheral alkyl chains.

In-depth probing of thermally-driven phase separation behavior of lamella-forming PS-b-PMMA films by infrared nanoscopy.

A non-invasive, image-based analytic method utilizing scattering-type scanning near-field optical microscopy (s-SNOM) is suggested to evaluate the phase separation behavior of lamella-forming polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymer films. Taking advantage of the penetrability of the tip-enhanced IR signal into the films, the spatio-spectral maps of each component are constructed. Subsequently, the effect of a sole and combinatorial applications of the self-assembly procedures, such as solvent vapor annealing (SVA) and/or thermal annealing (TA), on the spatial distribution of PS or PMMA components is quantitatively assessed in terms of the areal portions of the PS domain, PMMA domain, and the mixed zone that is adjacent to the domain border. Additionally, by statistically comparing the local concentration profiles, the chemical contrast between the domains turns out to be dependent upon the annealing procedures (namely, SVA and SVA + TA). This technique can pave the way to an uncomplicated but precise investigation of the polymer nanostructure-based thin film devices whose performances are critically governed by the spatial arrangement of the chemical elements.

Universal three-dimensional crosslinker for all-photopatterned electronics.

All-solution processing of large-area organic electronics requires multiple steps of patterning and stacking of various device components. Here, we report the fabrication of highly integrated arrays of polymer thin-film transistors and logic gates entirely through a series of solution processes. The fabrication is done using a three-dimensional crosslinker in tetrahedral geometry containing four photocrosslinkable azide moieties, referred to as 4Bx. 4Bx can be mixed with a variety of solution-processable electronic materials (polymer semiconductors, polymer insulators, and metal nanoparticles) and generate crosslinked network under exposure to UV. Fully crosslinked network film can be formed even at an unprecedentedly small loading, which enables preserving the inherent electrical and structural characteristics of host material. Because the crosslinked electronic component layers are strongly resistant to chemical solvents, micropatterning the layers at high resolution as well as stacking the layers on top of each other by series of solution processing steps is possible.

Temperature-Related Summer Mortality Under Multiple Climate, Population, and Adaptation Scenarios.

Projections of the magnitude and pattern of possible health risks from climate change should be based on multiple climate and development scenarios to describe the range of uncertainties, to inform effective and efficient policies. For a better understanding of climate change-related risks in seven metropolitan cities of South Korea, we estimated temperature-related summer (June to August) mortality until 2100 using projected changes in climate, population, and adaptation. In addition, we extracted the variations in the mortality estimates associated with uncertainties in climate, population, and adaptation scenarios using 25 climate models, two Representative Concentration Pathways (RCP 4.5 and 8.5), three population scenarios (high, medium and low variants), and four adaptation scenarios (absolute threshold shift, slope reduction in the temperature-mortality relationship, a combination of slope reduction and threshold shift, and a sigmoid function based on the historical trend). Compared to the baseline period (1991⁻2015), temperature-attributable mortality in South Korea during summer in the 2090s is projected to increase 5.1 times for RCP 4.5 and 12.9 times for RCP 8.5 due to climate and population changes. Estimated future mortality varies by up to +44%/-55%, -80%, -60%, and +12%/-11% associated with the choice of climate models, adaptation, climate, and population scenarios, respectively, compared to the mortality estimated for the median of the climate models, no adaptation, RCP 8.5, and medium population variant. Health system choices about adaptation are the most important determinants of future mortality after climate projections. The range of possible future mortality underscores the importance of flexible, iterative risk management.

Orientation of an Amphiphilic Copolymer to a Lamellar Structure on a Hydrophobic Surface and Implications for CO2 Capture Membranes.

The structural orientation of an amphiphilic crystalline polymer to a highly ordered microphase-separated lamellar structure on a hydrophobic surface is presented. It is formed by the surface graft polymerization of poly(ethylene glycol)behenyl ether methacrylate onto poly(trimethylsilyl) propyne in the presence of allylamine. In particular, allylamine plays a pivotal role in controlling the crystalline phase, configuration, and permeation properties. The resulting materials are effectively used to improve the CO2 capture property of membranes. Upon the optimization of the reaction conditions, a high CO2 permeability of 501 Barrer and a CO2 /N2 ideal selectivity of 77.2 are obtained, which exceed the Robeson upper bound limit. It is inspiring to surpass the upper bound limit via a simple surface modification method.

Irreversible Physisorption of PS-b-PMMA Copolymers on Substrates for Balanced Interfacial Interactions as a Versatile Surface Modification.

We present a direct approach to fabricating the perfect neutral layer for block copolymer (BCP) self-assembled thin films. An irreversible physisorption of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) itself onto the bottom substrates, though extremely thin, offers such a compositional randomness for the substrates, directing the balanced interfacial interactions toward both blocks of the top-layer PS-b-PMMA. Owing to the neutral property from the skin layers, the chemically identical BCP self-assembles into perpendicular microdomains on the adsorbed layer composed of itself, as identified in symmetric PS-b-PMMA films. Intriguingly, the compositional randomness turns out to be valid when the correlation length (ξ) of the BCP layer adsorbed on the substrates is shorter than equilibrium lamellar spacing (L0) of the BCP. Our strategy provides its versatility applicable to various substrates without any necessity of specific random copolymer brushes or mats, enabling the design of a neutral platform for PS-b-PMMA films.

Projection of Future Mortality Due to Temperature and Population Changes under Representative Concentration Pathways and Shared Socioeconomic Pathways.

The Paris Agreement aims to limit the global temperature increase to below 2 °C above pre-industrial levels and to pursue efforts to limit the increase to even below 1.5 °C. Now, it should be asked what benefits are in pursuing these two targets. In this study, we assessed the temperature⁻mortality relationship using a distributed lag non-linear model in seven major cities of South Korea. Then, we projected future temperature-attributable mortality under different Representative Concentration Pathway (RCP) and Shared Socioeconomic Pathway (SSP) scenarios for those cities. Mortality was projected to increase by 1.53 under the RCP 4.5 (temperature increase by 2.83 °C) and 3.3 under the RCP 8.5 (temperature increase by 5.10 °C) until the 2090s, as compared to baseline (1991⁻2015) mortality. However, future mortality is expected to increase by less than 1.13 and 1.26 if the 1.5 °C and 2 °C increase targets are met, respectively, under the RCP 4.5. Achieving the more ambitious target of 1.5 °C will reduce mortality by 12%, when compared to the 2 °C target. When we estimated future mortality due to both temperature and population changes, the future mortality was found to be increased by 2.07 and 3.85 for the 1.5 °C and 2 °C temperature increases, respectively, under the RCP 4.5. These increases can be attributed to a growing proportion of elderly population, who is more vulnerable to high temperatures. Meeting the target of 1.5 °C will be particularly beneficial for rapidly aging societies, including South Korea.

Surface functionalized nanostructures via position registered supramolecular polymer assembly.

Versatile control of cylindrical nanostructures formed by supramolecular assembly of end-functionalized polymer blends is demonstrated not only in their orientation over large areas but also in their surface chemical functionalities. Two binary blends consisting of supramolecular analogues of diblock copolymers with complementary end-sulfonated and aminated groups are investigated, viz., mono-end-functionalized polymers of (i) one-end-sulfonated polystyrene (SPS) and one-end-aminated poly(butadiene) (APBD) and (ii) one end-aminated polystyrene (APS) and one end-sulfonated poly(butadiene) (SPBD). The orientation of the cylinders with respect to the substrate surface depends on the solvent annealing time; either hexagonally ordered vertical cylinders or in-plane ones are readily obtained by controlling the solvent annealing time. Selective chemical etching of one of the polymers provides four different chemically modified nanostructures, viz., hexagonally ordered cylindrical holes and cylindrical posts with either sulfonate or amine surface functional groups. Additional supramolecular assembly is successfully achieved by solution coating either polymers or organic dyes that complementarily interact with the functional groups on the nanostructures. Furthermore, the supramolecularly assembled nanostructures are controlled by confining them to topographically pre-patterned Si substrates with pattern geometries of various shapes and sizes to produce globally ordered vertical or in-plane cylinders with chemical functionalities on their surfaces.

Cumulative energy analysis of thermally-induced surface wrinkling of heterogeneously multilayered thin films.

Wrinkling is a well-known example of instability-driven surface deformation that occurs when the accumulated compressive stress exceeds the critical value in multilayered systems. A number of studies have investigated the instability conditions and the corresponding mechanisms of wrinkling deformation. Force balance analysis of bilayer systems, in which the thickness of the capping layer is importantly considered, has offered a useful approach for the quantitative understanding of wrinkling. However, it is inappropriate for multilayer wrinkling (layer number > 3) consisting of heterogeneous materials (e.g. polymer/metal or inorganic), in which the thickness variation in the substrate is also crucial. Therefore, to accommodate the additive characteristics of multilayered systems, we thermally treated tri- or quad-layer samples of polymer/metal multilayers to generate surface wrinkles and used a cumulative energy balance analysis to consider the individual contribution of each constituent layer. Unlike the composite layer model, wherein the thickness effect of the capping layer is highly overestimated for heterogenously stacked multilayers, our approach precisely reflects the bending energy contribution of the given multilayer system, with results that match well with experimental values. Furthermore, we demonstrate the feasibility of this approach as a metrological tool for simple and straightforward estimation of the thermomechanical properties of polymers, whereby a delicate change in the Young's modulus of a thin polymeric layer near its glass transition temperature can be successfully monitored.

Effects of particulate matter on respiratory disease and the impact of meteorological factors in Busan, Korea.

BACKGROUND: Both air pollution and weather impact hospitalization for respiratory diseases. However, few studies have investigated the contribution of weather to hospitalization related to the adverse effects of air pollution. This study analyzed the effects of particulate matter (PM) on daily respiratory-related hospital admissions, taking into account meteorological factors. METHODS: Daily hospital admissions for respiratory diseases (acute bronchitis, allergic rhinitis, and asthma) between 2007 and 2010 were extracted from the National Health Insurance Corporation, Korea. Patients were divided into three age-based groups (0-15, 16-64, and ≥65 years). PM levels were obtained from 19 monitoring stations in Busan. RESULTS: The mean number of patients admitted for acute bronchitis, allergic rhinitis, and asthma was 5.8 ± 11.9, 4.4 ± 6.1, and 3.3 ± 3.3, respectively. During that time, the daily mean PM10 and PM2.5 concentrations were 49.6 ± 20.5 and 24.2 ± 10.9 µg/m3, respectively. The mean temperature anomaly was 7.0 ± 2.3 °C; the relative humidity was 62.0 ± 18.0%. Hospital admission rates for respiratory diseases increased with increasing PM and temperature, and with decreasing relative humidity. A multivariate analysis including PM, temperature anomaly, relative humidity, and age showed a significant increase in respiratory-related admissions with increasing PM levels and a decreasing relative humidity. Higher PM2.5 levels had a greater effect on respiratory-related hospital admission than did PM10 levels. Children and the elderly were the most susceptible to hospital admission for respiratory disease. CONCLUSIONS: PM levels and meteorological factors impacted hospitalization for respiratory diseases, especially in children and the elderly. The effect of PM on respiratory diseases increased as the relative humidity decreased.

Thermally Stable Bulk Heterojunction Prepared by Sequential Deposition of Nanostructured Polymer and Fullerene.

A morphologically-stable polymer/fullerene heterojunction has been prepared by minimizing the intermixing between polymer and fullerene via sequential deposition (SqD) of a polymer and a fullerene solution. A low crystalline conjugated polymer of PCPDTBT (poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]) has been utilized for the polymer layer and PC71BM (phenyl-C71-butyric-acid-methyl ester) for the fullerene layer, respectively. Firstly, a nanostructured PCPDTBT bottom layer was developed by utilizing various additives to increase the surface area of the polymer film. The PC71BM solution was prepared by dissolving it in the 1,2-dichloroethane (DCE), exhibiting a lower vapor pressure and slower diffusion into the polymer layer. The deposition of the PC71BM solution on the nanostructured PCPDTBT layer forms an inter-digitated bulk heterojunction (ID-BHJ) with minimized intermixing. The organic photovoltaic (OPV) device utilizing the ID-BHJ photoactive layer exhibits a highly reproducible solar cell performance. In spite of restricted intermixing between the PC71BM and the PCPDTBT, the efficiency of ID-BHJ OPVs (3.36%) is comparable to that of OPVs (3.87%) prepared by the conventional method (deposition of a blended solution of polymer:fullerene). The thermal stability of the ID-BHJ is superior to the bulk heterojunction (BHJ) prepared by the conventional method. The ID-BHJ OPV maintains 70% of its initial efficiency after thermal stress application for twelve days at 80 °C, whereas the conventional BHJ OPV maintains only 40% of its initial efficiency.