Residue Behavior of Methoxyfenozide and Pymetrozine in Chinese Cabbage and Their Health Risk Assessment.

Methoxyfenozide and pymetrozine are used for pest control in the cultivation of Chinese cabbage. This has raised concerns in recent years due to health risks. Therefore, this study aimed to determine the residual concentrations of pesticides in the target crop and associated health risks. The dynamics and influence of environmental factors on the dissipation of methoxyfenozide and pymetrozine residues in Chinese cabbage were investigated. Analyses were performed using a modified QuEchERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) and an optimized high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The observed half-lives of methoxyfenozide and pymetrozine in cabbage samples ranged between two sampling seasons: in May−June, half-lives of methoxyfenozide and pymetrozine were 1.20 days and 1.89 days, respectively; during October−November, half-lives of methoxyfenozide and pymetrozine were 11.8 and 2.80 days, respectively. Meanwhile, a negative Spearman correlation was found between the residual concentrations and temperature (p < 0.01). This indicates that higher temperatures resulted in higher dissipation rates for methoxyfenozide and pymetrozine, suggesting that these pesticides degraded faster at higher temperatures. Additionally, higher pesticide residues in Chinese cabbage during low-temperature seasons resulted in higher risk quotients (RQ) (RQ > 1) for both analyzed compounds, which suggests that the effect of temperature on pesticide degradation needs to be considered as an essential factor while setting up the maximum residue limits (MRL).

Structural, Optical, and Magnetic Properties of Erbium-Substituted Yttrium Iron Garnets.

We synthesized a series of slightly erbium-substituted yttrium iron garnets (Er:YIG), Y3-x Er x Fe5O12 at different Er concentrations (x = 0, 0.01, 0.05, 0.10, and 0.20) using a solid-state reaction and investigated their structural, magnetic, and optical properties as a function of Er concentration. The volume of the unit cell slightly increased with Er concentration and Er atoms predominately replaced Y atoms in the dodecahedrons of YIG. The optical properties exhibited certain decreases in reflectance in the 1500-1600 nm wavelength range due to the presence of Er3+. Despite the many unpaired 4f electrons in Er3+, the total magnetic moments of Er:YIG showed similar trends with temperatures and magnetic fields above 30 K. An X-ray magnetic circular dichroism study confirmed the robust Fe 3d magnetic moments. However, the magnetic moments suddenly decreased to below 30 K with Er substitution, and the residual magnetism (M R) and coercive field (H C) in the magnetic hysteresis loops decreased to below 30 K with Er substitution. This implies that Er substitution in YIG has a negligible effect on magnetic properties over a wide temperature range except below 30 K where the Er 4f spins are coupled antiparallel to the majority Fe 3d spins. Our studies demonstrated that above 30 K the magnetic properties of YIG are retained even with Er substitution, which is evidence that the Er doping scheme is applicable for YIG-based magneto-optical devices in the mid-infrared regime.

Healthcare Utilization for Lateral Epicondylitis: A 9-Year Analysis of the 2010-2018 Health Insurance Review and Assessment Service National Patient Sample Data.

This retrospective cross-sectional study examined healthcare utilization among 213,025 patients with lateral epicondylitis over a nine-year period using the 2010-2018 Health Insurance Review and Assessment Service (HIRA) data (ICD code M771). Healthcare utilization, types of treatment, and the route of the visit were analyzed with frequency analysis for Western medicine (WM) and Korean medicine (KM). The findings revealed that the number of patients visiting WM and KM facilities for lateral epicondylitis rose every year from 2010 to 2018. Over this period, the age distribution of patients was 45-54 years (39.93%), 55-64 (23.12%), and 35-44 years (21.07%), and there were slightly more female patients (53.66%) than male patients (46.34%). The number of claims for lateral epicondylitis tended to increase with decreasing average monthly temperature; an increased proportion of middle-aged patients (45-64 years) was the most evident. The most frequently performed interventions in WM were subcutaneous or intramuscular injection (injection), deep heat therapy (physical therapy), and spinal peripheral nerve block-axillary nerve block (treatment/operation); the most frequently performed intervention in KM was acupuncture (injection). For pharmacological treatment, analgesics and anti-inflammatory medications were most frequently prescribed. The findings can be useful for health policymakers and as foundational data for clinicians and researchers.

Uniform deposition method of monodispersed SiO2 nanoparticles on a 300-mm Si wafer surface.

A study of the uniform deposition of nanoparticles across a 300-mm wafer was conducted to assess the uniformity of the wafer center-to-edge cleaning technique. A new method of particle deposition was devised different from the conventional method using electrostatic force. The strategy implements wafer rotation and deposition through principles of convection and diffusion. In this study, we focused on the effect of wafer rotation speed on particle deposition. After determining optimum conditions, fine results were obtained with a well-deposited shape and an excellent particle size uniformity of above 70% over the entire area of the wafer except in unusual cases. Deposition results were confirmed with KLA-Tencor Surfscan SP5 commonly used by foundries, and logic and memory manufacturers around the world to increase node development and production. The inherent index of the refraction value by Surfscan SP5 caused a particle size shift in measurement results. However, scanning electron microscopy and scanning mobility particle sizer analysis results revealed that 80-, 60-, 40-, 30-, and 20-nm-sized silica nanoparticles were well deposited on the wafer. Through this research, we believe that standard wafers processed with this particle deposition method will be useful for performance evaluation of wafer cleaning technology and calibration of wafer inspection technology during development.

Gender differences in the effect of self-rated health (SRH) on all-cause mortality and specific causes of mortality among individuals aged 50 years and older.

Although different gender associations between self-rated health (SRH) and mortality have been reported, the results of the respective studies have been inconsistent and little is known about the cause-specific relation of mortality with SRH by gender. Therefore, to evaluate the gender differences in all-cause or specific causes of mortality by SRH, this retrospective cohort study was conducted using the data of 19,770 Korean adults aged 50 years and over who underwent health screening at Seoul National University Hospital between March 1995 and December 2008. SRH was surveyed using a simple questionnaire, and the all-cause mortality and cause-specific mortality were followed up from baseline screening until December 31, 2016. Results showed that the relationship between SRH and all-cause mortality differed by gender, and the differences also varied depending on the cause of death. In men, the adjusted hazard ratio (aHR) of all-cause mortality was higher in the poor SRH group than the very good SRH groups even after adjustment for socio-demographic, clinical, and behavioral risk factors (aHR:1.97, 95% CI 1.51-2.56), and these results were similar to those for cancer, cardiovascular, and respiratory disease mortalities (aHR:1.52, 95% CI 0.93-2.50; aHR: 2.11, 95% CI 1.19-3.74; aHR:10.30, 95% CI 2.39-44.44, respectively). However, in women, the association between SRH and all-cause mortality was insignificant, and inverse relationships were found for cardiovascular and respiratory disease mortalities in the poor and very good SRH groups. Cancer mortality had a positive relation with SRH (aHR: 1.14, 95% CI 0.75-1.72; aHR: 2.58, 95% CI 1.03-6.48; aHR: 0.49, 95% CI 0.24-0.98; aHR: 0.15, 95% CI 0.04-0.57: all-cause, cancer, cardiovascular, and respiratory disease mortalities, respectively). Clinicians need to take these gender differences by SRH into account when evaluating the health status of over-middle aged adults.

Molecular Oriented Charge Accumulation in High-Efficiency Polymer Solar Cells as Revealed by Operando Spin Analysis.

A low band-gap polymer, PTB7-Th, is one of the typical p-type semiconductors among the next-generation solar-cell materials that have achieved power conversion efficiencies of over 10%. However, the internal deterioration mechanism of high-efficiency polymer solar cells such as PTB7-Th-based cells is still an open issue and has been extensively studied. Here, we report a study with operando electron spin resonance (ESR) spectroscopy for PTB7-Th polymer solar cells with an n-type semiconductor PC71BM to clarify the internal deterioration mechanism at a molecular level. We have directly observed ambipolar charge accumulation with a face-on molecular orientation in the cells under simulated solar irradiation using an operando light-induced ESR technique. Moreover, we have found a clear correlation between the charge accumulation and performance deterioration of the cells. The charge accumulation sites have been clarified by the ESR analysis and density functional theory calculation. The prevention of such charge accumulation on the basis of the present finding would be important for the commercialization of high-efficiency polymer solar cells.

Operando Direct Observation of Charge Accumulation and the Correlation with Performance Deterioration in PTB7 Polymer Solar Cells.

Polymer solar cells are one of the promising energy sources because of the easy solution-processable production with large area at a low cost without toxicity. Among the polymer materials, a donor-acceptor conjugated copolymer PTB7 has been extensively studied because of the typical high-performance polymer solar cells. Here, we show operando direct observation of charge accumulation in PTB7:PC71BM blend solar cells from a microscopic viewpoint using electron spin resonance spectroscopy. The accumulation of ambipolar charges in the PTB7-based cells is directly observed for the first time, which shows a clear correlation with the performance deterioration during device operation. The sites of the ambipolar charge accumulation are elucidated at the molecular level, whose information would be useful for improving the cell durability in addition to the performance improvement.

New Mechanism for Ferroelectricity in the Perovskite Ca2-xMnxTi2O6 Synthesized by Spark Plasma Sintering.

Perovskite oxides hosting ferroelectricity are particularly important materials for modern technologies. The ferroelectric transition in the well-known oxides BaTiO3 and PbTiO3 is realized by softening of a vibration mode in the cubic perovskite structure. For most perovskite oxides, octahedral-site tilting systems are developed to accommodate the bonding mismatch due to a geometric tolerance factor t = (A-O)/[√2(B-O)] < 1. In the absence of cations having lone-pair electrons, e.g., Bi3+ and Pb2+, all simple and complex A-site and B-site ordered perovskite oxides with a t < 1 show a variety of tilting systems, and none of them become ferroelectric. The ferroelectric CaMnTi2O6 oxide is, up to now, the only one that breaks this rule. It exhibits a columnar A-site ordering with a pronounced octahedral-site tilting and yet becomes ferroelectric at Tc ≈ 650 K. Most importantly, the ferroelectricity at T < Tc is caused by an order-disorder transition instead of a displacive transition; this character may be useful to overcome the critical thickness problem experienced in all proper ferroelectrics. Application of this new ferroelectric material can greatly simplify the structure of microelectronic devices. However, CaMnTi2O6 is a high-pressure phase obtained at 7 GPa and 1200 °C, which limits its application. Here we report a new method to synthesize a gram-level sample of ferroelectric Ca2-xMnxTi2O6, having the same crystal structure as CaMnTi2O6 and a similarly high Curie temperature. The new finding paves the way for the mass production of this important ferroelectric oxide. We have used neutron powder diffraction to identify the origin of the peculiar ferroelectric transition in this double perovskite and to reveal the interplay between magnetic ordering and the ferroelectric displacement at low temperatures.

An Oligoimide Particle as a Pickering Emulsion Stabilizer.

A pyromellitic dianhydride (PMDA) and 4,4'-oxydianiline (ODA)-based oligoimide (PMDA-ODA) was synthesized by a one-step procedure using water as a solvent. The PMDA-ODA particles showed excellent partial wetting properties and were stably dispersed in both water and oil phases. A stable dispersion was not obtained with comparison PMDA-ODA particles that were synthesized by a conventional two-step method using an organic solvent. Both oil-in-water and water-in-oil Pickering emulsions were prepared using the oligoimide particles synthesized in water, and the size of the emulsion droplet was controlled based on the oligoimide particle concentration. The oligoimide particles were tested to prepare Pickering emulsions using various kinds of oils. The oil-in-water Pickering emulsions were successfully applied to prepare microcapsules of the emulsion droplets. Our new Pickering emulsion stabilizer has the advantages of easy synthesis, no need for surface modification, and the capability of stabilizing both oil-in-water and water-in-oil emulsions.

Significantly enhanced photoluminescence and thermal stability of La3Si8N11O4:Ce3+,Tb3+ via the Ce3+ → Tb3+ energy transfer: a blue-green phosphor for ultraviolet LEDs.

A series of Ce3+-, Tb3+- and Ce3+/Tb3+-doped La3Si8N11O4 phosphors were synthesized by gas-pressure sintering (GPS). The energy transfer between Ce3+ and Tb3+ occurred in the co-doped samples, leading to a tunable emission color from blue to green under the 360 nm excitation. The energy transfer mechanism was controlled by the dipole-dipole interaction. The Ce3+/Tb3+ co-doped sample had an external quantum efficiency of 46.7%, about 5.6 times higher than the Tb-doped La3Si8N11O4 phosphor (8.3%). The thermal quenching of the Tb3+ emission in La3Si8N11O4:Tb,Ce was greatly reduced from 74 to 30% at 250 °C, owing to the energy transfer from Ce3+ to Tb3+. The blue-green La3Si8N11O4:0.01Ce,0.05Tb phosphor was testified to fabricate a warm white LED that showed a high color rendering index of 90.2 and a correlated color temperature of 3570 K. The results suggested that the co-doped La3Si8N11O4:Ce,Tb phosphor could be a potential blue-green down-conversion luminescent material for use in UV-LED pumped wLEDs.

Synthesis and Photoluminescence Properties of a Blue-Emitting La3Si8N11O4:Eu2+ Phosphor.

Eu2+-doped La3Si8N11O4 phosphors were synthesized by the high temperature solid-state method, and their photoluminescence properties were investigated in this work. La3Si8N11O4:Eu2+ exhibits a strong broad absorption band centered at 320 nm, spanning the spectral range of 300-600 nm due to 4f7 → 4f65d1 electronic transitions of Eu2+. The emission spectra show a broad and asymmetric band peaking at 481-513 nm depending on the Eu2+ concentration, and the emission color can be tuned in a broad range owing to the energy transfer between Eu2+ ions occupying two independent crystallographic sites. Compared to the Ce3+-doped La3Si8N11O4, the Eu2+-doped one shows a larger thermal quenching, predominantly owing to photoionization. Under 320 nm excitation, the internal and external quantum efficiencies are 44 and 33%, respectively.

Transition of Emission Colours as a Consequence of Heat-Treatment of Carbon Coated Ce3+-Doped YAG Phosphors.

To modify the luminescence properties of Ce3+-doped Y3Al5O12 (YAG) phosphors, they have been coated with a carbon layer by chemical vapor deposition and subsequently heat-treated at high temperature under N2 atmosphere. Luminescence of the carbon coated YAG:Ce3+ phosphors has been investigated as a function of heat-treatment at 1500 and 1650 °C. The 540 nm emission intensity of C@YAG:Ce3+ is the highest when heated at 1650 °C, while a blue emission at 400-420 nm is observed when heated at 1500 °C but not at 1650 °C. It is verified by X-ray diffraction (XRD) that the intriguing luminescence changes are induced by the formation of new phases in C@YAG:Ce3+-1500 °C, which disappear in C@YAG:Ce3+-1650 °C. In order to understand the mechanisms responsible for the enhancement of YAG:Ce3+ emission and the presence of the blue emission observed for C@YAG:Ce3+-1500 °C, the samples have been investigated by a combination of several electron microscopy techniques, such as HRTEM, SEM-CL, and SEM-EDS. This local and cross-sectional analysis clearly reveals a gradual transformation of phase and morphology in heated C@YAG:Ce3+ phosphors, which is related to a reaction between C and YAG:Ce3+ in N2 atmosphere. Through reaction between the carbon layer and YAG host materials, the emission colour of the phosphors can be modified from yellow, white, and then back to yellow under UV excitation as a function of heat-treatment in N2 atmosphere.

Low-Temperature Self-Healing of a Microcapsule-Type Protective Coating.

Low-temperature self-healing capabilities are essential for self-healing materials exposed to cold environments. Although low-temperature self-healing concepts have been proposed, there has been no report of a microcapsule-type low-temperature self-healing system wherein the healing ability was demonstrated at low temperature. In this work, low-temperature self-healing of a microcapsule-type protective coating was demonstrated. This system employed silanol-terminated polydimethylsiloxane (STP) as a healing agent and dibutyltin dilaurate (DD) as a catalyst. STP underwent a condensation reaction at -20 °C in the presence of DD to give a viscoelastic product. The reaction behavior of STP and the viscoelasticity of the reaction product were investigated. STP and DD were separately microencapsulated by in situ polymerization and interfacial polymerization methods, respectively. The STP- and DD-loaded microcapsules were mixed into a commercial enamel paint, and the resulting formulation was applied to glass slides, steel panels, and mortars to prepare self-healing coatings. When the self-healing coatings were damaged at a low temperature (-20 °C), STP and DD were released from broken microcapsules and filled the damaged area. This process was effectively visualized using a fluorescent dye. The self-healing coatings were scratched and subjected to corrosion tests, electrochemical tests, and saline solution permeability tests. The temperature of the self-healing coatings was maintained at -20 °C before and after scratching and during the tests. We successfully demonstrated that the STP/DD-based coating system has good low-temperature self-healing capability.

Out-of-Plane Piezoelectricity and Ferroelectricity in Layered α-In2Se3 Nanoflakes.

Piezoelectric and ferroelectric properties in the two-dimensional (2D) limit are highly desired for nanoelectronic, electromechanical, and optoelectronic applications. Here we report the first experimental evidence of out-of-plane piezoelectricity and ferroelectricity in van der Waals layered α-In2Se3 nanoflakes. The noncentrosymmetric R3m symmetry of the α-In2Se3 samples is confirmed by scanning transmission electron microscopy, second-harmonic generation, and Raman spectroscopy measurements. Domains with opposite polarizations are visualized by piezo-response force microscopy. Single-point poling experiments suggest that the polarization is potentially switchable for α-In2Se3 nanoflakes with thicknesses down to ∼10 nm. The piezotronic effect is demonstrated in two-terminal devices, where the Schottky barrier can be modulated by the strain-induced piezopotential. Our work on polar α-In2Se3, one of the model 2D piezoelectrics and ferroelectrics with simple crystal structures, shows its great potential in electronic and photonic applications.

Microcapsule-Type Self-Healing Protective Coating for Cementitious Composites with Secondary Crack Preventing Ability.

A microcapsule-type self-healing protective coating with secondary crack preventing capability has been developed using a silanol-terminated polydimethylsiloxane (STP)/dibutyltin dilaurate (DD) healing agent. STP undergoes condensation reaction in the presence of DD to give a viscoelastic substance. STP- and DD-containing microcapsules were prepared by in-situ polymerization and interfacial polymerization methods, respectively. The microcapsules were characterized by Fourier-transform infrared (FT-IR) spectroscopy, optical microscopy, and scanning electron microscopy (SEM). The microcapsules were integrated into commercial enamel paint or epoxy coating formulations, which were applied on silicon wafers, steel panels, and mortar specimens to make dual-capsule self-healing protective coatings. When the STP/DD-based coating was scratched, self-healing of the damaged region occurred, which was demonstrated by SEM, electrochemical test, and water permeability test. It was also confirmed that secondary crack did not occur in the healed region upon application of vigorous vibration to the self-healing coating.

Mo6 cluster-based compounds for energy conversion applications: comparative study of photoluminescence and cathodoluminescence.

We report the photoluminescence (PL) and cathodoluminescence (CL) properties of face-capped [Mo6Xi8La6]2- (X = Cl, Br, I; L = organic or inorganic ligands) cluster units. We show that the emission of Mo6 metal atom clusters depends not only on the nature of X and L ligands bound to the cluster and counter-cations, but also on the excitation source. Seven members of the AxMo6Xi8La6 series (A = Cs+, (n-C4H9)4N+, NH4+) were selected to evaluate the influence of counter-cations and ligands on de-excitation mechanisms responsible for multicomponent emission of cluster units. This study evaluates the ageing of each member of the series, which is crucial for further energy conversion applications (photovoltaic, lighting, water splitting, etc.).

Low-energy Cathodoluminescence for (Oxy)Nitride Phosphors.

Nitride and oxynitride (Sialon) phosphors are good candidates for the ultraviolet and visible emission applications. High performance, good stability and flexibility of their emission properties can be achieved by controlling their composition and dopants. However, a lot of work is still required to improve their properties and to reduce the production cost. A possible approach is to correlate the luminescence properties of the Sialon particles with their local structural and chemical environment in order to optimize their growth parameters and find novel phosphors. For such a purpose, the low-voltage cathodoluminescence (CL) microscopy is a powerful technique. The use of electron as an excitation source allows detecting most of the luminescence centers, revealing their luminescence distribution spatially and in depth, directly comparing CL results with the other electron-based techniques, and investigating the stability of their luminescence properties under stress. Such advantages for phosphors characterization will be highlighted through examples of investigation on several Sialon phosphors by low-energy CL.

Grassy Silica Nanoribbons and Strong Blue Luminescence.

Silicon dioxide (SiO2) is one of the key materials in many modern technological applications such as in metal oxide semiconductor transistors, photovoltaic solar cells, pollution removal, and biomedicine. We report the accidental discovery of free-standing grassy silica nanoribbons directly grown on SiO2/Si platform which is commonly used for field-effect transistors fabrication without other precursor. We investigate the formation mechanism of this novel silica nanostructure that has not been previously documented. The silica nanoribbons are flexible and can be manipulated by electron-beam. The silica nanoribbons exhibit strong blue emission at about 467 nm, together with UV and red emissions as investigated by cathodoluminescence technique. The origins of the luminescence are attributed to various defects in the silica nanoribbons; and the intensity change of the blue emission and green emission at about 550 nm is discussed in the frame of the defect density. Our study may lead to rational design of the new silica-based materials for a wide range of applications.

Chemical Amination via Cycloaddition of Graphene for Use in a Glucose Sensor.

Graphene was chemically aminated via cycloaddition. Aziridine-ring linkages were formed by covalently modifying the C-C double bonds in graphene. The aminated graphene presents an enhanced hydrophilicity, the contact angle with water decreases from 80.5 degrees to 58.5 degrees. And the conductivity of aminated graphene exhibits exponential decay as the reaction time increase. If the reaction time is 90 min, the resistance of aminated graphene was increased from -32 Ω to -2744 Ω. Because the amino group has good biocompatibility, the aminated graphene is designed for use as an enzyme sensor platform, such as glucose sensor based on glucose oxidase. The aminated graphene exhibited a good detection response for glucose. The increase in device current is about 12% in 1.2 mg/mL glucose solution.