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Abstract Pyridazine derivatives hold significant interest due to their broad applications in pharmaceuticals and materials science, where they serve as valuable scaffolds for bioactive compounds and functional materials. Here, we report a formal [4 + 2] reaction for the synthesis of 5’-sulfonyl-4’-aryl-3-cyano substituted pyridazine compounds from the reaction between vinylogous enaminonitriles and sulfonyl hydrazides. The key features of our pyridazine synthesis include the transamidation of vinylogous enaminonitriles with sulfonyl hydrazide, radical sulfonylation of the resulting intermediate, and subsequent 6-endo-trig radical cyclization. This reaction proceeds smoothly to deliver a series of pyridazine derivatives in good to high yields. We also found that the sulfonyl group of the synthesized pyridazines can be transformed into C-, O-, or N-containing functional groups. A gram-scale experiment and a diverse transformation of synthesized pyridazines were also performed to validate the practicality of our developed process. In the synthesis of sulfonyl-substituted pyridazines, a 6-endo-trig cyclization via a radical pathway is both kinetically and thermodynamically favored over the cyclization via an ionic pathway, as supported by DFT calculations.

Purpose: This study reports on the effectiveness of using animated computer graphics to teach submicroscopic level science to secondary school (Form One) students. Method: A total of fifty-three secondary school (Form One) students of average spatial ability were selected to participate in this study. Three topics involving concepts at the submicroscopic level were identified in the Form One Science syllabus. Based on these topics, static graphics were prepared. The same static graphics were then animated using Adobe Flash. The animation was prepared in two versions, slow-motion mode and fast-motion mode. The respondents were given six lessons, two lessons for each topic. The first lesson was taught using static graphics and in the following lesson, the same content was taught again but with animated graphics instead. A pretest and a posttest were carried out at the beginning and at the end of each lesson respectively. The pre-test and post-test, consisting twenty true or false questions served as the instruments for assessing students' understanding. Analysis of the test scores was carried out by calculating the average difference in test scores between the pretests and posttests for the three topics taught. Findings: The analysis showed that when students were taught using static graphics, test scores increased by an average of 10% from pretest to posttest. When students were taught using animated graphics, test scores increased by an average of 30%. Hence, teaching Science using animated graphics was effective in enhancing students' understanding of the content taught. Significance: Animated computer graphics can be utilized as an effective tool in the teaching of submicroscopic level Science. For Form One students, slow-motioned animations help to enhance students' understanding of the content taught.

Extensive research has been conducted on hydrocarbon-based ionomers and membranes with high ionic conductivity and chemical stability for next-generation anion exchange membrane fuel cells (AEMFCs). However, it is well known that the benzene groups of hydrocarbon-based ionomers seriously poison the active sites of Pt catalysts, thereby reducing hydrogen oxidation reaction (HOR) activity and AEMFC performance. Over the past years, the development of benzene-tolerant catalysts has mainly focused on metal alloy nanoparticles such as PtRu, without pursuing the design of breakthrough catalyst structures that can more effectively reduce benzene poisoning. Here, we introduce an anti-poisoning catalyst structure promoted by the synergistic effect of carbon shell encapsulation and metal alloying. The porous carbon shell encapsulating the metal nanoparticles is expected to prevent direct adsorption of benzene groups, while the alloying of Pt and Ru can reduce the benzene adsorption energy itself. Comparative electrochemical analysis results confirm that the carbon shell-encapsulated metal alloy catalyst significantly alleviate benzene poisoning, exhibiting superior HOR activity than the conventional alloys in benzyltrimethylammonium hydroxide (BTMAOH) solution.

Abstract Chemotherapy-induced drug resistance remains a major cause of cancer recurrence and patient mortality. ATP binding cassette subfamily B member 1 (ABCB1) transporter overexpression in tumors contributes to resistance, yet current ABCB1 inhibitors have been unsuccessful in clinical trials. To address this challenge, we propose a new strategy using tryptophan as a lead molecule for developing ABCB1 inhibitors. Our idea stems from our studies on bat cells, as bats have low cancer incidences and high ABCB1 expression. We hypothesized that potential ABCB1 substrates in bats could act as competitive inhibitors in humans. By molecular simulations of ABCB1-substrate interactions, we generated a benzylated Cyclo-tryptophan (C3N-Dbn-Trp2) that inhibits ABCB1 activity with efficacy comparable to or better than the classical inhibitor, verapamil. C3N-Dbn-Trp2 restored chemotherapy sensitivity in drug-resistant human cancer cells with no adverse effect on cell proliferation. Our unique approach presents a promising lead toward developing effective ABCB1 inhibitors to treat drug-resistant cancers.

Exposure models for some criteria of air pollutants have been intensively developed in past research; multi-air-pollutant exposure models, especially for particulate chemical species, have been however overlooked in Asia. Lack of an integrated model framework to calculate multi-air-pollutant exposure has hindered the combined exposure assessment and the corresponding health assessment. This work applied the land-use regression (LUR) approach to develop an integrated model framework to estimate 2017 annual-average exposure of multiple air pollutants in a typical high-rise and high-density Asian city (Hong Kong, China) including four criteria of gaseous air pollutants (particulate matter with an aerodynamic diameter equal to or less than 10 µm (PM10) and 2.5 µm (PM2.5), nitrogen dioxide (NO2), and ozone (O3)), as well as four major PM10 chemical species. Our integrated multi-air-pollutant exposure model framework is capable of explaining 91 %–97 % of the variability of measured gaseous air pollutant concentration, with the leave-one-out cross-validation R2 values ranging from 0.73 to 0.93. Using the model framework, the spatial distribution of the concentration of various air pollutants at a spatial resolution of 500 m was generated. The LUR model-derived spatial distribution maps revealed weak-to-moderate spatial correlations between the PM10 chemical species and the criteria of air pollutants, which may help to distinguish their independent chronic health effects. In addition, further improvements in the development of air pollution exposure models are discussed. This study proposed an integrated model framework for estimating multi-air-pollutant exposure in high-density and high-rise urban areas, serving an important tool for multi-air-pollutant exposure assessment in epidemiological studies.

The core@shell nanostars composed of star-like Au nanocores with TiO2 shells (Au@TiO2 NSs) are synthesized in a one-pot reaction without any reducing or surface-controlling agents. The Au@TiO2 NSs exhibit strong absorption in the UV region based on the interaction between the Au nanocore and the TiO2 shell, and this optochemical property leads to the efficient laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS) analysis of small molecules with low background interference and high reproducible mass signals compared with spherical Au nanoparticles (NPs). The limit of detection and dynamic range values of various analytes also improved with Au@TiO2 NSs compared with those obtained with spherical Au NPs. Our findings successfully demonstrate that Au@TiO2 NSs are a promising matrix for the LDI-TOF-MS analysis of various small molecules as well as synthetic polymers.

Nowadays, mobile–mobile interaction is becoming a fundamental methodology for human–human networking services since mobile devices are the most common interfacing equipment for recent smart services such as food delivery, e-commerce, ride-hailing, etc. Unlike legacy ways of human interaction, on-site and in-person mutual recognition between a service provider and a client in mobile–mobile interaction is not trivial. This is because of not only the avoidance of face-to-face communication due to safety and health concerns but also the difficulty of matching up the online user using mobiles with the real person in the physical world. So, a novel mutual recognition scheme for mobile–mobile interaction is highly necessary. This paper comes up with a novel cyber-physical secure communication scheme relying on the digital twin paradigm. The proposed scheme designs the digital twin networking architecture on which real-world users form digital twins as their own online abstraction, and the digital twins authenticate each other for a smart service interaction. Thus, inter-twin communication (ITC) could support secure mutual recognition in mobile–mobile interaction. Such cyber-physical authentication (CPA) with the ITC is built on the dynamic BLE beaconing scheme with accurate proximity detection and dynamic identifier (ID) allocation. To achieve high accuracy in proximity detection, the proposed scheme is conducted using a wide variety of data pre-processing algorithms, machine learning technologies, and ensemble techniques. A location-dependent ID exploited in the CPA is dynamically generated by the physical user for their own digital twin per each mobile service.

Abstract Objectives Polo-like kinase 1 (Plk1) is an important mitotic protein. In particular, this protein is highly overexpressed in many types of tumors and has been identified as a potential biomarker for the treatment and diagnosis of tumors. Plk1 is composed of two domains, an N-terminal kinase domain and a C-terminal polo-box domain (PBD). Presently, inhibitors with improved selectivity and specificity for Plk1 are unavailable. Therefore, we aimed to develop an inhibitor targeting the C-terminal PBD present only in Plk1. Methods & results In this study, three derivatives targeting PBD for Plk1 were designed by protein–protein interactions, which showed high levels of selectivity and specificity for Plk1 PBD, and were evaluated to inhibit tumor cell proliferation through an apoptotic process during tumor cell division. The investigation of the in vitro and in vivo antitumor effects of these inhibitors demonstrated that one of the new small molecules, 1, is a promising anticancer agent. Conclusion Our findings can provide new insights for the design of novel Plk1 peptide inhibitors in the future.

Abstract Solution-based processable high-k 2-dimensional (2D) ferroelectrics have attracted significant interest for use in next-generation nanoelectronics. Although few studies on potential 2D ferroelectric nanosheets in local areas have been conducted, reports on the thin-film characteristics applicable to the device are insufficient. In this study, we successfully synthesize high-k 2D Sr1.8Bi0.2Nan-3NbnO3n+1 (octahedral units, n = 3–5) nanosheets by the engineering of the n of NbO6 octahedral layers with A-site modification, and realized ferroelectric characteristics in ultrathin films (below 10 nm). The nanosheets are synthesized by a solution-based cation exchange process and deposited using the Langmuir-Blodgett (LB) method. As increasing the NbO6 octahedral layer, the thickness of the nanosheets increased and the band gaps are tuned to 3.80 eV (n = 3), 3.76 eV (n = 4), and 3.70 eV (n = 5). In addition, the dielectric permittivity of the 5-layer stacked nanofilm increase to 26 (n = 3), 33 (n = 4), and 62 (n = 5). In particular, the increased perovskite layer exhibits large distortions due to the size mismatch of Sr/Bi/Na ions at the A-site and promotes local ferroelectric instability due to its spontaneous polarization along the c-axis caused by an odd n number. We investigate the stable ferroelectricity in Pt/ 5-layer Sr1.8Bi0.2Na2Nb5O16 / Nb:STO capacitor by polarization-electric field (P-E) hysteresis; the coercive electric field (Ec) was 338 kV cm−1 and the remnant polarization (Pr) 2.36 μC cm−2. The ferroelectric properties of ultrathin 2D materials could drive interesting innovations in next-generation electronics.

Porosification of fluoride can be effectively utilized in various applications, based on its abundance of exposed active sites. However, previous approaches have drawbacks in terms of application in fields that require meticulous control over porosity. Herein, an innovative strategy is suggested for achieving precise porosity tuning using a micelle‐carried MgF2 precursor intermediate. As the size of the MgF2 precursor clusters increases through micellization, the sizes of the resulting solidified MgF2 grains and the intergranular voids between the grains increase. Controlled MgF2 with intergranular voids can achieve very low‐refractive indices (≈1.04) with extremely fine refractive index control intervals (0.01–0.04). By employing extreme controllability of refractive index, graded refractive index antireflective coating is applied to the quartz window, and an average transmittance of ≈97.96% (250–1100 nm) is obtained. Finally, the coating is applied to a perovskite half‐cell enabling a ≈22.46% increase in the light‐absorption efficiency.

In this study, the effects of organic acid-soaking (malic, citric, tartaric, and succinic acid) and sonication on the formation of flavor and α-dicarbonyl compounds in Robusta (C. canephora syn. Coffea robusta) green beans were investigated. A total of 20 volatile compounds were identified in Robusta coffee. Furfural and 5-methyl furfural, two dominant volatile compounds in Arabica coffee, increased after organic acid pretreatment. In Robusta coffee processed from 3% malic acid-soaked coffee beans, furfural and 5-methyl furfural increased by 90.99% and 24.92%, respectively, compared to the control. In Robusta coffee processed from 3% malic acid-sonicated (280 W, 1 h) coffee beans, furfural and 5-methyl furfural increased by 236.03% and 114.77%, respectively. α-Dicarbonyls (glyoxal, methylglyoxal, and diacetyl) were significantly (p

This study examined the effects of an extract of the green algae Codium fragile (hereafter referred to as CFE) on dextran sulfate sodium (DSS)-induced colitis. As the administration of CFE increased, the proliferation of Akkermansia muciniphila, which is a key player in metabolic and gastrointestinal disorders, also increased. After CFE administration for 10 weeks, acetic acid was identified as the major metabolite in mouse cecum and β-glucuronidase activity in mouse fecesdecreased. Further, CFE significantly alleviated the acute intestinal injury induced by DSS administration, including DAI score, colon length, and histological score. The experimental group also displayed indications of significantly lower neutrophil activity and inflammation. In conclusion, the protective effect of CFE against DSS colitis suggests its clinical use by IBD patients.

Herein, fluorinate silicon monoxide (SiO-F) is prepared by heat treatment of SiO with ammonium bifluoride (NH4HF2) at low temperatures to improve the cycling stability of SiO. The fluorination of SiO is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier-Transform infrared spectroscopy (FT-IR). The SiO-F exhibits higher initial discharge capacity, rate capability, and cycling stability than untreated SiO (pristine SiO). The superior electrochemical performances of the SiO-F are attributed to the formation of a LiF-rich solid electrolyte interphase (SEI) layer formed by the reaction between Li-ion and F-groups on the surface of SiO during the charge and discharge cycle.

This paper presents a method to design a path tracking controller with a constraint on tire slip angles under low-friction road conditions. On a low-friction road surface, a lateral tire force is easily saturated and decreases as a tire slip angle increases by a large steering angle. Under this situation, a path tracking controller cannot achieve its maximum performance. To cope with this problem, it is necessary to limit tire slip angles to a value where the maximum lateral tire force is achieved. The most commonly used controllers for path tracking, linear quadratic regulator (LQR) and model predictive control (MPC), are adopted as a controller design methodology. The control inputs of LQR and MPC are front and rear steering angles and control yaw moment, which have been widely used for path tracking. The constraint derived from tire slip angles is imposed on the steering angles of LQR and MPC. To fully verify the performance of the path tracking controller with the constraint on tire slip angles, a simulation is conducted on vehicle simulation software. From the simulation results, it is shown that the path tracking controller with the constraint on tire slip angles presented in this paper is quite effective for path tracking on low-friction road surface.

Tropospheric ozone (O3) is one of the most important air pollutants in China and is projected to continue to increase in the near future. O3 and vegetation closely interact with each other and such interactions may not only affect plant physiology (e.g., stomatal conductance and photosynthesis) but also influence the overlying meteorology and air quality through modifying leaf stomatal behaviors. Previous studies have highlighted China as a hotspot in terms of O3 pollution and O3 damage to vegetation. Yet, few studies have investigated the effects of O3–vegetation interactions on meteorology and air quality in China, especially in the light of recent severe O3 pollution. In this study, a two-way coupled land–atmosphere model was applied to simulate O3 damage to vegetation and the subsequent effects on meteorology and air quality in China. Our results reveal that O3 causes up to 16 % enhancement in stomatal resistance, whereby large increases are found in the Henan, Hebei, and Shandong provinces. O3 damage causes more than 0.6 µmol CO2 m−2 s−1 reductions in photosynthesis rate and at least 0.4 and 0.8 g C m−2 d−1 decreases in leaf area index (LAI) and gross primary production (GPP), respectively, and hotspot areas appear in the northeastern and southern China. The associated reduction in transpiration causes a 5–30 W m−2 decrease (increase) in latent heat (sensible heat) flux, which induces a 3 % reduction in surface relative humidity, 0.2–0.8 K increase in surface air temperature, and 40–120 m increase in boundary-layer height in China. We also found that the meteorological changes further induce a 2–6 ppb increase in O3 concentration in northern and south-central China mainly due to enhanced isoprene emission following increased air temperature, demonstrating that O3–vegetation interactions can lead to strong positive feedback that can amplify O3 pollution in China. Our findings emphasize the importance of considering the effects of O3 damage and O3–vegetation interactions in air quality simulations, with ramifications for both air quality and forest management.

Satellite aerosol retrievals have been a popular alternative to monitoring the surface-based PM2.5 concentration due to their extensive spatial and temporal coverage. Satellite-derived PM2.5 estimations strongly rely on an accurate representation of the relationship between ground-level PM2.5 and satellite aerosol optical depth (AOD). Due to the limitations of satellite AOD data, most studies have examined the relationship at a coarse resolution (i.e., ≥ 10 km); thus, more effort is still needed to better understand the relationship between “in situ” PM2.5 and AOD at finer spatial scales. While PM2.5 and AOD could have obvious temporal variations, few studies have examined the diurnal variation in their relationship. Therefore, considerable uncertainty still exists in satellite-derived PM2.5 estimations due to these research gaps. Taking advantage of the newly released fine-spatial-resolution satellite AOD data derived from the Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm and real-time ground aerosol and PM2.5 measurements, this study explicitly explored the relationship between PM2.5 and AOD as well as its plausible impact factors, including meteorological parameters and topography, in mainland China during 2019, at various spatial and temporal scales. The coefficient of variation, the Pearson correlation coefficient and the slope of the linear regression model were used. Spatially, stronger correlations mainly occurred in northern and eastern China, and the linear slope was larger on average in northern inland regions than in other areas. Temporally, the PM2.5–AOD correlation peaked at noon and in the afternoon, and reached a maximum in winter. Simultaneously, considering relative humidity (RH) and the planetary boundary layer height (PBLH) in the relationship can improve the correlation, but the effect of RH and the PBLH on the correlation varied spatially and temporally with respect to both strength and direction. In addition, the largest correlation occurred at 400–600 m primarily in basin terrain such as the Sichuan Basin, the Shanxi–Shaanxi basins and the Junggar Basin. MAIAC 1 km AOD can better represent the ground-level fine particulate matter in most domains with exceptions, such as in very high terrain (i.e., Tibetan Plateau) and northern central China (i.e., Qinghai and Gansu). The findings of this study have useful implications for satellite-based PM2.5 monitoring and will further inform the understanding of the aerosol variation and PM2.5 pollution status of mainland China.

The planetary boundary layer (PBL) governs the vertical transport of mass, momentum, and moisture between the surface and the free atmosphere, and thus the determination of PBL height (BLH) is recognized as crucial for air quality, weather, and climate analysis. Although reanalysis products can provide important insight into the global view of BLH in a seamless way, the BLH observed in situ on a global scale remains poorly understood due to the lack of high-resolution (1 or 2 s) radiosonde measurements. The present study attempts to establish a near-global BLH climatology at synoptic times (00:00 and 12:00 UTC) and in the daytime using high-resolution radiosonde measurements over 300 radiosonde sites worldwide for the period 2012 to 2019, which is then compared against the BLHs obtained from four reanalysis datasets, including ERA5, MERRA-2, JRA-55, and NCEP-2. The variations in daytime BLH exhibit large spatial and temporal dependence, and as a result the BLH maxima are generally discerned over the regions such as the western United States and western China, in which the balloon launch times mostly correspond to the afternoon. The diurnal variations in BLH are revealed with a peak at 17:00 local solar time (LST). The most promising reanalysis product is ERA5, which underestimates BLH by around 130 m as compared to radiosondes released during daytime. In addition, MERRA-2 is a well-established product and has an underestimation of around 160 m. JRA-55 and NCEP-2 might produce considerable additional uncertainties, with a much larger underestimation of up to 400 m. The largest bias in the reanalysis data appears over the western United States and western China, and it might be attributed to the maximal BLH in the afternoon when the PBL has risen. Statistical analyses further indicate that the biases of reanalysis BLH products are positively associated with orographic complexity, as well as the occurrence of static instability. To our best knowledge, this study presents the first near-global view of high-resolution radiosonde-derived boundary layer height and provides a quantitative assessment of the four frequently used reanalysis products.

This study analyzed the nature, mechanisms and drivers for hot-and-polluted episodes (HPEs) in the Pearl River Delta, China. Numerical model simulations were conducted for the summer and autumn of 2009–2011. A total of eight HPEs were identified, mainly occurring in August and September. K-means clustering was applied to group the HPEs into three clusters based on their characteristics and mechanisms. We found three HPEs were driven by weak subsidence and convection induced by approaching tropical cyclones (TC-HPE) and two HPEs were controlled by calm (stagnant) conditions (ST-HPE) with low wind speed in the lower atmosphere, whereas the remaining three HPEs were driven by the combination (hybrid) of both aforementioned systems (HY-HPE). A positive synergistic effect between the HPE and urban heat island (UHI; ∼ 1.1 ∘C increase) was observed in TC-HPE and ST-HPE, whereas no discernible synergistic effect was found in HY-HPE. Total aerosol radiative forcing (TARF) caused a reduction in temperature (0.5–1.0 ∘C) in TC-HPE and ST-HPE but an increase (0.5 ∘C) in HY-HPE.

Lanthanide-based supramolecular complexes have labile and hard-topredict chemical structures. Here the authors show controlled formation of either helicates or tetrahedron shaped cages based on the interplay between the metal ionic radius and the ligand composition.

Irreversible electroporation (IRE) is a recognized ablation technique that induces apoptosis via potent electric fields. Nonetheless, the heterogeneity of biological tissues often results in inconsistent treatment outcomes, leaving residual viable cells and leading to potential relapse. To address this, previous strategies incorporated chemical enhancers to IRE, but these faced limitations such as limited tissue diffusion and hyperpigmentation. In this study, we explore the synergistic application of near-infrared (NIR) irradiation with IRE. Using an in vivo rat gastric tissue model, we pre-irradiated samples with NIR at 3 J/cm2 prior to IRE. The combined treatment, termed NIRE, produced a change in tissue impedance of 13.5 Ohm compared to IRE alone, indicating NIR’s potential in modulating tissue electrical properties. Subsequent histopathological and molecular assessments revealed a 1.12-fold increase in apoptosis for NIRE over IRE. Notably, the apoptosis-related proteins BCL and p21 exhibited a 1.24-fold and 1.29-fold overexpression following NIRE treatment, respectively, emphasizing NIRE’s enhanced apoptotic activation. In essence, our findings underscore the augmented therapeutic efficacy of IRE when complemented with NIR, presenting a promising avenue for bolstering treatment outcomes in tissue ablation.

This study examined the eye movement patterns of 317 elementary students across reading conditions (audio-assisted reading (AR) and reading-only (R)) and text types (fiction and non-fiction) and identified eye movement parameters that predict their literal comprehension (LC) and inferential comprehension (IC). Participants, randomly assigned to either reading condition and either text type, answered questions assessing their LC and IC. Average fixation duration (AFD), total fixation duration (TFD), and scanpath length were used as eye movement parameters. The main effects of age were observed on all parameters, along with interaction effects between age and reading condition on TFD and scanpath length. These results indicate that children employ different reading strategies, depending on reading modalities and text types. When controlling for age, TFD had a positive impact on the LC of both text types in the AR, while in the R, it had a negative effect on the IC of both text types. Longer scanpaths predicted the IC of fiction in the AR; the LC and IC of non-fiction under the AR; and the LC of non-fiction within the R. AFD had a negative influence on the IC of fiction in the AR, as well as on the LC and IC of non-fiction in the AR, and the LC of non-fiction under the R. These findings highlight the importance of selecting appropriate reading strategies, based on reading modality and text type, to enhance reading comprehension. This study offers guidance for educators when providing reading instruction to school-age children.

Flow reactors have applications in reaction screening and optimisation, but typically operate in linear or radial configurations. Here a bench-top parallel flow synthesiser which distributes reagents between sixteen microreactors allows for rapid optimisation of chemical libraries, with uniform flow distribution even when clogging occurs.

Perovskite La2/3xLi3xTiO3 (LLTO) materials are promising solid-state electrolytes for lithium metal batteries (LMBs) due to their intrinsic fire-resistance, high bulk ionic conductivity, and wide electrochemical window. However, their commercialization is hampered by high interfacial resistance, dendrite formation, and instability against Li metal. To address these challenges, we first prepared highly dense LLTO pellets with enhanced microstructure and high bulk ionic conductivity of 2.1×10−4 S cm−1 at room temperature. Then, the LLTO pellets were coated with three polymer-based interfacial layers, including pure (polyethylene oxide) (PEO), dry polymer electrolyte of PEO-LITFSI (lithium bis (trifluoromethanesulfonyl) imide) (PL), and gel PEO-LiTFSI-SN (succinonitrile) (PLS). It is found that each layer has impacted the interface differently; the soft PLS gel layer significantly reduced the total resistance of LLTO to a low value of 84.88 Ω cm−2. Interestingly, PLS layer has shown excellent ionic conductivity but performs inferior in symmetric Li cells. On the other hand, the PL layer significantly reduces lithium nucleation overpotential and shows a stable voltage profile after 20 cycles without any sign of Li dendrite formation. This work demonstrates that LLTO electrolytes with denser microstructure could reduce the interfacial resistance and when combined with polymeric interfaces show improved chemical stability against Li metal.

To provide long-term air pollutant exposure estimates for epidemiological studies, it is essential to test the feasibility of developing land-use regression (LUR) models using only routine air quality measurement data and to evaluate the transferability of LUR models between nearby cities. In this study, we developed and evaluated the intercity transferability of annual-average LUR models for ambient respirable suspended particulates (PM10), fine suspended particulates (PM2.5), nitrogen dioxide (NO2) and ozone (O3) in the Taipei–Keelung metropolitan area of northern Taiwan in 2019. Ambient PM10, PM2.5, NO2 and O3 measurements at 30 fixed-site stations were used as the dependent variables, and a total of 156 potential predictor variables in six categories (i.e., population density, road network, land-use type, normalized difference vegetation index, meteorology and elevation) were extracted using buffer spatial analysis. The LUR models were developed using the supervised forward linear regression approach. The LUR models for ambient PM10, PM2.5, NO2 and O3 achieved relatively high prediction performance, with R2 values of > 0.72 and leave-one-out cross-validation (LOOCV) R2 values of > 0.53. The intercity transferability of LUR models varied among the air pollutants, with transfer-predictive R2 values of > 0.62 for NO2 and < 0.56 for the other three pollutants. The LUR-model-based 500 m × 500 m spatial-distribution maps of these air pollutants illustrated pollution hot spots and the heterogeneity of population exposure, which provide valuable information for policymakers in designing effective air pollution control strategies. The LUR-model-based air pollution exposure estimates captured the spatial variability in exposure for participants in a cohort study. This study highlights that LUR models can be reasonably established upon a routine monitoring network, but there exist uncertainties when transferring LUR models between nearby cities. To the best of our knowledge, this study is the first to evaluate the intercity transferability of LUR models in Asia.

Abstract Background One of the most critical issues concerning in situ mass spectrometry lies in accounting for elements and molecules that overlap target isotopes of analytical interest in a sample. This study traced the instrumental mass fractionation of Rb and Sr isotopes during laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS) to obtain reliable 87Sr/86Sr ratios for high-Rb/Sr samples. Findings In the LA-MC-ICPMS analysis, Kr interferences were corrected using Ar and He gas blanks measured without ablating material. Contributions from doubly charged Er and Yb ions were corrected using the intensities of half masses and isotopic compositions reported in the literature. After Kr correction, the calculated 166Er2+ intensity of NIST SRM 610 approached the measured intensity at mass 83, and the 173Yb2+/171Yb2+ ratio agreed with the recommended value within error ranges. Kr- and REE2+-stripped peak intensities were further corrected for Rb interference. Use of the Sr mass bias factor for the calculation of measured 87Rb/85Rb yielded 87Sr/86Sr ratios consistent with the recommended and expected values for low-Rb/Sr materials, such as NIST SRM 616, modern shark teeth, and plagioclase collected from Jeju Island, but failed to account for the 87Rb interference from high-Rb/Sr materials including NIST SRM 610 and SRM 612. We calculated in situ mass bias factor of Rb from the known 87Sr/86Sr ratios of the standards and observed a correlation between Rb and Sr mass fractionation, which allowed inference of the Rb bias from the standard run. Reliable 87Sr/86Sr and 85Rb/86Sr ratios were obtained for SRM 610 and SRM 612 using the inferred mass bias factor of Rb calculated by the standard bracketing method. Conclusions This study revealed that Rb and Sr isotopes behave differently during LA-MC-ICPMS and suggests the potential usefulness of the standard bracketing method for measuring the Rb–Sr isotopic compositions of high-Rb/Sr materials.

The Controller Area Network (CAN) is a widely used communication protocol in automobiles, but it is vulnerable to various types of attacks. To address this issue, researchers have been exploring the use of intrusion detection systems (IDS) for the CAN bus. Deep learning and machine learning have been proven to be powerful tools for detecting intrusions accurately and quickly. However, deep learning models require large amounts of data to achieve optimal performance, which can be challenging in the case of a CAN bus IDS. To overcome this challenge, we propose a novel machine learning-based IDS called CANPerFL that uses a personalized federated learning scheme to aggregate datasets from different car models. By building a universal model trained on a small amount of data from each manufacturer, we can provide global knowledge that can be transferred to improve the performance of each participant. To demonstrate the efficiency of the proposed model, we collected a real CAN dataset consisting of three different car models: KIA, BMW, and Tesla. The experimental results show that the proposed model increases F1 scores by 4% overall, compared to baselines. Moreover, the proposed system provides significant advantages when the local dataset of each participant is relatively small. According to our experiments, the proposed models can achieve F1 scores of more than 90% with at least 30k training samples on each client. Finally, we show empirically that each participant takes benefits from joining the CANPerFL system.

During the implementation of a crypto system, distributed cryptographic libraries are unable to endure situations where the execution environment rapidly changes because of a structural vulnerability that is by design. For this reason, Microsoft announced a CNG library to solve this problem; however, the CNG does not comprise verification tools regarding the execution results for developers, users, or experts to assess the crypto system. In addition, the CNG design means that it is difficult to ensure that the encryption or decryption keys can be found in real-time processing because almost all cryptographic functions are processed by handles. This paper analyzes the way that key information is found to assure the security of the implemented products or to debug them in the development process. For this reason, we analyze the key storage mechanism of asymmetric-key-related functions in the CNG library. This study provides more convenient ways to identify key-related information, such as debugging and evaluation, when a crypto system is implemented using the CNG library.

Owing to multiple physicochemical properties, the combination of hybrid elemental compositions of nanoparticles can be widely utilized for a variety of applications. To combine pristine tellurium nanorods, which act as a sacrificing template, with another element, iridium–tellurium nanorods (IrTeNRs) were synthesized via the galvanic replacement technique. Owing to the coexistence of iridium and tellurium, IrTeNRs exhibited unique properties, such as peroxidase-like activity and photoconversion. Additionally, the IrTeNRs demonstrated exceptional colloidal stability in complete media. Based on these properties, the IrTeNRs were applied to in vitro and in vivo cancer therapy, allowing for the possibility of multiple therapeutic methodologies. The enzymatic therapy was enabled by the peroxidase-like activity that generated reactive oxygen species, and the photoconversion under 473, 660 and 808 nm laser irradiation induced cancer cell apoptosis via photothermal and photodynamic therapy.

Elucidation of the molecular mechanism of therapeutic agents and potential candidates is in high demand. Interestingly, rhenium-based complexes have shown a highly selective anticancer effect, only on cancer cells, unlike platinum-based drugs, such as cisplatin and carboplatin. These differences might be attributed to their different molecular targets. We confirmed that the target of tricarbonyl rhenium isonitrile polypyridyl (TRIP) complex is a protein, not DNA, using ICP-MS analysis and identified heat shock protein 60 (HSP60) as its target protein using a label-free target identification method. The subsequent biological evaluation revealed that TRIP directly inhibits the chaperone function of HSP60 and induces the accumulation of misfolded proteins in mitochondria, thereby leading to the activation of mitochondrial unfolded protein response (mtUPR)-mediated JNK2/AP-1/CHOP apoptotic pathway.

This paper proposes an S/X-band single-layer shared-aperture array antenna for the multifunction radars of military ships. A unit cell of the proposed antenna consists of one S-band element and four X-band elements. The S- and X-band elements are printed on the same layer to prevent a blockage effect by upper elements in the stacked shared-aperture antenna. Herein, the S-band element has a mutual complementary configuration for the X-band elements. In addition, the unit cell of the proposed antenna is designed in a symmetrical structure, which can be flexibly extended to a full array configuration. To verify the antenna feasibility, antenna performances are measured in a full anechoic chamber. The fractional bandwidths of the S- and X-band elements are 13.6% and 13.4%, respectively. Moreover, in the 2 × 2 array configuration, the S-band array gain in the bore-sight direction varies from 5.4 dBi to 3.5 dBi when the main beam is steered from 0° to 45°. Under the same conditions, the measured X-band array gain in the bore-sight direction decreases from 13.4 dBi to 11.6 dBi.

According to the Fire-eye’s M-Trends Annual Threat Report 2022, there are many advanced persistent threat (APT) attacks that are currently in use, and such continuous and specialized APT attacks cause serious damages attacks. As APT attacks continue to be active, there is a need for countermeasures to detect new and existing malicious codes. An APT attack is a type of intelligent attack that analyzes the target and exploits its vulnerabilities. It attempts to achieve a specific purpose, and is persistent in continuously attacking and threatening the system. With this background, this paper analyzes attack scenarios based on attack cases by malicious code, and surveys and analyzes attack techniques used in attack cases. Based on the results of the analysis, we classify and analyze malicious code detection techniques into security management systems, pattern-based detection, heuristic-based detection, reputation-based detection, behavior-based detection, virtualization-based detection, anomaly detection, data analysis-based detection (big data-based, machine learning-based), and others. This paper is expected to serve as a useful reference for detecting and preventing malicious codes. Specifically, this article is a surveyed review article.

A torrential rainfall case, which happened in Guangdong Province during 14–16 December 2013, broke the historical rainfall record in the province in terms of duration, affected area, and accumulative precipitation. The influence of anthropogenic aerosols on this extreme rainfall event is examined using a coupled meteorology–chemistry–aerosol model. Up to 33.7 mm precipitation enhancement in the estuary and near the coast is mainly attributed to aerosol–cloud interactions (ACI), whereas aerosol–radiation interaction partially offsets 14 % of the precipitation increase. Our further analysis of changes in hydrometeors and latent heat sources suggests that the ACI effects on the intensification of precipitation can be divided into two stages: cold rain enhancement in the former stage followed by warm rain enhancement in the latter. Responses of precipitation to the changes in anthropogenic aerosol concentration from local (i.e., Guangdong Province) and remote (i.e., outside Guangdong Province) sources are also investigated through simulations with reduced aerosol emissions from either local or remote sources. Accumulated aerosol concentration from local sources aggregates mainly near the ground surface and dilutes quickly after the precipitation initiated. By contrast, the aerosols from remote emissions extend up to 8 km above ground and last much longer before decreasing until peak rainfall begins, because aerosols are continuously transported by the strong northerly winds. The patterns of precipitation response to remote and local aerosol concentrations resemble each other. However, compared with local aerosols through warm rain enhancement, remote aerosols contribute more than twice the precipitation increase by intensifying both cold and warm rain, occupying a predominant role. A 10-time emission sensitivity test shows about 10 times the PM2.5 concentration compared with the control run. Cold (warm) rain is drastically enhanced (suppressed) in the 10× run. In response to 10× aerosol emissions, the pattern of precipitation and cloud property changes resembles the differences between CTL and CLEAN, but with a much greater magnitude. The precipitation average over Guangdong decreases by 1.0 mm in the 10× run but increases by 1.4 mm in the control run compared with the CLEAN run. We note that the precipitation increase is concentrated within a more narrowed downstream region of the aerosol source, whereas the precipitation decrease is more dispersed across the upstream region. This indicates that the excessive aerosols not only suppress rainfall, but also change the spatial distribution of precipitation, increasing the rainfall range, thereby potentially exacerbating flood and drought elsewhere. This study highlights the importance of considering aerosols in meteorology to improve extreme weather forecasting. Furthermore, aerosols from remote emissions may outweigh those from local emissions in the convective invigoration effect.

Numerous studies have reported that ambient air pollution, which has both local and long-range sources, causes adverse impacts on the environment and human health. Previous studies have investigated the impacts of transboundary air pollution (TAP) in East Asia, albeit primarily through analyses of episodic events. In addition, it is useful to better understand the spatiotemporal variations in TAP and the resultant impact on the environment and human health. This study aimed at assessing and quantifying the air quality impacts in Japan and South Korea due to local emissions and TAP from sources in East Asia - one of the most polluted regions in the world. We applied state-of-the-science atmospheric models to simulate air quality in East Asia and then analyzed the air quality and acid deposition impacts of both local emissions and TAP sources in Japan and South Korea. Our results show that ∼ 30 % of the annual average ambient PM2.5 concentrations in Japan and South Korea in 2010 were contributed to by local emissions within each country, while the remaining ∼ 70 % were contributed to by TAP from other countries in the region. More detailed analyses also revealed that the local contribution was higher in the metropolises of Japan (∼ 40 %–79 %) and South Korea (∼ 31 %–55 %) and that minimal seasonal variations in surface PM2.5 occurred in Japan, whereas there was a relatively large variation in South Korea in the winter. Further, among all five studied anthropogenic emission sectors of China, the industrial sector represented the greatest contributor to annual surface PM2.5 concentrations in Japan and South Korea, followed by the residential and power generation sectors. Results also show that TAP's impact on acid deposition (SO42- and NO3-) was larger than TAP's impact on PM2.5 concentrations (accounting for over 80 % of the total deposition), and that seasonal variations in acid deposition were similar for both Japan and South Korea (i.e., higher in both the winter and summer). Finally, wet deposition had a greater impact on mixed forests in Japan and savannas in South Korea. Given these significant impacts of TAP in the region, it is paramount that cross-national efforts should be taken to mitigate air pollution problems across East Asia.

Abstract Early detection and accurate diagnosis are essential for the effective prevention and treatment of tumors. Optical imaging methods can provide real-time and high-resolution in vivo images for tumor diagnostic applications. Pro-Leu-His-Ser-Thr(PO3H2) (PLHSpT) is an inhibitor of polo-like kinase 1, which is overexpressed in various tumors, and the transactivator of transcription (TAT) is a peptide known to penetrate tumor cells. In this study, we used a fragment of the TAT sequence, YARVRRRGPRR, to produce a YARVRRRGPRR-conjugated PLHSpT peptide using solid-phase peptide synthesis. Subsequently, the cyanine 5 NHS ester (Cy5) fluorescent dye was attached to YARVRRRGPRRPLHSpT (1) to obtain the Cy5-YARVRRRGPRRPLHSpT peptide (2), which was used to identify tumor targets through optical imaging. 2 was injected into HeLa xenograft tumor-bearing mice. After in vivo imaging at 3 h, 6 h, and 24 h post-injection, mice were sacrificed for ex vivo fluorescence intensity assessment. Optical imaging scans of 2 revealed significantly high uptake by tumor cells at all in vivo scan times. The highest fluorescence intensity difference between tumor and muscles was observed at 6 h. Ex vivo results also showed a high variation in the tumor-to-muscle uptake ratios at 6 h. In conclusion, we synthesized and evaluated 2 for cancer diagnosis in mice. Our optical imaging results demonstrated that 2 has remarkable cancer-detection ability in vivo, establishing this peptide as a potential imaging probe for tumor diagnosis.

Hydrogen fuel cell electric vehicles are emerging as a means of transportation using renewable and carbon-free energy due to global warming and air pollution. Hydrogen fuel cell electric vehicles are typically refueled at a wide range of temperatures (−40 °C to 85 °C) in hydrogen refueling stations in accordance with globally accepted standards. Currently, there is no traceable method by which to verify and calibrate the Coriolis mass flowmeters used at hydrogen refueling stations, except for a water calibration process as a conventional method for mass flowrate calibration. To verify the hydrogen flow metering to a suitable level of accuracy under the challenging condition of high pressures and a wide range of temperatures, necessary methodologies and calibration facilities are developed in the present study. A flow measurement characteristic test of the hydrogen mass flowmeter under identical density conditions of the refueled hydrogen was conducted using the high-pressure gas flow standard system of the Korea Research Institute of Standards and Science to assess the effects on the medium and pressure of the mass flowmeter in a density-matching approach. To investigate the pressure dependence of the mass flowmeter at a hydrogen refueling station, a high-pressure water flow test was conducted in the pressure range of 2 bar to 700 bar, which is a pressure-matching approach. Finally, the KRISS Hydrogen Field Test Standard based on the gravimetric principle was developed to verify the measurement accuracy of the mass flowmeter to be used at hydrogen refueling stations for the first time in Korea.

Herein is described the introduction of lipid moieties onto a simplified teixobactin pharmacophore using a modified Cysteine Lipidation on a Peptide or Amino acid (CLipPA) technique, whereby cysteine was substituted for 3-mercaptopropionic acid (3-MPA). A truncated teixobactin analog was prepared with the requisite thiol handle, thus enabling an array of vinyl esters to be conveniently conjugated onto the simplified teixobactin pharmacophore to yield S-lipidated cyclic lipopeptides.

Background. The treatment of coronary stenosis is decided by performing high risk invasive surgery to generate the fractional flow reserve diagnostics index, a ratio of distal to proximal pressures in respect of coronary atherosclerotic plaques. Non-invasive methods are a need of the times that necessitate the use of mathematical models of coronary hemodynamic physiology. This study proposes an extensible mathematical description of the coronary vasculature that provides an estimate of coronary fractional flow reserve. Methods. By adapting an existing computational model of human coronary blood flow, the effects of large vessel stenosis and microvascular disease on fractional flow reserve were quantified. Several simulations generated flow and pressure information, which was used to compute fractional flow reserve under several conditions including focal stenosis, diffuse stenosis, and microvascular disease. Sensitivity analysis was used to uncover the influence of model parameters on fractional flow reserve. The model was simulated as coupled non-linear ordinary differential equations and numerically solved using our implicit higher order method. Results. Large vessel stenosis affected fractional flow reserve. The model predicts that the presence, rather than severity, of microvascular disease affects coronary flow deleteriously. Conclusions. The model provides a computationally inexpensive instrument for future in silico coronary blood flow investigations as well as clinical-imaging decision making. A combination of focal and diffuse stenosis appears to be essential to limit coronary flow. In addition to pressure measurements in the large epicardial vessels, diagnosis of microvascular disease is essential. The independence of the index with respect to heart rate suggests that computationally inexpensive steady state simulations may provide sufficient information to reliably compute the index.

The cities of Chengdu, Deyang, and Mianyang in the northwest Sichuan Basin are part of a rapidly developing urban agglomeration adjoining the eastern slopes of the Tibetan Plateau. Heavy air pollution events have frequently occurred over these cities in recent decades, but the effects of meteorological conditions on these pollution events are unclear. We explored the effects of weather systems on winter heavy air pollution from 1 January 2006 to 31 December 2012 and from 1 January 2014 to 28 February 2017. A total of 10 heavy air pollution events occurred during the research period and 8 of these took place while the region was affected by a dry low-pressure system at 700 hPa. When the urban agglomeration was in front of the low-pressure system and the weather conditions were controlled by a warm southerly air flow, a strong temperature inversion appeared above the atmospheric boundary layer acting as a lid. Forced by this strong inversion layer, the local secondary circulation was confined to the atmospheric boundary layer, and the horizontal wind speed in the lower troposphere was low. As a result, vertical mixing and horizontal dispersion in the atmosphere were poor, favoring the formation of heavy air pollution events. After the low-pressure system had transited over the region, the weather conditions in the urban agglomeration were controlled by a dry and cold air flow from the northwest at 700 hPa. The strong inversion layer gradually dissipated, the secondary circulation enhanced and uplifted, and the horizontal wind speed in the lower troposphere also increased, resulting in a sharp decrease in the concentration of air pollutants. The strong inversion layer above the atmospheric boundary layer induced by the low-pressure system at 700 hPa thus played a key role in the formation of heavy air pollution during the winter months in this urban agglomeration. This study provides scientific insights for forecasting heavy air pollution in this region of China.

Severe haze events in Southeast Asia caused by particulate pollution have become more intense and frequent in recent years. Widespread biomass burning occurrences and particulate pollutants from human activities other than biomass burning play important roles in degrading air quality in Southeast Asia. In this study, numerical simulations have been conducted using the Weather Research and Forecasting (WRF) model coupled with a chemistry component (WRF-Chem) to quantitatively examine the contributions of aerosols emitted from fire (i.e., biomass burning) versus non-fire (including fossil fuel combustion, and road dust, etc.) sources to the degradation of air quality and visibility over Southeast Asia. These simulations cover a time period from 2002 to 2008 and are driven by emissions from (a) fossil fuel burning only, (b) biomass burning only, and (c) both fossil fuel and biomass burning. The model results reveal that 39 % of observed low-visibility days (LVDs) can be explained by either fossil fuel burning or biomass burning emissions alone, a further 20 % by fossil fuel burning alone, a further 8 % by biomass burning alone, and a further 5 % by a combination of fossil fuel burning and biomass burning. Analysis of an 24 h PM2.5 air quality index (AQI) indicates that the case with coexisting fire and non-fire PM2.5 can substantially increase the chance of AQI being in the moderate or unhealthy pollution level from 23 to 34 %. The premature mortality in major Southeast Asian cities due to degradation of air quality by particulate pollutants is estimated to increase from ∼ 4110 per year in 2002 to ∼ 6540 per year in 2008. In addition, we demonstrate the importance of certain missing non-fire anthropogenic aerosol sources including anthropogenic fugitive and industrial dusts in causing urban air quality degradation. An experiment of using machine learning algorithms to forecast the occurrence of haze events in Singapore is also explored in this study. All of these results suggest that besides minimizing biomass burning activities, an effective air pollution mitigation policy for Southeast Asia needs to consider controlling emissions from non-fire anthropogenic sources.

Continuous control of blood glucose levels is important for the effective treatment of diabetes. The short-term use of enzymatic continuous monitoring systems involves expensive maintenance and is inconvenient, which limits their widespread use by diabetes patients. The fluorescent diboronic anthracene-embedded system has demonstrated in vivo continuous glucose monitoring for 12 times longer than enzymatic systems by protecting the dye from reactive oxygen species. However, its small Stokes shift and low excitation and emission wavelength should be heavily considered for easy fabrication. We successfully synthesized a derivative of bis-phenyl boronate with a large Stokes shift and long excitation wavelength by adding an acetyl moiety to the anthracene ring. This resulted in a ~90-nm Stokes shift and 15-nm and 80-nm redshifts of the excitation and emission wavelengths, respectively. The fluorescence of the synthesized probe increased proportionally with the glucose concentration because the formation of the boronic acid-glucose complex prevented photoinduced electron transfer. The association constant and quantum yield for acetyl-substituted diboronic anthracene with glucose was 20% and 13% higher than that of the analog, respectively. While keeping resistance to the oxidation by reactive oxygen species, the improved optical properties and glucose-detecting performances of the newly synthesized dye will allow better pairing of the source and detecting unit for in vivo continuous glucose monitoring, leading to easy fabrication and then contributing more to utilization by diabetes patients.

The traces of carbon fibers along the cracked surfaces of mortar prisms, being 40 mm x 40 mm x 160 mm in size, are studied, assuming that the cracked surfaces in the prisms are the places with the lowest resistance to the stresses they are exposed to. This is to explain why the prisms with 1.0% carbon fibers in volume reveal higher flexural strength than those with 0.5%, 1.5% and 2.0% of fibers. Five distinctive traces of carbon fibers, such as uprootedness, avulsion, separation, overlay and dividedness are observed in the cracked surfaces. As the percentage increases by more than 1.0%, the number of the uprooted fibers reduces, while the numbers of the divided, avulsed and separated fibers increase. The percentage increase induces more fibers to be clustered together and overlap each other to make more divided, avulsed and separated fiber traces. At the same time, the fiber strands are mixed with the mortar to a greater extent. Consequently, the crack surfaces of the prisms with fiber percentages of 1.5% and 2.0% become mostly covered with fiber-laden mortar and cemented fiber clusters. Since the cemented fiber clusters work as air pockets of various volumes and act as the inhomogeneities together with the fiber-laden mortar, the cohesiveness of the mortar is greatly reduced. The deteriorating cohesiveness of the mortar and the increased inhomogeneity cause the reduction in the flexural strength of the prisms in comparison with those with 1.0% carbon fibers.

Estimation of the critical latency that can cause collision in remote maneuvering of autonomous ships can provide a clue to avoid collisions. The concept of estimating the critical latency was established using the turning circle formed by the turning maneuver of the own ship, and critical latency was estimated using the radius of the turning circle with the turning time ratio. The turning circle was observed using the turning trajectory of the give-way vessel measured in the ship maneuvering simulation experiment. Experimental results demonstrated that the proposed method is capable of identifying both the location and time of the collision due to critical latency. As a result, a clue to avoid possible collision in remote maneuvering caused by critical latency was deduced.