Initial Deposition Research Articles

Achieving stable lithium metal anode via constructing lithiophilicity gradient and regulating Li3N-rich SEI

Three-dimensional (3D) current collectors are studied for the application of Li metal anodes in high-energy battery systems. However, they still suffer from the preferential accumulation of Li on the outermost surface, resulting from an inadequate regulation of the Li+ transport. Herein, we propose a deposition regulation strategy involving the creation of a 3D lithiophilicity gradient structure of MoN on Cu3N nanowire-grown Cu foam (MCNCF) to induce a “bottom-up” Li deposition. During the initial Li deposition, the reaction between Li and Cu3N leads to the formation of Li3N while the lithiophilic MoN located at the bottom promotes the downward Li+ migration, resulting in the generation of a Li3N gradient. Such a “bottom-up” Li3N distribution results in the formation of a stable and Li3N-rich solid electrolyte interphase layer, facilitating the Li⁺ transport and promoting a uniform Li nucleation. Computational simulations and experimental results corroborate the preferential deposition of Li on the bottom of the substrate, leading to a uniform Li nucleation and growth throughout the electrode. The MCNCF electrode offers a significantly improved reversibility of the Li deposition, achieving a lifespan of more than 1200 h at a current density of 1 mA cm−2 in symmetric Li||Li cells. Furthermore, full-cells incorporating MCNCF@Li as the negative electrode and LiFePO4 cathodes exhibit outstanding electrochemical performance with a capacity retention of over 99.5 % after 250 cycles at 1 C, which significantly surpasses the performance achieved with CF@Li or CCF@Li electrodes. This innovative design strategy for 3D metallic current collectors, featuring a lithiophilicity gradient, provides new perspectives for the development of stable Li metal anodes and, as a result, for the advancement of Li-metal batteries.

Ambient pressure x-ray photoelectron spectroscopy study on the initial atomic layer deposition process of platinum

The initial adsorption of MeCpPtMe3 is investigated using synchrotron-based ambient pressure x-ray photoelectron spectroscopy (XPS). The experiments are done on a native oxide-covered Si substrate. In addition, a reaction with O2 and the created Pt surface was investigated. Inspiration for the reaction studies was found from atomic layer deposition of metallic Pt, process that uses the same compounds as precursors. With time-resolved XPS, we have been able to observe details of the deposition process and especially see chemical changes on the Pt atoms during the initial deposition of the Pt precursor. The change of the binding energy of the Pt 4f core level appears to occur on a different timescale than the growth of the active surface sites. The very long pulse of the Pt precursor resulted in a metallic surface already from the beginning, which suggest chemical vapor deposition-like reactions occurring between the surface and the precursor molecules in this experiment. Additionally, based on the XPS data measured after the Pt precursor pulse, we can make suggestions for the reaction pathway, which point toward a scenario that leaves carbon from the MeCpPtMe3 precursor on the surface. These carbon species are then efficiently removed by the subsequent coreactant pulse, leaving behind a mostly metallic Pt film.

Grey correlation analysis of the main influencing factors of wax deposition of waxy crude oil and determination of pigging period based on dynamic analysis

Normal temperature gathering and transportation has significant advantages in reducing energy consumption and cost. Due to the high wax content of crude oil in carbonate reservoirs, obvious wax deposition will occur in the process of gathering and transportation at room temperature. In this paper, according to the component analysis results of crude oil on site, the HEATANALOGY wax deposition model was used to calculate the wax deposition of different gathering pipelines. The main influencing factors of wax deposition were analyzed by grey correlation method. Finally, according to the pigging mechanical balance model, the safe pigging period is derived, and the relationship diagram of different pipe diameters, throughput and ground temperature is drawn. The results show that the wellhead temperature has the greatest influence on the initial wax deposition position and the peak wax deposition position of the pipe section. The flow rate has the greatest influence on the maximum wax deposition thickness of the tube wall. According to the relationship between the working conditions and the pigging cycle, it can be found that with the increase of the throughput, the pigging cycle decreases first and then increases. With the increase of ground temperature, the pigging cycle increases.

Significant role of secondary electrons in the formation of a multi-body chemical species spur produced by water radiolysis.

Scientific insights into water photolysis and radiolysis are essential for estimating the direct and indirect effects of deoxyribonucleic acid (DNA) damage. Secondary electrons from radiolysis intricately associated with both effects. In our previous paper, we simulated the femtosecond (1 × 10- 15s) dynamics of secondary electrons ejected by energy depositions of 11-19eV into water via high-energy electron transport using a time-dependent simulation code. The results contribute to the understanding of simple "intra-spur" chemical reactions of tree-body chemical species (hydrated electrons, hydronium ion and OH radical) in subsequent chemical processes. Herein, we simulate the dynamics of the electrons ejected by energy depositions of 20-30eV. The present results contribute to the understanding of complex "inter-spur" chemical reactions of the multi-body chemical species as well as for the formation of complex DNA damage with redox site and strand break on DNA. The simulation results present the earliest formation mechanism of an unclear multi-body chemical species spur when secondary electrons induce further ionisations or electronic excitations. The formation involves electron-water collisions, i.e. ionisation, electronic excitation, molecular excitation and elastic scattering. Our simulation results indicate that (1) most secondary electrons delocalise to ~ 12nm, and multiple collisions are sometimes induced in a water molecule at 22eV deposition energy. (2) The secondary electrons begin to induce diffuse band excitation of water around a few nm from the initial energy deposition site and delocalise to ~ 8nm at deposition energies ~ 25eV. (3) The secondary electron can cause one additional ionisation or electronic excitation at deposition energies > 30eV, forming a multi-body chemical species spur. Thus, we propose that the type and density of chemical species produced by water radiolysis strongly depend on the deposition energy. From our results, we discuss formation of complex DNA damage.

Isotope Encoded chemical Imaging Identifies Amyloid Plaque Age Dependent Structural Maturation, Synaptic Loss, and Increased Toxicity.

It is of critical importance to our understanding of Alzheimer's disease (AD) pathology to determine how key pathological factors are interconnected and implicated in nerve cell death, clinical symptoms, and disease progression. The formation of extracellular beta-amyloid (Aβ) plaques is the major pathological hallmark of AD and Aβ has been suggested to be a critical inducer of AD, driving disease pathogenesis. Exactly how Aβ plaque formation begins and how ongoing plaque deposition proceeds and initiates subsequent neurotoxic mechanisms is not well understood. The primary aim of our research is to elucidate the biochemical processes underlying early Aβ plaque formation in brain tissue. We recently introduced a chemical imaging paradigm based on mass spectrometry imaging (MSI) and metabolic isotope labelling to follow stable isotope labelling kinetics (iSILK) in vivo to track the in vivo build-up and deposition of Aβ. Herein, knock-in Aβ mouse models ( App NL-F ) that develop Aβ pathology gradually are metabolically labeled with stable isotopes. This chemical imaging approach timestamps amyloid plaques during the period of initial deposition allowing the fate of aggregating Aβ species from before and during the earliest events of plaque pathology through plaque maturation to be tracked. To identify the molecular and cellular response to plaque maturation, we integrated iSILK with single plaque transcriptomics performed on adjacent tissue sections. This enabled changes in gene expression to be tracked as a function of plaque age (as encoded in the Aβ peptide isotopologue pattern) distinct from changes due to the chronological age or pathological severity. This approach identified that plaque age correlates negatively with gene expression patterns associated with synaptic function as early as in 10-month-old animals but persists into 18 months. Finally, we integrated hyperspectral confocal microscopy into our multiomic approach to image amyloid structural isomers, revealing a positive correlation between plaque age and amyloid structural maturity. This analysis identified three categories of plaques, each with a distinct impact on the surrounding microenvironment. Here, we identified that older, more compact plaques were associated with the most significant synapse loss and toxicity. These data show how isotope-encoded MS imaging can be used to delineate Aβ toxicity dynamics in vivo. Moreover, we show for the first time a functional integration of dynamic MSI, structural plaque imaging and whole genome-wide spatial transcriptomics at the single plaque level. This multiomic approach offers an unprecedented combination of temporal and spatial resolution enabling a description of the earliest events of precipitating amyloid pathology and how Aβ modulates synaptotoxic mechanisms.

Tailoring Lithium Horizontal Deposition for Long-Lasting High-Loading NCA (≥5 mA h cm-2)||Lithium-Metal Full Cells in Carbonate Electrolytes.

We report a design for a synergistic lithium (Li) metal hosting layer for high-loading Li(Ni,Co,Al)O2 (NCA) (≥5 mA h cm-2)||Li-metal full cells in carbonate electrolytes. Based on density functional theory calculations, the hosting layer was designed as a three-dimensional silver/carbon composite nanofiber (Ag/CNF) network with high Li affinity and a platinum (Pt)-coated polypropylene separator with low Li affinity. This design enabled the tailoring of horizontal Li deposition on the Ag/CNF hosting layer. The Li deposition behavior modulated by the hosting layer was thoroughly examined based on the initial Li deposition and cycling behaviors of the Li||Li symmetric cell configuration. Cryogenic focused-ion beam cross-sectional images of the cycled Li anodes clearly demonstrated that dense lithium deposition was enabled by the synergistic hosting layer high-loading NCA (≥5 mA h cm-2)||Li-metal full cells. When the hosting layer was used, the average cycling performance improved by 78.27% under various cycling conditions. Our work demonstrates that the synergistic hosting layer design is a fruitful pathway to accelerate the commercialization of high-energy-density Li-metal batteries in carbonate electrolytes.

Variable preservation of the 1991 Hudson tephra in small lakes and on land

Volcanic ash (tephra) preserved in terrestrial environments and lake sediments contains information about volcanic processes and can be used to infer eruptive parameters and frequency of past eruptions, contributing to the understanding of volcanic hazards. However, tephra deposits can undergo transformation from their initial fallout sedimentation to being preserved as a tephra layer in the sedimentary record. The process is likely to be different in lakes and in terrestrial (soil) sequences. Here we compare the thickness, mass loading and grain size of tephra layers from the 1991 eruption of Cerro Hudson, Chile, from small lakes and adjacent terrestrial settings to measurements of the tephra made shortly after the eruption. We analysed samples from 35 cores in total from six small lakes (<0.25 km2), located 76 and 109 km from the volcano in two contrasting climatic areas (cool and humid northern site, and warm and dry southern site), and made 73 measurements of tephra thickness and 11 measurements of grain size in adjacent terrestrial areas. The major element geochemistry of our samples confirmed they were from the 1991 Hudson eruption. We found that some of the measured characteristics of the preserved tephra layers were comparable to those recorded in 1991 shortly after initial deposition, but that there was considerable variability within and between locations. This variability was not predictable and lake sediments did not preserve a notably more accurate record of the fallout than terrestrial sites. However, in aggregate the characteristics of the preserved tephra was similar to those recorded at the time of deposition, suggesting that, for palaeotephra research, a sampling strategy involving a wide range of environments is more robust than one that relies on a single sedimentary record or a single type of sedimentary environment.

Growth of single crystalline GeSn alloy epilayer on Gd2O3/Si (111) engineered insulating substrate using RF sputtering and solid phase epitaxy

The article showcases a low-cost, low-temperature deposition andHVMtechnique to develop single crystalline GeSn alloy epilayers on Gd2O3/Si (111) substrate. First, GeSn alloy amorphous layer is deposited on the insulating substrates using an Radio Frequency (RF) sputtering apparatus. Subsequently, an inductively coupled plasma-assisted chemical vapor deposition (ICP-CVD) process is used to deposit a SiO2 capping layer to protect against Sn out-diffusion during heat treatment. The samples are then subjected to solid phase epitaxy (SPE) at 450 °C, 550 °C, and 650 °C. Sample processed for SPE at 450 °C has weak crystallinity and only shows Type-A stacking. Those processed for SPE at 550 °C and 650 °C, on the other hand, have revealed formation of the single-crystalline GeSn alloy epilayer with Type-A and Type-B stacking. However, SPE at 650 °C revealed tin out-diffusion and segregation effects. This work is significant for enabling the preparation of high-Sn-content GeSn alloy epilayers on insulating Gd2O3/Si (111) substrates, as it requires the initial deposition of a GeSn amorphous alloy epilayer using RF sputtering. This advancement promises benefits which includes advantages such as lower operating voltage, reduced leakage current, and minimized parasitic and short-channel effects, making it ideal for advancing RF technology.

Assessment of Machine Learning Techniques for Simulating Reacting Flow: From Plasma-Assisted Ignition to Turbulent Flame Propagation

Combustion involves the study of multiphysics phenomena that includes fluid and chemical kinetics, chemical reactions and complex nonlinear processes across various time and space scales. Accurate simulation of combustion is essential for designing energy conversion systems. Nonetheless, due to its multiscale, multiphysics nature, simulating these systems at full resolution is typically difficult. The massive and complex data generated from experiments and simulations, particularly in turbulent combustion, presents both a challenge and a research opportunity for advancing combustion studies. Machine learning facilitates data-driven techniques to manage the substantial amount of combustion data that is either obtained through experiments or simulations, and thereby can find the hidden patterns underlying these data. Alternatively, machine learning models can be useful to make predictions with comparable accuracy to existing models, while reducing computational costs significantly. In this era of big data, machine learning is rapidly evolving, offering promising opportunities to explore its integration with combustion research. This work provides an in-depth overview of machine learning applications in turbulent combustion modeling and presents the application of machine learning models: Decision Trees (DT) and Random Forests (RF), for the spatio-temporal prediction of plasma-assisted ignition kernels, based on the initial degree of ionization, with model validations against DNS data. The results demonstrate that properly trained machine learning models can accurately predict the spatio-temporal ignition kernel profile based on the initial energy deposition and distribution.

Historical vegetation shifts in southeastern Amazonia: Unraveling ecotone dynamics in the Carajás region over the last ∼14000 cal yr BP

This study investigates the Pleistocene–Holocene transition in Serra Leste, a highly endangered southeastern Amazonian ecotone, with a focus on the lake-filling process, climate changes, and potential consequences to forest and savanna dynamics. The lake's development began at approximately 14000 cal yr BP, resulting from the collapse of the fractured lateritic crust. Sedimentation patterns and geochemical, palynological and micro-charcoal proxies reveal shifts in detrital input and redox conditions, forest/savanna areas, and local and regional fire events, indicating a highly dynamic environmental history. The evolution of the lake is characterized by initial deltaic lobe deposition and forest dominance, followed in the Middle Holocene by sedimentary gaps or reduced detrital input; woody vegetation dominance, with a notable shift toward a more open landscape; and savanna and semideciduous dry forest, accompanied by a decrease in ombrophilous forests. A resurgence in arboreal elements recorded in the Late Holocene indicates an expansion of ombrophilous forests under wetter climate conditions and the establishment of a more continuous forest matrix, with the presence of likely “hyperdominant” taxa. Frequent local fire events and the occurrence of temporarily correlated archeological sites in the Serra Leste region suggest the influence of ancient indigenous communities on vegetation changes during the Late Holocene.

Observations on the reproductive morphology of the female short-beaked echidna, Tachyglossus aculeatus.

Although monotremes diverged from the therian mammal lineage approximately 187 million years ago, they retain various plesiomorphic and/or reptilian-like anatomical and physiological characteristics. This study examined the morphology of juvenile and adult female reproductive tracts across various stages of the presumptive oestrous cycle, collected opportunistically from cadaver specimens submitted to wildlife hospitals during the breeding season. In adult females, ovaries had a convoluted cortex with follicles protruding from the ovarian surface. While protruding antral follicles were absent from the ovaries of juvenile echidnas, histological analysis identified early developing primordial and primary follicles embedded into the ovarian cortex. The infundibulum epithelial cells of the oviducts were secretory during the follicular phase but not at other stages, the ampulla region was secretory at all stages and is likely responsible for the mucoid layer deposited around the zona pellucida, and the isthmus region of the oviduct appeared to be responsible for initial deposition of the shell coat, as in marsupials. Female echidnas have two separate uteri, which never merge and enter separately into the urogenital sinus (UGS). This study confirmed that both uteri are functional and increase in glandular activity during the luteal phase. In the juvenile uteri, the endometrium was immature with minimal, small uterine glands. A muscular cervical region at the caudal extremity of each uterus, just before the cranial region of the UGS was defined by the absence of glandular tissue in all female echidnas, including the juveniles. There was no evidence of a definitive vaginal region. A clitoris was also detected that possessed a less developed but similar structural (homologous) anatomy to the male penis; urethral ducts while present did not appear to be patent.

Molecular Dynamics Analysis of Multi-Factor Influences on Structural Defects in Deposited Mg-Matrix Zn Atom Films.

Mg metal vascular stents not only have good mechanical support properties but also can be entirely absorbed by the human body as a trace element beneficial to the human body, but because Mg metal is quickly dissolved and absorbed in the human body, magnesium metal alone cannot be ideally used as a vascular stent. Since the dense oxide Zn film formed by Zn contact with oxygen in the air has good anti-corrosion performance, the Zn nanolayer film deposited on the Mg matrix vascular scaffold by magnetron sputtering can effectively inhibit the rapid dissolution of Mg metal. However, there are few studies on the molecular dynamic structural defects of Mg-matrix Zn atomic magnetron sputtering, and the atomic level simulation of Mg-matrix Zn thin-film depositions can comprehensively understand the atomic level structural defects in the deposition process of Zn thin films from a theoretical perspective to further guide experimental research. Based on this, this research first studied and analyzed the atomic layer structure defects, surface morphology, surface roughness, atomic density of different deposited layers, radial distribution function, and residual stress of the thin-film deposition layer of 1500 deposited Zn atoms at the initial deposition stage, during and after deposition under Mg-matrix thermal layer 500K and a deposited velocity 5 Å/ps by molecular dynamics. At the same time, the effects of temperature and deposited velocity of the Mg-matrix thermal layer on the surface morphology, roughness, and biaxial stress of the deposited films were studied.

Dissipation Kinetics, Decontamination and Safety Evaluation of Quinalphos Residues in Cauliflower Curd.

A field experiment was conducted to study the persistence and reduction of quinalphos residues in cauliflower curd by applying quinalphos 25 EC twice at 250g a.i./ha at 10 days intervals. The limit of quantification (LOQ) was 0.05µg/g, recovery ranged from 97 to 113%, and the relative standard deviation was less than 7%. The initial deposition of quinalphos residues in cauliflower curd was 1.72µg/g and reached below LOQ level after 15 days of application. Dissipation of the residue followed first-order kinetics with a half-life of 2.32 days. The reduction of quinalphos residue was evaluated using various household processes. The greatest reduction (82%) was observed when washing was followed by cooking or boiling, while the smallest reduction (55.8%) was found when washing alone was performed. A waiting period of 9 days is recommended for safe consumption of cauliflower based on the FSSAI MRL value of 0.1µg/g.

Towards enhanced corrosion resistance of PS-PVD TBCs in marine environments by structural design

Thermal barrier coatings (TBCs) prepared by plasma spray-physical vapor deposition (PS-PVD) applied in marine environments encounter a critical challenge of corrosion-induced failure. In this paper, yttria-stabilized zirconia (YSZ) TBCs with different microstructures were prepared via PS-PVD by varying powder feeding rates to investigate the influence of microstructural modifications on corrosion resistance. The effects of structural gradient, initial deposition mechanism, and pore distribution on corrosion resistance were explored. Additionally, the inhibition mechanisms of capillary effect and chemical reaction on molten salt penetration were confirmed. Finally, a microstructure gradient strategy for PS-PVD TBCs was proposed. The structurally graded TBCs tailored using this strategy exhibited excellent corrosion resistance, with the molten salt corrosion resistance surpassing that of conventionally processed PS-PVD TBC by over 50 %. These outcomes highlight the promising potential of the microstructure gradient strategy for enhancing the corrosion resistance of PS-PVD TBCs.

Phase-field modeling of lithium dendrite deposition process: When an internal short circuit occurs

Lithium dendrite growth is the main trigger for internal short circuits (ISC) of lithium-ion batteries. This paper investigates the lithium dendrite growth during the whole short circuit evolution process. In this paper, the lithium dendrite growth is divided into the initial deposition of the initial operation and the secondary deposition due to the internal short circuit. Firstly, a two-dimensional model based on the phase-field theory is developed and the growth in static electrolyte is investigated. Secondly, we summarize the whole evolution process and analyze the internal structural changes as well as the external features due to the internal short circuit. Based on this analysis, a model of secondary deposition in a flowing electrolyte is proposed. The model takes into account the effect of the flowing electrolyte on the dendrites. Finally, we investigate the growth of dendrites during secondary deposition. Due to an internal short circuit that damages the separator, a flowing electrolyte appears around the damaged region. This flowing electrolyte leads to uneven growth of dendrites, with “splitting” and “branch inhibition”. This phenomenon will accelerate the continued deposition of dendrites and induce a secondary internal short circuit. This work provides a quantitative simulation model for dendrite growth when an ISC occurs. Moreover, it also provides a reference for designing the structure of liquid batteries with high cycle times and safety.

Skin deposition and permeation kinetics of cannabidiol and delta-9-tetrahydrocannabinol from cannabis extract containing gels

The study aimed to investigate the deposition and permeation characteristics of phytocannabinoids, namely delta-9-tetrahydrocannabinol (THC) and cannabidiol (CBD), from cannabis extract containing gels. Cannabis extract with 26.3 % CBD and 28.4 % THC was used. The impact of permeation enhancers, namely propylene glycol, diethylene glycol monoethyl ether (DEGEE), ethanol (EtOH), and terpenes (eucalyptol and menthol), was examined. All cannabis extract gels had a pH range of 6.71–6.81 and a viscosity range of 456.6–4068.7 mPa⋅s. The phytocannabinoid release from the gels followed Zero-order kinetics with a rate of 14.5–25.7 μg⋅h−1 for CBD and 10.0−22.6 μg⋅h−1 for THC. A gel containing 12.5 % DEGEE and 12.5 % EtOH exhibited the highest release rate. The initial skin deposition followed Zero-order kinetics and reached a maximum level after 4 h. Permeation of phytocannabinoids closely followed Higuchi kinetics, with a rate of 0.14–54.21 μg⋅h−1/2 for CBD and 0.23−67.02 μg⋅h−1/2 for THC. A gel containing 25 % DEGEE and 25 % EtOH exhibited the highest apparent skin partition coefficient (K) value, resulting in the greatest phytocannabinoid deposition and permeation. Terpene introduction (5 %) significantly reduced the release rate, K value, and total skin absorption of phytocannabinoids. These findings offer useful insights into selecting the appropriate vehicle for cannabis extract topical products.

Abstract P374: Systolic blood pressure burden better predicts tau accumulation than a one-time measurement

In our past work, our group identified a significant relationship between uncontrolled hypertension and greater accumulations of total-tau and phospho-tau181 in cerebrospinal fluid over time. Here, we tested whether blood pressure is related to brain tau deposition assessed using MK-6240 PET. Blood pressure is dynamic in nature, making it difficult to draw conclusions about their risk from a single measurement. To address this issue, different measurement methods have surfaced to better utilize blood pressure as a predictor of disease pathology. Previous studies have found cumulative diastolic blood pressure to increase cardiovascular disease stratification beyond that of a single diastolic blood pressure measurement. In this project, we studied another method of quantifying blood pressure. We examined whether systolic blood pressure (SBP) burden was better related to tau accumulation than a one-time BP measurement taken at the time of PET scan. SBP load was defined as the percentage of SBP values >=140 mmHg taken in the period spanning from 6 months before tau imaging to 6 months after. SUVR (standardized uptake value ratio) was created using the cerebellar gray matter as the reference region. We assessed SUVR in Braak regions 1-6. Pearson correlation was used to test the associations between the variables of interest. We studied cognitively healthy subjects from a brain aging research center (n=72, 40% women, 60% with hypertension). Medians of our group were 72 years of age (interquartile range (IQR) 10.6), education of 18 years (IQR 2), and 8 BP measurements (IQR 14). While one-time SBP measurements and tau were not related, SBP load was progressively correlated with SUVR across Braak stages. In the entire group, the correlations ranged from -0.18 (p = 0.133) in Braak region 1 to 0.19 (p = 0.114) in Braak region 3 to 0.24 (p = 0.042) in Braak region 6. In the hypertensive group, these correlations were stronger and ranged from -0.06 (p = 0.713) in Braak region 1 to 0.38 (p = 0.012) in Braak region 3 to 0.50 (p < 0.001) in Braak region 6. We show that SBP load instead of singular SBP measurements is a stronger predictor of tau accumulation. Furthermore, stronger associations with brain regions known to be affected in more advanced stages suggest that blood pressure control is more critical to tau progression than initial deposition.

(Invited) Plasmonic Nanofabrication of Chiral Nanodisk Ensembles

Chiral plasmonic nanostructures attract attention because those could be applied to enantioselective chemical sensors, optical isolators, light sources for circularly polarized light (CPL), metasurfaces, and metamaterials. In many cases, chiral plasmonic nanostructures are fabricated by a top-down method such as electron beam lithography (EBL). Since EBL is time-consuming and expensive, we have developed photoelectrochemical methods in which a site-selective reaction is driven by optical near field generated around anisotropic metal nanoparticles under right- or left-CPL. As anisotropic metal precursors for preparation of chiral nanoparticles, we have used gold or silver nanocuboids, nanorods, nanocubes, and triangular or hexagonal nanoplates so far.1-5 In the present work we demonstrate that laterally isotopic, circular nanodisks can also be used as precursors for the preparation of chiral nanostructures.We prepared ensembles of circular gold nanodisks on a glass plate by a nanosphere lithography method. A glass plate was coated with a gold thin film, and an array of polystyrene spheres (500 nm diameter) was prepared on the gold film. The polystyrene spheres were etched by oxygen plasma, and the exposed gold film was etched by argon ion milling. As a result, an ensemble of gold nanodisks (~200 nm diameter) was obtained. Each nanodisk was capped with a polystyrene cone, and the cap was removed by sonication in toluene if necessary. We used both capped and uncapped nanodisk ensembles. The ensemble was irradiated with visible right- or left-CPL in the presence of silver ions and sodium citrate. The obtained Au-Ag nanostructures exhibited circular dichroism (CPL), indicating that the nanostructures have chirality. Initial deposition at arbitrary site may break the geometric symmetry, resulting in the growth into chiral structures. Saito, K.; Tatsuma, T. Nano Lett. 2018, 18, 3209–3212.Morisawa, K.; Ishida, T.; Tatsuma, T. ACS Nano 2020, 14, 3603–3609.Shimomura, K.; Nakane, Y.; Ishida, T.; Tatsuma, T. Appl. Phys. Lett. 2023, 122, 151109.Homma, T.; Sawada, N.; Ishida, T.; Tatsuma, T. ChemNanoMat 2023, 9, e202300096.Ishida, T.; Isawa, A.; Kuroki, S.; Kameoka, Y.; Tatsuma, T. Appl. Phys. Lett. 2023, 123, 061111.

Deposition, dissipation, metabolism, and dietary risk assessment of chlorothalonil on pakchoi

For the scientific application of chlorothalonil, a thorough understanding of chlorothalonil deposition, distribution, and dissipation on pakchoi is required so as to reduce its application dosage. In this study, the effects of the application dosage, application season, planting environment, initial deposition, field dissipation and metabolism of pakchoi were investigated. The chlorothalonil deposition amount gradually increased with increasing dosage and application frequency. The deposition law in each application strategy was leaf > edible parts > petiole > planting soil. The half-lives of chlorothalonil in pakchoi in May, October, and December were 2.86–5.79, 3.08–5.87, and 6.41–11.32 days, respectively. The deposition concentration and dissipation half-life of chlorothalonil in different parts of pakchoi and the planting soil in greenhouse environments were higher than those in open-field environments. The initial deposition concentration and half-life of chlorothalonil in pakchoi gradually decreased from north to south: Beijing >Hefei >Changsha in April and Hefei >Sanya in December. Chlorothalonil can be converted to metabolite I (C8HCl3N2O) in pakchoi plants, which can gradually dechlorinate to produce metabolite II (C8HCl3N2), metabolite III (C8H2Cl2N2), and metabolite IV (C8H3ClN2). Within an application interval of 7 days, the long-term consumption of pakchoi leaves and edible parts poses unacceptable dietary risks. This study improves chlorothalonil utilization rates and provides technical guidance for its scientific application in the pakchoi planting ecosystem.

Enhancement of Tricyclazole Analysis Efficiency in Rice Samples Using an Improved QuEChERS and Its Application in Residue: A Study from Unmanned Arial Spraying

Enhancements to the analytical method for the determination of tricyclazole in rice samples have been applied to monitor residues during unmanned aerial spraying. The acetonitrile extraction technique QuEChERS was improved by the incorporation of ethyl acetate and 0.1% formic acid, which significantly elevated the recovery rates. Furthermore, the purification process was refined by integrating both primary–secondary amine (PSA) and C18 in the dSPE method, achieving a substantial improvement in reducing matrix effects (MEs) and increasing recovery efficiency. The optimized method demonstrated an impressive % ME value at −3.1%, with a limit of quantitation (LOQ) established at 0.01 mg/kg, and recovery rates between 94.7 and 95.6% at 0.01, 0.1, and 2 mg/kg. Using two types of adjuvants (stickers) during multi-copter spraying markedly improved the initial tricyclazole deposition on rice panicles, with residue levels initially increasing from 0.35 mg/kg to between 0.68 and 1.60 mg/kg. Residues in hulled rice at harvest (10 days post-application) remained well below the maximum residue limit (MRL) of 0.7 mg/kg, ranging from 0.02 to 0.11 mg/kg, thus affirming the safety and efficacy of adjuvants in residue management.