Crystal-Structure Matches in Solid-Solid Phase Transitions.

The exploration of solid-solid phase transition suffers from the uncertainty of how atoms in two crystal structures match. We devised a theoretical framework to describe and classify crystal-structure matches (CSM). Such description fully exploits the translational and rotational symmetries and is independent of the choice of supercells. This is enabled by the use of the Hermite normal form, an analog of reduced echelon form for integer matrices. With its help, exhausting all CSMs is made possible, which goes beyond the conventional optimization schemes. In an example study of the martensitic transformation of steel, our enumeration algorithm finds many candidate CSMs with lower strains than known mechanisms. Two long-sought CSMs accounting for the most commonly observed Kurdjumov-Sachs orientation relationship and the Nishiyama-Wassermann orientation relationship are unveiled. Given the comprehensiveness and efficiency, our enumeration scheme provide a promising strategy for solid-solid phase transition mechanism research.

Precisely Controlled Polymerization of Two-Dimensional Conducting Polymers in Quasi-Liquid Layer Enables Ultrahigh Sensing Performance.

Gas sensors based on conducting polymers offer great potential for high-performance room temperature applications due to their cost-effectiveness, high-sensitivity, and operational advantage. However, their current performance is limited by the deficiency of control in conventional polymerization methods, leading to poor crystallinity and inconsistent material properties. Here, the quasi-liquid layer (QLL) on the ice surface acts as a self-regulating nano-reactor for precise control of thermodynamics and kinetics in the polymerization, resulting in a 7.62 nm thick two-dimensional (2D) polyaniline (PANI) film matching the QLL thickness. The ultra-thin film optimizes the exposure of active sites, enhancing the detection of analyte gases at low concentrations. It is validated by fabricating a chemiresistive gas sensor with the 2D PANI film, demonstrating stable room-temperature detection of ammonia down to 10 ppt in ambient air with an impressive 10% response. This achievement represents the highest sensitivity among sensors of this kind while maintaining excellent selectivity and repeatability. Moreover, the QLL-controlled polymerization strategy offers an alternative route for precise control of the polymerization process for conducting polymers, enabling the creation of advanced materials with enhanced properties.

Negative Poisson's ratio of sulfides dominated by strong intralayer electron repulsion.

Geometrical variations in a particular structure or other mechanical factors are often cited as the cause of a negative Poisson's ratio (NPR). These factors are independent of the electronic properties of the materials. This work investigates a class of two-dimensional (2D) sulfides with the chemical formula MX2 (M = Ti, Cr, Mn, Fe, Co, X = S) using first-principles calculations. Among them, monolayered TiS2, CrS2, and MnS2 were found to exhibit a structure-independent NPR. The strong strain response of intra-layer interactions is responsible for this unique phenomenon. This can be traced to the lone pair of electrons of the S atoms and the weak electronegativity of the central atoms in multi-orbital hybridization. Our study provides valuable insights and useful guidelines for designing innovative NPR materials.

Interfacial Electron Potential Well Facilitates the Design of Cobalt Phosphide Heterojunctions for Hydrogen Evolution.

The interfacial electron modulation of electrocatalysts is an effective way to realize efficient hydrogen production, which is of great importance for future renewable energy systems. However, systematic theory-guided design of catalysts in heterojunction coupling is lacking. In this work, a multi-level theoretical calculation is performed to screen optimal candidates to form a heterojunction with CoP (101) surface for electrocatalytic hydrogen production. To overcome the weak adsorption of H+ on CoP (101), rational design of electrons potential well at the heterojunction interface can effectively enhance the hydrogen adsorption. All p-type cobalt-based phosphides are considered potential candidates at the beginning. After screening for conductivity, stability, interface matching screening, and ΔGH* evaluation, the CoP/Co2 P-H system is identified to be able to display optimal hydrogen production performance. To verify the theoretical design, CoP, CoP/Co2 P-H, and CoP/Co2 P-O are synthesized and the electrochemical analysis is carried out. The hydrogen evolution reaction (HER) performance is consistent with the prediction. This work utilizes the electron potential well effect and multi-level screening calculations to design highly efficient heterojunction catalysts, which can provide useful theoretical guidance for the rational design of heterojunction-type catalysts.

Semiclassical Vibrational Spectroscopy of Real Molecular Systems by Means of Cross-Correlation Filter Diagonalization.

We applied the harmonic inversion technique to extract vibrational eigenvalues from the semiclassical initial value representation (SC-IVR) propagator of molecular systems described by explicit potential surfaces. The cross-correlation filter-diagonalization (CCFD) method is used for the inversion problem instead of the Fourier transformation, which allows much shorter propagation time and is thus capable of avoiding numerical divergence issues while getting rid of approximations like the separable one to the pre-exponential factor. We also used the "Divide-and-Conquer" technique to control the total dimensions under consideration, which helps to further enhance the numerical behavior of SC-IVR calculations and the stability of harmonic inversion methods. The technique is tested on small molecules and water trimer to justify its applicability and reliability. Results show that the CCFD method can effectively extract the vibrational eigenvalues from short trajectories and reproduce the original spectra conventionally obtained from long-time ones, with no loss on accuracy while the numerical behavior is much better. This work demonstrates the possibility to apply the combined method of CCFD and SC-IVR to real molecular potential surfaces, which might be a new way to overcome the numerical instabilities caused by the increase of dimensions.

Accurate calculation of tunneling splittings in water clusters using path-integral based methods.

Tunneling splittings observed in molecular rovibrational spectra are significant evidence for tunneling motion of hydrogen nuclei in water clusters. Accurate calculations of the splitting sizes from first principles require a combination of high-quality inter-atomic interactions and rigorous methods to treat the nuclei with quantum mechanics. Many theoretical efforts have been made in recent decades. This Perspective focuses on two path-integral based tunneling splitting methods whose computational cost scales well with the system size, namely, the ring-polymer instanton method and the path-integral molecular dynamics (PIMD) method. From a simple derivation, we show that the former is a semiclassical approximation to the latter, despite that the two methods are derived very differently. Currently, the PIMD method is considered to be an ideal route to rigorously compute the ground-state tunneling splitting, while the instanton method sacrifices some accuracy for a significantly smaller computational cost. An application scenario of such a quantitatively rigorous calculation is to test and calibrate the potential energy surfaces of molecular systems by spectroscopic accuracy. Recent progress in water clusters is reviewed, and the current challenges are discussed.

A PRPD-Based UHF Filtering and Noise Reduction Algorithm for GIS Partial Discharge.

The online detection of partial discharge (PD) in gas-insulated switchgear (GIS) is a crucial and powerful tool for maintaining their reliability. However, extracting weak discharge signals from strong disturbances is a significant challenge. The presence of noise can hamper the identification and localization of PD types, making the extraction of pure PD signals the focus of current research. This paper proposes a PRPD-based PD filtering algorithm that analyzes interference using the output information from PRPD and sets threshold parameters for noise reduction processing. This method is mainly used for secondary noise reduction at a later stage, without analyzing the noise source, to achieve effective signal acquisition while retaining the characteristics of the PD signals, thereby improving the system's sensitivity and the signal's purity.

A Smart Grid Overvoltage Identification System Associated with Partial Discharge Signal and Dielectric Loss Detection.

Capacitive equipment refers to its insulation design using the principle of capacitance of electrical equipment, mainly by a variety of different capacitive components in series. Most of the equipment in the substation is capacitive equipment. Once an insulation failure occurs, it will lead to extremely serious consequences. Monitoring grid overvoltage and insulation degradation of capacitive equipment is an effective means to ensure the stable operation of the power system. Therefore, in order to enhance the health management of capacitive equipment, including transformers, bushings, and current transformers, and to mitigate the risk of severe failures, it is imperative to conduct broad-spectrum frequency-domain online monitoring of overvoltages, dielectric losses, and partial discharge. However, the current monitoring work requires the utilization of multiple detection apparatuses. Aiming at the disadvantage that the existing inspection is not well integrated and requires a combination of multiple devices. This paper proposes a smart grid overvoltage identification system that utilizes partial discharge (PD) signals in correlation with dielectric loss detection. The system achieves synchronous detection of dielectric loss and high-frequency partial discharge by synchronously and in real-time acquiring four current signals from the power grid, enhancing the integration level of the hardware system.

Torsional Tunneling Splitting in a Water Trimer.

Using a full-dimensional quantum method for nuclei and a new first-principles water potential, we show that the torsional tunneling splitting in a water trimer can be reproduced with accuracy up to ∼1 cm-1. We quantify the coupling constants of the nuclear quantum states between nonadjacent wells and show that they are the main reason for shifting the quartet-split levels in spectra from a 1:2:1 spacing. This demonstrates the limitation of treatments using simplified models such as the Hückel model and emphasizes the nonlocal nature of the quantum interactions in this system. With such an ab initio endeavor, we examine the quality of the water potential developed and provide a rigorous scheme to decipher the experimental spectra with unprecedented accuracy, which is applicable to more general systems.

Determination of concerted or stepwise mechanism of hydrogen tunneling from isotope effects: Departure between experiment and theory.

Isotope substitution is an important experimental technique that offers deep insight into reaction mechanisms, as the measured kinetic isotope effects (KIEs) can be directly compared with theory. For multiple proton transfer processes, there are two types of mechanisms: stepwise transfer and concerted transfer. The Bell-Limbach model provides a simple theory to determine whether the proton transfer mechanism is stepwise or concerted from KIEs. Recent scanning tunneling microscopy (STM) experiments have studied the proton switching process in water tetramers on NaCl(001). Theoretical studies predict that this process occurs via a concerted mechanism; however, the experimental KIEs resemble the Bell-Limbach model for stepwise tunneling, raising questions on the underlying mechanism or the validity of the model. We study this system using ab initio instanton theory, and in addition to thermal rates, we also considered microcanonical rates, as well as tunneling splittings. The instanton theory predicts a concerted mechanism, and the KIEs for tunneling rates (both thermal and microcanonical) upon deuteration are consistent with the Bell-Limbach model for concerted tunneling but could not explain the experiments. For tunneling splittings, partial and full deuteration change the size of it in a similar fashion to how they change the rates. We further examined the Bell-Limbach model in another system, porphycene, which has both stepwise and concerted tunneling pathways. The KIEs predicted by instanton theory are again consistent with the Bell-Limbach model. This study highlights differences between KIEs in stepwise and concerted tunneling and the discrepancy between theory and recent STM experiments. New theory/experiments are desired to settle this problem.

Binary and ternary toxicological interactions of clothianidin and eight commonly used pesticides on honey bees (Apis mellifera).

Although many toxicological evaluations have been conducted for honey bees (Apis mellifera), most of these studies have only focused on the effects of individual chemicals. However, honey bees are usually exposed to pesticide mixtures under field conditions. In this study, we examined the effects of individual pesticides and mixtures of clothianidin (CLO) with eight other pesticides [carbaryl (CAR), thiodicarb (THI), chlorpyrifos (CHL), beta-cyfluthrin (BCY), gamma-cyhalothrin (GCY), tetraconazole (TET), spinosad (SPI) and indoxacarb (IND)] on honey bees using a feeding method. Toxicity tests of a 4-day exposure to individual pesticides revealed that CLO had the highest toxicity to A. mellifera, with an LC50 value of 0.24 µg a.i. mL-1, followed by IND and CHL with LC50 values of 3.40 and 3.56 µg a.i. mL-1, respectively. SPI and CAR had relatively low toxicities, with LC50 values of 7.19 and 8.42 µg a.i. mL-1, respectively. In contrast, TET exhibited the least toxicity, with an LC50 value of 258.7 µg a.i. mL-1. Most binary mixtures of CLO with other pesticides exerted additive and antagonistic effects. However, all the ternary mixtures containing CLO and TET (except for CLO+TET+THD) elicited synergistic responses to bees. Either increased numbers of components in the mixture or/and a unique mode of action appeared to be responsible for the higher toxicity of mixtures. Our findings emphasized the need for risk assessment of pesticide mixtures rather than the individual chemicals. Our data also provided information that might help growers avoid increased toxicity and unnecessary injury to pollinators.

Pseudogene MSTO2P enhances hypoxia-induced osteosarcoma malignancy by upregulating PD-L1.

Hypoxia has been shown to be related to osteosarcoma development and progression. Pseudogene MSTO2P was reported to be dysregulated in hepatocellular carcinoma and lung cancer. However, the mechanism by which MSTO2P-modulated osteosarcoma remains unclear. MSTO2P and PD-L1 expression levels were examined by RT-qPCR and westernblot. Tumor cell invasion was determined by tranwell assay. EMT process was probed by determining E-cadherin and Vimentin levels. Soft agar assay was used to examine anchorage-independent growth of osteosarcoma cells. In vivo tumor growth was measured by xenografting tumor experiment. Hypoxia treatment promoted cell growth, invasion and EMT of osteosarcoma cells. MSTO2P knockdown led to attenuated cell growth, invasion and EMT of osteosarcoma cells under hypoxia condition. More interestingly, our data revealed that MSTO2P was positively associated with tumor growth in immunodeficient mice and human clinical tissues. PD-L1 was shown to act as a key effector for MSTO2P-regulated osteosarcoma progression under hypoxia condition. In conclusion, we unravel a novel mechanism for explaining MSTO2P-involved osteosarcoma progression under hypoxia condition, which will facilitate development of potential diagnostic and therapeutical strategies for osteosarcoma.

Enhancing the Efficacy of Photodynamic Therapy through a Porphyrin/POSS Alternating Copolymer.

Aggregation-induced quenching (AIQ) of photosensitizers greatly reduces the quantum yield of singlet oxygen generation and mitigates the efficacy of photodynamic therapy (PDT). We have prepared an alternating copolymer starting from 4-vinylbenzyl-terminated tetraphenylporphyrin (VBTPP) and maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS), via alternating reversible addition-fragmentation chain transfer (RAFT) polymerization. Porphyrin and POSS are installed on the amphiphilic block copolymers backbone in an alternating fashion and POSS completely inhibits the aggregation of porphyrin units via stacking. The amphiphilic block copolymer can self-assemble into nanoparticles and its application in PDT treatment was tested. These porphyrin-containing polymeric nanoparticles display high photochemical yield and phototoxicity in vitro and in vivo, providing a novel strategy to enhance the PDT efficacy.

Comparisons of Transcriptional Profiles of Gut Genes between Cry1Ab-Resistant and Susceptible Strains of Ostrinia nubilalis Revealed Genes Possibly Related to the Adaptation of Resistant Larvae to Transgenic Cry1Ab Corn.

A microarray developed on the basis of 2895 unique transcripts from larval gut was used to compare gut gene expression profiles between a laboratory-selected Cry1Ab-resistant (R) strain and its isoline susceptible (S) strain of the European corn borer (Ostrinia nubilalis) after the larvae were fed the leaves of transgenic corn (MON810) expressing Cry1Ab or its non-transgenic isoline for 6 h. We revealed 398 gut genes differentially expressed (i.e., either up- or down-regulated genes with expression ratio ≥2.0) in S-strain, but only 264 gut genes differentially expressed in R-strain after being fed transgenic corn leaves. Although the percentages of down-regulated genes among the total number of differentially expressed genes (50% in S-strain and 45% in R-strain) were similar between the R- and S-strains, the expression ratios of down-regulated genes were much higher in S-strain than in R-strain. We revealed that 17 and 9 significantly up- or down-regulated gut genes from S and R-strain, respectively, including serine proteases and aminopeptidases. These genes may be associated with Cry1Ab toxicity by degradation, binding, and cellular defense. Overall, our study suggests enhanced adaptation of Cry1Ab-resistant larvae on transgenic Cry1Ab corn as revealed by lower number and lower ratios of differentially expressed genes in R-strain than in S-strain of O. nubilalis.

Identification of Genes Potentially Responsible for extra-Oral Digestion and Overcoming Plant Defense from Salivary Glands of the Tarnished Plant Bug (Hemiptera: Miridae) Using cDNA Sequencing.

Saliva is known to play a crucial role in tarnished plant bug (TPB, Lygus lineolaris [Palisot de Beauvois]) feeding. By facilitating the piercing, the enzyme-rich saliva may be used for extra-oral digestion and for overcoming plant defense before the plant fluids are ingested by TPBs. To identify salivary gland genes, mRNA was extracted from salivary glands and cDNA library clones were sequenced. A de novo-assembling of 7,000 Sanger sequences revealed 666 high-quality unique cDNAs with an average size of 624 bp, in which the identities of 347 cDNAs were determined using Blast2GO. Kyoto Encyclopedia of Genes and Genomes analysis indicated that these genes participate in eighteen metabolic pathways. Identifications of large number of enzyme genes in TPB salivary glands evidenced functions for extra-oral digestion and feeding damage mechanism, including 45 polygalacturonase, two α- amylase, one glucosidase, one glycan enzyme, one aminopeptidase, four lipase, and many serine protease cDNAs. The presence of multiple transcripts, multigene members, and high abundance of cell wall degradation enzymes (polygalacturonases) indicated that the enzyme-rich saliva may cause damage to plants by breaking down plant cell walls to make nutrients available for feeding. We also identified genes potentially involved in insect adaptation and detoxifying xenobiotics that may allow insects to overcome plant defense responses, including four glutathione S-transferases, three esterases, one cytochrome P450, and several serine proteases. The gene profiles of TPB salivary glands revealed in this study provides a foundation for further understanding and potential development of novel enzymatic inhibitors, or other RNAi approaches that may interrupt or minimize TPB feeding damage.

Comparison of perpendicular to the coronal plane versus medial inclination for atlas pedicle screw insertion: an anatomic and radiological study in human cadavers.

PURPOSE: To ascertain the anatomic and radiological parameters of the atlas (C1) pedicle and to explore a preferable method of C1 pedicle screw insertion. METHODS: Thirty-four conserved human cadaveric cervical spines (20 males, 14 females) underwent computed tomography (CT) scanning. Trajectories P (perpendicular to the coronal plane) and I (with medial inclination) were designed for each C1 pedicle on CT images. External pedicle wall width, medullary cavity width, transverse angle, and optimal entry point along each trajectory were measured. Cortical screws of 3.5 mm in diameter were inserted into C1 pedicles along trajectory P and I, respectively, and wall perforation was assessed (post-operative CT scanning). RESULTS: The external pedicle wall width and medullary cavity width along trajectory I were significantly wider than trajectory P (P < 0.01). Although external pedicle wall widths were all greater than 3.5 mm, medullary cavity width <3.5 mm was found in 16.1 % pedicles along trajectory P and only 2.9 % along trajectory I. Transverse angle was 21.8° along trajectory I and 0° along trajectory P. Optimal entry point of trajectory I was 4.1 mm lateral from that of trajectory P. The lateral wall perforation rate was significantly lower along trajectory I than trajectory P (P < 0.05). CONCLUSIONS: C1 pedicle screw trajectory with medial inclination and more lateral entry points yielded wider medullary cavity width than that perpendicular to the coronal plane, and might minimize lateral wall perforation.

A H2 S-Generated Supramolecular Photosensitizer for Enhanced Photodynamic Antibacterial Infection and Relieving Inflammation.

Photodynamic therapy (PDT) is a promising treatment against bacteria-caused infections. By producing large amounts of reactive oxygen species (ROS), PDT can effectively eliminate pathogenic bacteria, without causing drug resistance. However, excessive ROS may also impose an oxidative stress on surrounding tissues, resulting in local inflammation. To avoid this major drawback and limit pro-inflammation during PDT, this work prepared a supramolecular photosensitizer (TPP-CN/CP5) based on host-guest interactions between a cysteine-responsive cyano-tetraphenylporphyrin (TPP-CN) and a water-soluble carboxylatopillar[5]arene (CP5). TPP-CN/CP5 not only possesses excellent photodynamic antibacterial properties, but also shows good anti-inflammatory and cell protection capabilities. Under 660 nm light irradiation, TPP-CN/CP5 could rapidly produce abundant ROS for sterilization. After the PDT process, the addition of cysteine (Cys) triggers the release of H2 S from TPP-CN. H2 S then stops the induced inflammation by inhibiting the production of related inflammatory factors. Both in vitro and in vivo experiments show the excellent antibacterial effects and anti-inflammatory abilities of TPP-CN/CP5. These results will certainly promote the clinical application of PDT in the treatment of bacterial infectious diseases.

Orienting people-centred disaster shelter planning based on risk assessing with semi-supervised learning.

Climate-related disasters have been escalating worldwide, incurring major losses. Landslides have become one of the most destructive disasters, especially in China's mountainous areas. To address this, constructing emergency shelters and designing evacuation routes are critical to ensure public safety and minimize impacts on affected residents. This study proposes a novel two-phase, people-centric approach. The first phase applies stakeholder theory and risk economics to develop a landslide hazard assessment model considering vulnerable populations. The model effectively classified 28 landslide points in Bazhou Town, with 35.71 % deemed high-risk and low-risk 64.29 %, reflecting the model's comprehensive risk differentiation capability. The second phase utilizes public choice theory to construct a bi-level multiple objective programming (BLMOP) model addressing conflicting government and resident goals. The algorithm produced 4 Pareto-optimal shelter plans for each village assessed, results demonstrate the proposed approach generates shelter plans meeting government aims while maximizing resident satisfaction, accounting for local conditions. Grounded in field data and a people-focused lens, this two-stage methodology provides a multiple objective optimization framework balancing stakeholder need. A case study of Bazhou Town validates the method's effectiveness.

Can public opinions improve the effect of financial early warning ? -- an empirical study on the new energy industry.

Public opinion will significantly affect investor decision-making and stock prices, which ultimately has an impact on the long-term development of the new energy industry. This paper mainly aims to delve in the impact of public opinion on the efficacy of financial risk early warning effect and try to establish an enhanced financial risk early warning model for the new energy list companies. To achieve this, we collect the financial data and public evaluation texts of 185 new energy listed companies, converting the text into emotional indicators which are combined with financial indicators to build a financial risk early warning model for new energy listed companies. The contributions of this paper are as follows: (1) The experiment validation demonstrates that the combination of 7 deep learning models and Bagging algorithm highly improves the accuracy of the sentiment analysis model, achieving an accuracy of 84.09%. (2) The accuracy of financial early warning models is generally enhanced after adding sentiment indicators, among which the accuracy of the BP neural network model reached 95.78%. (3) Through clustering analysis, the evaluation models can productively divide the warning intervals, thereby bolstering the interpretability and applicability of early warning results. Therefore, we suggest that when establishing the financial early warning system, it's necessary to take public opinions into consideration. Aside from improving the early warning effect, it also can be used as a separate indicator for daily monitoring.

A Feasible Strategy for High-Performance Aqueous Zinc-Ion Batteries: Introducing Conducting Polymer.

Aqueous zinc ion batteries (AZIBs) offer great potential for large-scale energy storage because of their high safety, low cost and acceptable energy density. However, the cycle life of AZIBs is inevitably affected by parasitic reactions and dendritic growth caused by multiple factors such as electrode, electrolyte and separator, which pose significant obstacles to the practical application of AZIBs. To address these challenges, conducting polymer (CP) based materials have gained widespread attention in the realm of rechargeable batteries due to the adjustable band gap, controllable morphology, and excellent flexibility of CPs. In particular, CPs exhibit remarkable conductivity, low dimensionality, and doping characteristics, making them highly promising for integration into the AZIB system. In this review, the problems associated with the cathode, anode, electrolyte, and separator of AZIBs are discussed, and the application of CPs for their modification is summarized. The review provides a comprehensive analysis of the action mechanisms involved in the CP modification process and offers valuable insights for the design and development of CPs that can be effectively utilized in AZIBs. Additionally, the review presents a promising outlook of this research field, aiming to further advance the application of low-cost and high-performance CPs and their composites in AZIBs.