Ropivacaine synergizes with sorafenib to induce apoptosis of hepatocellular carcinoma cells via the IL-6/STAT3 pathway.

The development of resistance in hepatocellular carcinoma (HCC) cells limits the effectiveness of sorafenib, but combination therapy with other drugs may have a positive effect. However, the effect of ropivacaine combined with sorafenib on the treatment of HCC cells and its potential regulatory mechanisms remain unclear. The proliferation and apoptosis of HCC cells treated with ropivacaine, sorafenib, and ropivacaine plus sorafenib were analyzed by cell-counting kit 8 and flow cytometry. The protein levels were measured by Western blot. The antitumor effect of ropivacaine, sorafenib, and their combination was verified by a tumor xenograft model. Ropivacaine and sorafenib markedly impeded the viability of HCC cells in a concentration-dependent manner. Compared with ropivacaine or sorafenib treatment alone, ropivacaine and sorafenib combination treatment impeded HCC cell proliferation, facilitated apoptosis, enhanced cleaved caspase-3, cleaved caspase-9, and cyclin D1 protein expression, while it reduced IL-6 and p-STAT3 expression and inhibited tumor growth in vivo. Importantly, the activation of the IL-6/STAT3 pathway could reverse the repressive or stimulative effects of ropivacaine and sorafenib on the proliferation and apoptosis in HCC cells. In summary, ropivacaine synergistically induces sorafenib-stimulated apoptosis of HCC cells via the IL-6/STAT3 pathway. Ropivacaine is a potential drug for the treatment of HCC when combined with sorafenib.

Sophisticated Structural Ceramics Shaped from 3D Printed Hydrogel Preceramic Skeleton.

Shaping ceramic materials into sophisticated architecture with 3D hierarchical structure is desirable in multiapplication yet remains challenge due to their brittle and stiff nature. Herein, a new method to achieve ceramic architectures with unsupported and large-spanning structure by shaping vat photopolymerization 3D printed hydrogel preceramic skeleton with unique flexible and deformable character is proposed. Specifically, the present photopolymerizable hydrogel preceramic achieves one stone, two birds: the photosensitive polymer matrix coupled with ceramic nanoparticles for the first shaping by vat photopolymerization 3D printing and the secondary plasticity of the 3D printed ceramic body through flexible shape deformation of hydrogel networks. Inorganic binder aluminum dihydrogen phosphate serves as hydrogel dispersion medium to achieve ultralow shrinkage photopolymerization ceramic. Compared with conventional polymer-derived photocuring ceramics, the linear shrinkage of lamina structure is solely 2%, and which of cubic ceramic structure is just 13.3%. More importantly, one 3D printed preceramic is conducted to reshape repeatedly myriad constructions, realizing reusability of intrinsic brittle ceramic, improving manufacturing fault tolerance rate. Finally, a variety of paradigms for ceramic structure applications are proposed toward stereo circuit, biomedicine, and catalytic applications, breaking the limitation of intrinsic brittleness of ceramic in high-precision manufacturing of complex ceramic devices.

Topology and giant circular dichroism of enantiomorphic Kagome bands in a designed covalent organic framework.

Covalent organic frameworks (COFs) are an emerging class of crystalline organic materials that have shown potential to be a new physical platform. In this work, a designed COF named AB-COF, which has novel enantiomorphic Kagome bands, is proposed and a feasible route to synthesize it is given. Via a combination of first-principles calculations and tight-binding analysis, we investigate the electronic structures and the phase interference of the COF. It becomes topologically nontrivial when doping one iodine atom in a unit cell. The Berry curvatures of the valence band (VB) and conduction band (CB) of the iodine-doped AB-COF show opposite values and different distributions. This provides an opportunity to study the new mechanism of circular dichroism from the different Berry curvatures of the VB and CB. Surprisingly, the circular-dichroism dissymmetry factor of AB-COF reaches a theoretical maximum value, and the oscillator strength data are in agreement with this result. When two iodine atoms are doped in a unit cell, the Berry curvatures of the VB and CB also have different values, but with more symmetry and similar distributions. This behavior enhances the circular dichroism with a wider range of dissymmetric absorption, and the circular dichroism dissymmetry factor also reaches its theoretical maximum value.

Investigation of the photocatalytic activity of magnetically recoverable g-C3N4/CoFe2O4/Bi2MoO6 particles for purifying tetracycline antibiotics: synthesis, characterization, ecotoxicity analysis, and plant toxicity test.

To purify water polluted by tetracycline antibiotics, a new visible light-driven magnetically recoverable photocatalyst, g-C3N4/CoFe2O4/Bi2MoO6, was prepared in this study, and it effectively removed tetracycline antibiotics. Its rapid recycling was achieved by external magnets, which greatly increased material utilization. After four repeated uses, the degradation rate of tetracycline antibiotics by the g-C3N4/CoFe2O4/Bi2MoO6 composite photocatalyst remained at a high level, and the magnetic separation performance remained stable. Subsequently, it was further discovered that the degradation mechanism of this photocatalytic system was consistent with a double Z-type mechanism, which enabled two transport channels for photogenerated electrons, and was favorable for the separation of the photogenerated electron-hole pairs and prolonged the lifetime of the photogenerated carriers. The active substances playing an important role in the photocatalytic system were ˙O2- and h+. In addition, the possible intermediates in the photocatalytic process were detected by GC-MS analysis, and a degradation mechanism was proposed. The ecotoxicity of the degradation products and intermediates was evaluated using the Toxicity Estimation Software Tool (TEST), and the mung bean seed cultivation test was carried out to visually and efficiently illustrate that the g-C3N4/CoFe2O4/Bi2MoO6 photocatalyst can effectively degrade antibiotics, with low ecotoxicity of the degradation products. This provides a new idea for the removal of organic pollutants using light energy.

Long non-coding RNA NORAD regulates megakaryocyte differentiation and proplatelet formation via the DUSP6/ERK signaling pathway.

Megakaryopoiesis and platelet production is a complex process that is underpotential regulation at multiple stages. Many long non-coding RNAs (lncRNAs) are distributed in hematopoietic stem cells and platelets. lncRNAs may play important roles as key epigenetic regulators in megakaryocyte differentiation and proplatelet formation. lncRNA NORAD can affect cell ploidy by sequestering PUMILIO proteins, although its direct effect on megakaryocyte differentiation and thrombopoiesis is still unknown. In this study, we demonstrate NORAD RNA is highly expressed in the cytoplasm during megakaryocyte differentiation. Interestingly, we identified for the first time that NORAD has a strong inhibitory effect on megakaryocyte differentiation and proplatelet formation from cultured megakaryocytes. DUSP6/ERK1/2 pathway is activated in response to NORAD knockdown during megakaryocytopoiesis, which is achieved by sequestering PUM2 proteins. Finally, compared with the wild-type control mice, NORAD knockout mice show a faster platelet recovery after severe thrombocytopenia induced by 6 Gy total body irradiation. These findings demonstrate lncRNA NORAD has a key role in regulating megakaryocyte differentiation and thrombopoiesis, which provides a promising molecular target for the treatment of platelet-related diseases such as severe thrombocytopenia.

miR-199a-5p targets DUSP14 to regulate cell proliferation, invasion and stemness in non-small cell lung cancer.

Background: Non-small cell lung cancer (NSCLC) shows the highest morbidity among malignant tumors worldwide. Despite improvements of diagnosis and treatment, patient prognosis remains unfavorable. Therefore, there is a need to discover a novel treatment strategy for NSCLC. DUSP14 is related to various cancers as the regulatory factor for cellular processes. However, its specific roles in NSCLC and the upstream modulator remain largely unclear. Methods: DUSP14 expression patterns within the lung cancer patient cohort from TCGA database were analyzed using UALCAN online tool. Different databases including miRDB, starbase, and Targetscan were employed to screen the upstream regulator of DUSP14. DUSP14 and miR-199a-5p expression was determined by qRT-PCR and Western blot techniques. To confirm binding interaction of DUSP14 with miR-199a-5p, we conducted a dual-luciferase reporter assay. Cell viability, migration, and stemness properties were assessed using CCK-8, EdU (5-ethynyl-2'-deoxyuridine) incorporation, transwell invasion, and sphere formation assays. The effect of DUSP14 silencing on tumorigenesis was assessed with the NSCLC cell xenograft mouse model. Results: Our study discovered that DUSP14 exhibited high expression within NSCLC tumor samples, which is related to the dismal prognostic outcome in NSCLC patients. Silencing DUSP14 impaired NSCLC cell proliferation, migration, and tumor sphere formation. Besides, we identified miR-199a-5p as the upstream regulatory factor for DUSP14, and its expression was negatively related to DUSP14 level within NSCLC tissues. Introducing miR-199a-5p recapitulated the function of DUSP14 silencing in NSCLC cell aggressiveness and stemness. Moreover, knocking down DUSP14 efficiently inhibited tumor formation in NSCLC cells of the xenograft model. Conclusions: Our study suggests that DUSP14 is negatively regulated by miR-199a-5p within NSCLC, whose overexpression is required for sustaining NSCLC cell proliferation, invasion and stemness.

Low frequency of SLC26A4 c.919-2A > G variant among patients with nonsyndromic hearing loss in Yunnan of Southwest China.

BACKGROUND: Gene variants are responsible for more than half of hearing loss, particularly in nonsyndromic hearing loss (NSHL). The most common pathogenic variant in SLC26A4 gene found in East Asian populations is c.919-2A > G followed by c.2168A > G (p.H723R). This study was to evaluate their variant frequencies in patients with NSHL from special education schools in nine different areas of Southwest China's Yunnan. METHODS: We performed molecular characterization by PCR-products directly Sanger sequencing of the SLC26A4 c.919-2AG and c.2168 A > G variants in 1167 patients with NSHL including 533 Han Chinese and 634 ethnic minorities. RESULTS: The SLC26A4 c.919-2A > G variant was discovered in 8 patients with a homozygous state (0.69%) and twenty-five heterozygous (2.14%) in 1167 patients with NSHL. The total carrier rate of the c.919-2A > G variant was found in Han Chinese patients with 4.50% and ethnic minority patients with 1.42%. A significant difference existed between the two groups (P < 0.05). The c.919-2A > G allele variant frequency was ranged from 3.93% in Kunming to zero in Lincang and Nvjiang areas of Yunnan. We further detected the SLC26A4 c.2168 A > G variant in this cohort with one homozygotes (0.09%) and seven heterozygotes (0.60%), which was detected in Baoshan, Honghe, Licang and Pu`er areas. Between Han Chinese group (0.94%) and ethnic minority group (0.47%), there was no statistical significance (P > 0.05). Three Han Chinese patients (0.26%) carried compound heterozygosity for c.919-2A > G and c.2168 A > G. CONCLUSION: These data suggest that the variants in both SLC26A4 c.919-2A > G and c.2168 A > G were relatively less frequencies in this cohort compared to the average levels in most regions of China, as well as significantly lower than that in Han-Chinese patients. These results broadened Chinese population genetic information resources and provided more detailed information for regional genetic counselling for Yunnan.

Probabilistic Hesitant Fuzzy Evidence Theory and Its Application in Capability Evaluation of a Satellite Communication System.

Evaluating the capabilities of a satellite communication system (SCS) is challenging due to its complexity and ambiguity. It is difficult to accurately analyze uncertain situations, making it difficult for experts to determine appropriate evaluation values. To address this problem, this paper proposes an innovative approach by extending the Dempster-Shafer evidence theory (DST) to the probabilistic hesitant fuzzy evidence theory (PHFET). The proposed approach introduces the concept of probabilistic hesitant fuzzy basic probability assignment (PHFBPA) to measure the degree of support for propositions, along with a combination rule and decision approach. Two methods are developed to generate PHFBPA based on multi-classifier and distance techniques, respectively. In order to improve the consistency of evidence, discounting factors are proposed using an entropy measure and the Jousselme distance of PHFBPA. In addition, a model for evaluating the degree of satisfaction of SCS capability requirements based on PHFET is presented. Experimental classification and evaluation of SCS capability requirements are performed to demonstrate the effectiveness and stability of the PHFET method. By employing the DST framework and probabilistic hesitant fuzzy sets, PHFET provides a compelling solution for handling ambiguous data in multi-source information fusion, thereby improving the evaluation of SCS capabilities.

Ropivacaine combined with sorafenib attenuates hepatocellular carcinoma cell proliferation and metastasis by inhibiting the miR-224/HOXD10 axis.

OBJECTIVE: The development of drug resistance in hepatocellular carcinoma (HCC) cells limits the effectiveness of sorafenib (Sor). However, the regulatory mechanisms underlying the effects of the combination Sor and ropivacaine (Rop) on HCC cells remain unclear. METHODS: miR-224 and HOXD10 mRNA expression in HCC cells was analyzed using qRT-PCR. CCK-8, Transwell assays and tumor formation experiments in nude mice were used to assess HCC cell proliferation, migration, and invasion. Migration of HCC cells was also analyzed using a cell scratch assay. Hematoxylin and eosin staining was used to detect tumor area. RESULTS: miR-224 expression profoundly increased in HepG2 and Huh7 cells. Treatment with Rop and/or Sor blocked miR-244 expression, especially the combination treatment. Transfection of miR-224 mimic increased HCC cell proliferation and tumor size in nude mice, and migration and invasion in vitro in the presence of Rop and Sor compared to the negative control mimic. Dual-luciferase reporter assays showed that HOXD10 was targeted by miR-224. HOXD10 protein expression and was markedly reduced in HepG2 and Huh7 cells. Rop and/or Sor treatment increased HOXD10 protein expression, particularly the combination treatment. miR-224 negatively regulated HOXD10 expression in HCC cells treated with Rop and Sor. Transfection-mediated silencing of HOXD10 increased HCC cell proliferation, migration, and invasion in the presence of Rop and Sor compared with negative control transfection. CONCLUSION: The combination of Rop and Sor attenuates HCC cell proliferation and metastasis via the miR-224/HOXD10 axis.

A Sensitive Ultra-performance Liquid Chromatography-Tandem Mass Spectrometric Method for Determination of Secalonic Acid F in Rat Plasma and Its Application to Pharmacokinetic Study.

Secalonic acid F (SAF) is a fungal secondary metabolite exhibited interesting pharmacological effect. In this study, a simple and sensitive ultra-performance liquid chromatography-tandem mass spectrometric (UPLC-MS/MS) method was developed and validated for the determination of SAF in rat plasma. Emodin was selected as the internal standard (IS), and plasma samples were prepared by liquid-liquid extraction with ethyl acetate. Chromatographic separation was operated on an Agilent SB-C18 column, and the mobile phase was a mixture of 0.5% formic acid in water and methanol (V:V = 20:80) at a flow rate of 0.3 mL/min. Detection was carried out with a 6460 triple-quadrupole mass spectrometer using electrospray ionization in the multiple-reaction monitoring mode. The MS/MS ion transitions monitored were m/z 639.3 â†’ 415.4 and 269.0 â†’ 225.1 for SAF and IS, respectively. Results showed the calibration curve of SAF was linear in the range of 2-500 ng·mL-1 with the correlation coefficient > 0.99. The matrix effect, extraction recovery, dilution effect, intraday and inter-day precision and accuracy were all in acceptable limits. The analytes were also stable under different conditions. The validated method was successfully applied to a pharmacokinetic study after oral administration in Sprague-Dawley rats at a dose of 10 mg/kg.

Enantiomorphic kagome bands in a two-dimensional covalent organic framework with non-trivial magnetic and topological properties.

The kagome lattice is one of the most intriguing topics to study. It has a frustrated flat band touching a set of Dirac bands and can possess various promising properties, such as ferromagnetism, superconductivity, and a non-trivial topology. Covalent organic frameworks (COFs) are a rare type of inorganic material, however, they can provide a platform for generating certain required lattices. Based on first-principles density functional theory calculations, we show that a newly synthesized two-dimensional COF named COF-SH has novel enantiomorphic kagome bands, which include two sets of flat bands touching the Dirac bands around the Fermi level. The Bloch wave of the flat-valence band at the K-point shows the kagome nature of the phase interference. Under charge doping, the COF-SH exhibits a ferromagnetic ground state. Moreover, when COF-SH is doped with iodine atoms, a sizable gap in the system is opened between the flat bands and the Dirac bands due to the spin-orbit coupling (SOC) effect. Meanwhile, the spin degeneracy is lifted since the organic layer loses electrons due to the oxidizing property of iodine. In addition, our tight-binding analysis with the SOC effect shows that the flat valence band separates from the Dirac bands and holds a nonzero Chern number. Consequently, this I-doped COF can give rise to a quantum anomalous Hall effect.

Successful therapy using high-dose furmonertinib for non-small cell lung cancer with leptomeningeal metastasis: a case report and literature review.

Background: Lung cancer is the second most common form of malignant tumor and has the highest mortality rate worldwide. Among its subtypes, lung adenocarcinoma is the most prevalent. Leptomeningeal metastasis (LM) is rare and is characterized by a dismal prognosis, with overall survival periods typically spanning 4 to 6 weeks without treatment. However, in specific cases, survival can be extended to 4 to 6 months with appropriate therapy. The recent approval of third-generation tyrosine kinase inhibitors (TKIs), such as osimertinib, aumolertinib, and furmonertinib, has introduced promising treatment options for individuals with non-small cell lung cancer (NSCLC) who develop LM after developing resistance to first- and second-generation TKIs. These third-generation TKIs exhibit an enhanced ability to penetrate the blood-brain barrier (BBB), opening up new avenues for managing this challenging condition. Case summary: We report the case of a 48-year-old Chinese man diagnosed with advanced NSCLC harboring an epidermal growth factor receptor (EGFR) mutation. Following a pulmonary lobectomy and postoperative adjuvant therapy with gefitinib, the patient was diagnosed with LM, which was confirmed by his neurologic symptoms, cerebrospinal fluid cytologic analysis, and cranial enhancement magnetic resonance imaging. Subsequently, he received oral treatment in the form of 160 mg of furmonertinib daily. After 5 days of furmonertinib therapy, the patient recovered from lethargy, with an obvious improvement in cognitive function. Follow-up visits revealed a 6-month survival period following the LM diagnosis. Patients with NSCLC and LM typically present with severe symptoms, and the efficacy of systemic treatment, intrathecal chemotherapy, and radiotherapy remains unsatisfactory. We hope that this specific case provide valuable insights into the management of patients with EGFR mutation-associated NSCLC with LM. Conclusion: Furmonertinib, a third-generation EGFR TKI with notable BBB penetration, shows promise in LM control and the rapid alleviation of intracranial symptoms. Further investigations into appropriate dosage and toxicity management are imperative.

Alkaloid diversity expansion of a talent fungus Penicillium raistrichii through OSMAC-based cultivation.

Introduction: Alkaloidal natural products are attractive for their broad spectrum of pharmaceutical bioactivities. In the present work, the highly productive saline soil derived fungus, Penicillium raistrichii, was subjected to the strategy of OSMAC (one strain many compounds) with changes of cultivation status. Then, the work-flow led to the expansion of the alkaloid chemical diversity and subsequently induced the accumulation of four undescribed alkaloids, named raistrimides A-D (1-4), including three ß-carbolines (1-3), one 2-quinolinone (4), and one new natural product, 2-quinolinone (5), along with five known alkaloid chemicals (6-10). Methods: A set of NMR techniques including 1H, 13C, HSQC and HMBC, along with other spectroscopic data of UV-Vis, IR and HRESIMS, were introduced to assign the plain structures of compounds 1-10. The absolute configuration of 1-3 were elucidated by means of X-ray crystallography or spectroscopic analyses on optical rotation values and experimental electronic circular dichroism (ECD) data. In addition, it was the first report on the confirmation of structures of 6, 7 and 9 by X-ray crystallography data. The micro-broth dilution method was applied to evaluate antimicrobial effect of all compounds towards Staphylococcus aureus, Escherichia coli, and Candida albicans. Results and discussion: The results indicated compounds 1, 3 and 4 to be bioactive, which may be potential for further development of anti-antimicrobial agents. The finding in this work implied that OSMAC strategy was a powerful and effective tool for promotion of new chemical entities from P. raistrichii.

A Comparative Study of the Electronic Transport and Gas-Sensitive Properties of Graphene+, T-graphene, Net-graphene, and Biphenylene-Based Two-Dimensional Devices.

The electronic transport properties of the four carbon isomers: graphene+, T-graphene, net-graphene, and biphenylene, as well as the gas-sensing properties to the nitrogen-based gas molecules including NO2, NO, and NH3 molecules, are systematically studied and comparatively analyzed by combining the density functional theory with the nonequilibrium Green's function. The four carbon isomers are metallic, especially with graphene+ being a Dirac metal due to the two Dirac cones present at the Fermi energy level. The two-dimensional devices based on these four carbon isomers exhibit good conduction properties in the order of biphenylene > T-graphene > graphene+ > net-graphene. More interestingly, net-graphene-based and biphenylene-based devices demonstrate significant anisotropic transport properties. The gas sensors based on the above four structures all have good selectivity and sensitivity to the NO2 molecule, among which T-graphene-based gas sensors are the most prominent with a maximum ΔI value of 39.98 µA, being only three-fifths of the original. In addition, graphene+-based and biphenylene-based gas sensors are also sensitive to the NO molecule with maximum ΔI values of 29.42 and 25.63 µA, respectively. However, the four gas sensors are all physically adsorbed for the NH3 molecule. By the adsorption energy, charge transfer, electron localization functions, and molecular projection of self-consistent Hamiltonian states, the mechanisms behind all properties can be clearly explained. This work shows the potential of graphene+, T-graphene, net-graphene, and biphenylene for the detection of toxic molecules of NO and NO2.

Enhancing Gating Performance in Organic Molecular Field-Effect Transistors by Introducing Polar Azulene Components.

Organic molecular field-effect transistors (FETs) are promising building components for future electronic circuits. Efficient control of charge transport properties is one key issue in the design of organic molecular FETs. In this study, we propose a redesign of a naphthalene-based FET by introducing two azulene components in opposite dipole moment directions. Using density functional theory combined with non-equilibrium Green's function, the simulated electronic transport characteristics reveal that the introduction of polar azulene components effectively narrows the frontier molecular orbitals gap, leading to an increase in the ON-state current. Meanwhile, the OFF-state current is significantly suppressed by highly localizing the dominant electronic transport channel. As a result, improved gate controllability is achieved with a higher ON-OFF current ratio, which is nearly seven times higher than that of the naphthalene-based FET device. These findings provide theoretical directions for future design of organic molecular FET devices with enhanced gating regulation efficiency.

Dissipation, residue, and dietary risk assessment of dimethachlon in grapes.

Dimethachlon, a dicarboximide fungicide, has gained widespread usage in Asian countries. While considered a low-toxicity fungicide, concerns regarding potential health effects, such as nephrotoxicity, have emerged. To date, neither China nor other countries have established maximum residue limit (MRL) for dimethachlon on grapes, and exposure risk assessment of dimethachlon is lacking. Here, we developed a QuEChERS method coupled with gas chromatography-mass spectrometry (GC-MS) to investigate the dissipation rates and terminal residues of dimethachlon in grapes, along with an assessment of dietary risk to consumers. Our results indicated that the average recoveries of dimethachlon in grapes ranged from 74 to 76%. The limit of quantification (LOQ) was 0.050 mg/kg. After undergoing 112 days of storage at -18 °C, the dissipation rate of dimethachlon in grapes was found to be less than 30%, suggesting a state of stable storage. In the context of good agricultural practice (GAP) guidelines, the half-lives of dimethachlon in grapes were 14.3-18.1 days, which is notably longer compared to the reported values for other crops. The terminal residues of dimethachlon in grapes at 14 and 21 days were found to be < 0.05-0.53 mg/kg and < 0.05-0.29 mg/kg, respectively. Regarding the dietary risk assessment, the calculated risk quotient (RQ) value was significantly below 100%, indicating a negligible chronic risk of dimethachlon in grapes at the recommended dosage. This study provides an important reference for the analysis of dimethachlon and offers valuable empirical data to support the establishment of MRL.

Effects of Inorganic Substitutions and Different Metal Electrode Materials on Electronic Transport Properties of Organic Molecular Devices.

Incorporating inorganic components into organic molecular devices offers one novel alternative to address challenges existing in the fabrication and integration of nanoscale devices. In this study, using a theoretical method of density functional theory combined with the nonequilibrium Green's function, a series of benzene-based molecules with group III and V substitutions, including borazine molecule and XnB3-nN3H6 (X = Al or Ga, n = 1-3) molecules/clusters, are constructed and investigated. An analysis of electronic structures reveals that the introduction of inorganic components effectively reduces the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, albeit at the cost of reduced aromaticity in these molecules/clusters. Simulated electronic transport characteristics demonstrate that XnB3-nN3H6 molecules/clusters coupled between metal electrodes exhibit lower conductance compared to prototypical benzene molecule. Additionally, the choice of metal electrode materials significantly impacts the electronic transport properties, with platinum electrode devices displaying distinct behavior compared to silver, copper, and gold electrode devices. This distinction arises from the amount of transferred charge, which modulates the alignment between molecular orbitals and the Fermi level of the metal electrodes by shifting the molecular orbitals in energy. These findings provide valuable theoretical insights for the future design of molecular devices incorporating inorganic substitutions.

Mapping the Environmental Risk of Beech Leaf Disease in the Northeastern United States.

The recently emerged beech leaf disease (BLD) is causing the decline and death of American beech in North America. First observed in 2012 in northeast Ohio, U.S.A., BLD had been documented in 10 northeastern states and the Canadian province of Ontario as of July 2022. A foliar nematode has been implicated as the causal agent, along with some bacterial taxa. No effective treatments have been documented in the primary literature. Irrespective of potential treatments, prevention and prompt eradication (rapid responses) remain the most cost-effective approaches to the management of forest tree disease. For these approaches to be feasible, however, it is necessary to understand the factors that contribute to BLD spread and use them in estimation of risk. Here, we conducted an analysis of BLD risk across northern Ohio, western Pennsylvania, western New York, and northern West Virginia, U.S.A. In the absence of symptoms, an area cannot necessarily be deemed free of BLD (i.e., absence of BLD cannot be certain) due to its fast spread and the lag in symptom expression (latency) after infection. Therefore, we employed two widely used presence-only species distribution models (SDMs), one-class support vector machine (OCSVM), and maximum entropy (Maxent) to predict the spatial pattern of BLD risk based on BLD presence records and associated environmental variables. Our results show that both methods work well for BLD environmental risk modeling purposes, but Maxent outperforms OCSVM with respect to both the quantitative receiver operating characteristics (ROC) analysis and the qualitative evaluation of the spatial risk maps. Meanwhile, the Maxent model provides a quantification of variable contribution for different environmental factors, indicating that meteorological (isothermality and temperature seasonality) and land cover type (closed broadleaved deciduous forest) factors are likely key contributors to BLD distribution. Moreover, the future trajectories of BLD risk over our study area in the context of climate change were investigated by comparing the current and future risk maps obtained by Maxent. In addition to offering the ability to predict where the disease may spread next, our work contributes to the epidemiological characterization of BLD, providing new lines of investigation to improve ecological or silvicultural management. Furthermore, this study shows strong potential for extension of environmental risk mapping over the full American beech distribution range so that proactive management measures can be put in place. Similar approaches can be designed for other significant or emerging forest pest problems, contributing to overall management efficiency and efficacy.

Ferric chloride assisted QuEChERS method for separate detection of bifenazate and bifenazate-diazene in citrus fruits and its field validation.

Bifenazate is widely recognized as an effective acaricide for citrus production in various regions. Detecting both the parent compound of bifenazate and its metabolite, bifenazate-diazene, simultaneously can be challenging owing to their tendency to undergo chemical interconversion. Current methods developed for detecting bifenazate or bifenazate-diazene residues often involve lengthy incubation periods and may not effectively separate the two compounds. In this study, we developed a convenient and fast method based on a modified QuEChERS method assisted by oxidants to concurrently detect bifenazate and bifenazate-diazene. Based on preliminary analysis, it appears that ferric chloride has the ability to react with a reducing substance present in citrus, which may prevent the reduction of bifenazate-diazene. The method was validated and applied in a field trial. This work reports a novel strategy to establish a balanced 'neutral' condition to create a potential method for efficient determination of bifenazate acaricide residues in fruit matrices.

In situ boron-doped cellulose-based biochar for effective removal of neonicotinoids: Adsorption mechanism and safety evaluation.

Biochar materials have been widely employed for adsorption of pollutants, which necessitates further consideration of their efficiency and safety in environmental remediation. In this study, a porous biochar (AC) was prepared through the combination of hydrothermal carbonization and in situ boron doping activation to effectively adsorb neonicotinoids. The adsorption process was shown to be a spontaneous endothermic physical adsorption process, where the predominant interaction forces between the acetamiprid and AC were electrostatic and hydrophobic interactions. The maximum adsorption capacity was 227.8 mg g-1for acetamiprid and the safety of AC was verified by simulating the situation where the aquatic organism (D. magna) was exposed to the combined system (AC & neonicotinoids). Interestingly, AC was observed to reduce the acute toxicity of neonicotinoids owing to the reduced bioavailability of acetamiprid in D. magna and the newly generated expression of cytochrome p450. Thus, it enhanced the metabolism and detoxification response in D. magna, which reducing the biological toxicity of acetamiprid. This study not only demonstrates the potential application of AC from a safety perspective, but also provides insight into the combined toxicity caused by biochar after adsorption of pollutants at the genomic level, which fills the gap in related research.