Entropy in catalyst dynamics under confinement.

Entropy during the dynamic structural evolution of catalysts has a non-trivial influence on chemical reactions. Confinement significantly affects the catalyst dynamics and thus impacts the reactivity. However, a full understanding has not been clearly established. To investigate catalyst dynamics under confinement, we utilize the active learning scheme to effectively train machine learning potentials for computing free energies of catalytic reactions. The scheme enables us to compute the reaction free energies and entropies of O2 dissociation on Pt clusters with different sizes confined inside a carbon nanotube (CNT) at the timescale of tens of nanoseconds while keeping ab initio accuracy. We observe an entropic effect owing to liquid-to-solid phase transitions of clusters at finite temperatures. More importantly, the confinement effect enhances the structural dynamics of the cluster and leads to a lower melting temperature than those of the bare cluster and cluster outside the CNT, consequently facilitating the reaction to occur at lower temperatures and preventing the catalyst from forming unfavorable oxides. Our work reveals the important influence of confinement on structural dynamics, providing useful insight into entropy in dynamic catalysis.

Impact of Surface Enhanced Raman Spectroscopy in Catalysis.

Catalysis stands as an indispensable cornerstone of modern society, underpinning the production of over 80% of manufactured goods and driving over 90% of industrial chemical processes. As the demand for more efficient and sustainable processes grows, better catalysts are needed. Understanding the working principles of catalysts is key, and over the last 50 years, surface-enhanced Raman Spectroscopy (SERS) has become essential. Discovered in 1974, SERS has evolved into a mature and powerful analytical tool, transforming the way in which we detect molecules across disciplines. In catalysis, SERS has enabled insights into dynamic surface phenomena, facilitating the monitoring of the catalyst structure, adsorbate interactions, and reaction kinetics at very high spatial and temporal resolutions. This review explores the achievements as well as the future potential of SERS in the field of catalysis and energy conversion, thereby highlighting its role in advancing these critical areas of research.

Hydrophilicity Dependent Distribution of Water at Ionic Liquids/Metal Interface Monitored by Electrochemical SERS.

The understanding of the interfacial processes is critically important for extending the practical application of ionic liquids, particularly for the role of interfacial water. In the electrochemical system based on ionic liquid electrolytes, small amounts of water at the interface generate a significant change in the electrochemical behaviors of ionic liquids. Therefore, the investigation on the interfacial behavior of water is highly desired in ionic liquids with different anions, water content, and hydrophilicity. Herein, based on the probe strategy, in situ surface enhanced Raman spectroscopy (SERS) combined with electrochemical control (EC-SERS) was developed to investigate the influence of hydrophilicity/hydrophobicity of ionic liquids on the interfacial water. The water-sensitive transformation reaction of 4,4'-dimercaptoazobenzene (DMAB) to para-aminothiophenol (PATP) was employed as a probe reaction for investigating the behavior of interfacial water. The changes of relative SERS intensities of DMAB to PATP served as an indication of the quantity variation of interfacial water. The results show that the transformation reaction efficiencies were critically dependent on the additional water contents, potential, and hydrophilicity of ionic liquids. With a very low molar fraction of additional water (Xw = 0.01), transformation efficiency of DMAB (the amount of interfacial water) followed the sequence of [BMIm]BF4 < [BMIm]PF6 < [BMIm]Tf2N. It was in agreement with the hydrophobicity order of the ionic liquids. With the increase in additional water content, the potential for the full transformation was positively moved, and the efficiency increased significantly. The stronger hydrophobicity allowed more water molecules to migrate to the interface, which was attributed to the difference in interactions between water and the anions of ionic liquids. It demonstrated that the small amount of water tended to gather at the interface in hydrophobic ionic liquids. Compared to traditional cyclic voltammetry, the EC-SERS technique combined with probe reactions is more sensitive to interfacial water. It is anticipated to develop as a promising tool for the investigating water-related issues at interfaces and to provide guidance to screen ionic liquids for practical application.

Transgenic poplar (Populus davidiana×P. bolleana Loucne) expressing dsRNA of insect chitinase gene: lines identification and resistance assay.

Poplar is a valuable tree species that is distributed all over the world. However, many insect pests infest poplar trees and have caused significant damage. To control poplar pests, we transformed a poplar species, Populus davidiana × P. bolleana Loucne, with the dsRNA of the chitinase gene of a poplar defoliator, Clostera anastomosis (Linnaeus) (Lepidoptera: Notodontidae), employing an Agrobaterium-mediated approach. The transgenic plant has been identified by cloning the T-DNA flanking sequences using TAIL-PCR and quantifying the expression of the dsRNA using qPCR. The toxicity assay of the transgenic poplar lines was carried out by feeding the target insect species (C. anastomosis). The results showed that, in C. anastomosis, the activity of chitinase was significantly decreased, consistent with the expression on mRNA levels, and the larval mortality was significantly increased. These results suggested that the transgenic poplar of dsRNA could be used for pest control.

A novel RAV transcription factor from pear interacts with viral RNA-silencing suppressors to inhibit viral infection.

In plants, RNA silencing constitutes a strong defense against viral infection, which viruses counteract with RNA-silencing suppressors (RSSs). Understanding the interactions between viral RSSs and host factors is crucial for elucidating the molecular arms race between viruses and host plants. We report that the helicase motif (Hel) of the replicase encoded by apple stem grooving virus (ASGV)-the main virus affecting pear trees in China-is an RSS that can inhibit both local and systemic RNA silencing, possibly by binding double-stranded (ds) siRNA. The transcription factor related to ABSCISIC ACID INSENSITIVE3/VIVIPAROUS1 from pear (PbRAV1) enters the cytoplasm and binds Hel through its C terminus, thereby attenuating its RSS activity by reducing its binding affinity to 21- and 24-nt ds siRNA, and suppressing ASGV infection. PbRAV1 can also target p24, an RSS encoded by grapevine leafroll-associated virus 2 (GLRaV-2), with similar negative effects on p24's suppressive function and inhibition of GLRaV-2 infection. Moreover, like the positive role of the PbRAV1 homolog from grapevine (VvRAV1) in p24's previously reported RSS activity, ASGV Hel can also hijack VvRAV1 and employ the protein to sequester 21-nt ds siRNA, thereby enhancing its own RSS activity and promoting ASGV infection. Furthermore, PbRAV1 neither interacts with CP, an RSS encoded by grapevine inner necrosis virus, nor has any obvious effect on CP's RSS activity. Our results identify an RSS encoded by ASGV and demonstrate that PbRAV1, representing a novel type of RAV transcription factor, plays a defensive role against viral infection by targeting viral RSSs.

Boron-Doped Single-Molecule van der Waals Diode.

Single-molecule diode was the first proposed device in molecular electronics. Despite the great efforts and advances over 50 years, the reported rectification ratios, the most critical parameter of a diode, remain moderate for the single-molecule diode. Herein, we report an approach to achieve a larger rectification ratio by adopting the combined strategies of p-type boron doping, the single-layer graphene nodes, and the van der Waals layer-by-layer architecture. Measured current-voltage curves showed one of the as-fabricated single-molecule diodes hit an unprecedented large rectification ratio of 457 at ±1 V. Break junction operations and spectroscopic measurements revealed the three-atom-thick configuration of the single-molecule diodes. With the experimental and theoretical calculation results, we demonstrated the doped boron atoms induced holes to redistribute the electron density, making the asymmetric coupling at positive and negative biases, and the van der Waals interaction promoted asymmetric coupling and significantly boosted diode performance.

Vesicular neurotransmitters exocytosis monitored by amperometry: theoretical quantitative links between experimental current spikes shapes and intravesicular structures.

Single cell amperometry has proven to be a powerful and well-established method for characterizing single vesicular exocytotic events elicited at the level of excitable cells under various experimental conditions. Nevertheless, most of the reported characteristics are descriptive, being mostly concerned with the morphological characteristics of the recorded current spikes (maximum current intensities, released charge, rise and fall times, etc.) which are certainly important but do not provide sufficient kinetic information on exocytotic mechanisms due to lack of quantitative models. Here, continuing our previous efforts to provide rigorous models rationalizing the kinetic structures of frequently encountered spike types (spikes with unique exponential decay tails and kiss-and-run events), we describe a new theoretical approach enabling a quantitative kinetic modeling of all types of exocytotic events giving rise to current spikes exhibiting exponential decay tails. This model follows directly from the fact that the condensation of long intravesicular polyelectrolytic strands by high concentrations of monocationic neurotransmitter molecules leads to a matrix structure involving two compartments in constant kinetic exchanges during release. This kinetic model has been validated theoretically (direct and inverse problems) and its experimental interest established by the analysis of the amperometric spikes relative to chromaffin and PC12 cells previously published by some of us.

Step-induced double-row pattern of interfacial water on rutile TiO2(110) under electrochemical conditions.

Metal oxides are promising (photo)electrocatalysts for sustainable energy technologies due to their good activity and abundant resources. Their applications such as photocatalytic water splitting predominantly involve aqueous interfaces under electrochemical conditions, but in situ probing oxide-water interfaces is proven to be extremely challenging. Here, we present an electrochemical scanning tunneling microscopy (EC-STM) study on the rutile TiO2(110)-water interface, and by tuning surface redox chemistry with careful potential control we are able to obtain high quality images of interfacial structures with atomic details. It is interesting to find that the interfacial water exhibits an unexpected double-row pattern that has never been observed. This finding is confirmed by performing a large scale simulation of a stepped interface model enabled by machine learning accelerated molecular dynamics (MLMD) with ab initio accuracy. Furthermore, we show that this pattern is induced by the steps present on the surface, which can propagate across the terraces through interfacial hydrogen bonds. Our work demonstrates that by combining EC-STM and MLMD we can obtain new atomic details of interfacial structures that are valuable to understand the activity of oxides under realistic conditions.

Taking Photoacoustic Force into Account in Liquid-Phase Peak Force Infrared Microscopy.

The microscopic structure of the material's solid-liquid interface significantly influences its physicochemical properties. Peak force infrared microscopy (PFIR) is a powerful technique for analyzing these interfaces at the nanoscale, revealing crucial structure-activity relationships. PFIR is recognized for its explicit photothermal signal generation mechanism but tends to overlook other photoinduced forces, which can disturb the obtained infrared spectra, thereby reducing spectral signal-to-noise ratio (SNR) and sensitivity. We have developed a multiphysics-coupled theoretical model to assess the magnitudes of various photoinduced forces in PFIR experiments and have found that the magnitude of the photoacoustic force is comparable to that of the photothermal expansion force in a liquid environment. Our calculations show that through simple modulation of the pulse waveform it is possible to effectively suppress the photoacoustic interference, thereby improving the SNR and sensitivity of PFIR. This work aims to alert researchers to the potential for strong photoacoustic interference in liquid-phase PFIR measurements and enhance the performance of PFIR by clarifying the photoinduced forces entangled in the signals.

Spatial Pattern of Host Tree Size, Rather than of Host Tree Itself, Affects the Infection Likelihood of a Fungal Stem Disease.

The spatial pattern of diseased forest trees is a product of the spatial pattern of host trees and the disease itself. Previous studies have focused on describing the spatial pattern of diseased host trees, and it remains largely unknown whether an antecedent spatial pattern of host/nonhost trees affects the infection pattern of a disease and how large the effect sizes of the spatial pattern of host/nonhost trees and host size are. The results from trivariate random labeling showed that the antecedent pattern of the host ash tree, Fraxinus mandshurica, but not of nonhost tree species, impacted the infection pattern of a stem fungal disease caused by Inonotus hispidus. To investigate the effect size of the spatial pattern of ash trees, we employed the SADIE (Spatial Analysis by Distance IndicEs) aggregation index and clustering index as predictors in the GLMs. Globally, the spatial pattern (vi index) of ash trees did not affect the infection likelihood of the focal tree; however, the spatial pattern of DBH (diameter at breast height) of ash trees significantly affected the infection likelihood of the focal tree. We sampled a series of circular plots with different radii to investigate the spatial pattern effect of host size on the infection likelihood of the focal tree locally. The results showed that the location (patch/gap) of the DBH of the focal tree, rather than that of the focal tree itself, significantly affected its infection likelihood in most plots of the investigated sizes. A meta-analysis was employed to settle the discrepancy between plots of different sizes, which led to results consistent with those of global studies. The results from meta-regression showed that plot size had no significant effects.

A systematic review and meta-analysis of the relative safety and efficacy of treating lower extremity deep vein thrombosis via pharmacomechanical thrombectomy and catheter-directed thrombolysis.

OBJECTIVE: To evaluate the safety and efficacy of pharmacomechanical thrombectomy and catheter-directed thrombolysis (CDT) as approaches to treating deep venous thrombosis of lower extremities (LEDVT). METHODS: The PubMed, Web of Science, Wanfang, Embase, Chinese Science and Technology Journal, Cochrane, and China National Knowledge Infrastructure (CNKI) databases were systematically searched for relevant articles published through October 2023, after which appropriate inclusion and exclusion criteria were used to screen out relevant articles. Review Manager 5.4.1 was used to extract key data from these studies, and pooled analyses were conducted based on mead difference (MD) or odds ratio (OR) values and corresponding 95% confidence interval (CI). Study quality was assessed with the Newcastle-Ottawa scale. TRIAL REGISTRATION: This study has been registered at INPLASY.COM (No. INPLASY2023100075). RESULTS: In total, 31 relevant studies enrolling 2413 patients were included in this meta-analysis, with 1184 and 1229 patients in the AngioJet and CDT groups, respectively. These analyses revealed that the AngioJet group exhibited significantly higher rates of early postoperative deep vein patency (MD = 7.73, 95% CI (3.29, 12.17), p = .0006) and affected limb symptom improvement (MD = 6.31, 95% CI (1.82,10.80), p = .006) relative to the CDT group, whereas no differences in grade II or III thrombus clearance rates (OR = 1.30, 95% CI (0.95, 1.77), p = .10) or changes in thigh circumference before and after treatment (MD = 0.01, 95% CI (-0.80, 0.83), p = .97) were observed. The AngioJet group also exhibited lower urokinase doses (MD = -145.33, 95% CI (-164.28,126.38), p < .00001), shorter thrombolysis time (MD = -2.35, 95% CI(-2.80, -1.90), p < .00001), a less prolonged hospital stay (MD = -3.13, 95% CI(-3.81, -2.45), p < .00001), lower rates of PTS incidence (OR = 0.56, 95% CI(0.36, 0.88), p = .01), and reduced complication rates (OR = 0.51, 95% CI(0.31, 0.83), p = .0007). CONCLUSION: Studies published to date suggest that relative to CDT treatment, pharmacomechanical thrombectomy is associated with improved thrombus clearance, fewer complications, and lower complication rates in LEDVT patients, underscoring the safety and efficacy of this therapeutic strategy.

Associations between Plant-Based Dietary Patterns and Sensory Impairments among Chinese Older Adults: Based on the Chinese Longitudinal Healthy Longevity Survey.

INTRODUCTION: The aim of this study was to investigate the relationship between the plant-based dietary index and vision impairment (VI), hearing impairment (HI), and dual sensory impairment (DSI) among Chinese aged 65 and older. METHODS: Based on the 2018 data from the Chinese Longitudinal Healthy Longevity Survey (CLHLS), a cross-sectional study was conducted on 14,859 samples. The assessment of dietary quality utilized the plant-based diet index (PDI), healthy plant-based diet index (hPDI), and unhealthy plant-based diet index (uPDI). Logistic regression analysis was used to examine the associations between PDIs and sensory impairments. Additionally, restricted cubic spline analysis was utilized to investigate the nonlinear association between PDIs and sensory impairments. RESULTS: Participants in the highest quintile of PDI exhibited reduced prevalence of VI (OR 0.78, 95% CI: 0.67-0.90, ptrend <0.001), HI (OR 0.83, 95% CI: 0.70-0.99, ptrend <0.001), and DSI (OR 0.62, 95% CI: 0.51-0.77, ptrend <0.001) relative to those in the lowest quintile. Moreover, individuals who ranked in the highest quintile for hPDI exhibited a 25% reduced risk of VI disease. Conversely, those in the highest quintile of uPDI were associated with increased prevalence of VI (OR 1.37, 95% CI: 1.17-1.61, ptrend <0.001), HI (OR 1.36, 95% CI: 1.12-1.65, ptrend <0.001), and DSI (OR 1.56, 95% CI: 1.25-1.95, ptrend <0.001). The relationship between PDIs increasing by every 10 units and sensory impairments showed similar patterns. Notably, hPDI demonstrated a nonlinear relationship with HI (pfor nonlinearity = 0.001), while the others exhibited linear associations. CONCLUSION: The increase in PDI and hPDI correlates with a reduced prevalence of one or more sensory impairments. Conversely, an increase in uPDI is associated with an elevated prevalence of multiple sensory impairments. Our study findings emphasize the significance of plant-based food quality, advocating for adherence to a plant-based dietary pattern while reducing the intake of less healthy plant foods and animal-based products.

Boosting Reactive Oxygen Species Generation via Contact-Electro-Catalysis with FeIII-Initiated Self-cycled Fenton System.

Contact Electro-Catalysis (CEC) using commercial dielectric materials in contact-separation cycles with water can trigger interfacial electron transfer and induce the generation of reactive oxygen species (ROS). However, the inherent hydrophobicity of commercial dielectric materials limits the effective reaction sites, and the generated ROS inevitably undergo self-combination to form hydrogen peroxide (H2O2). In typical CEC systems, H2O2 does not further decompose into ROS, leading to suboptimal reaction rates. Addressing the generation and activation of H2O2 is therefore crucial for advancing CEC. Here, we synthesized a catalyst by loading the dielectric material polytetrafluoroethylene (PTFE) onto ZSM-5 (PTFE/ZSM-5, PZ for short), achieving uniform dispersion of the catalyst in water for the first time. The introduction of an FeIII-initiated self-cycling Fenton system (SF-CEC), with the synergistic effects of O2 activation and FeIII-activated H2O2, further enhanced ROS generation. In the FeIII-initiated SF-CEC system, the synergistic effects of ROS and protonated azo dyes enabled nearly 99 % degradation of azo dyes within 10 minutes, a sixfold improvement compared to the CEC system. This represents the fastest degradation rate of methyl orange dye induced by ultrasound to date. Without extra oxidants, this system enabled stable dissolution of precious metals in weakly acidic solutions at room temperature, achieving 80 % gold dissolution within 2 hours, 2.5 times faster than similar CEC systems. This study also corrects the unfavorable perception of CEC applications under acidic conditions, providing new insights for the fields of dye degradation and precious metal recovery.

Broadband and fabrication-tolerant 3-dB couplers with topological valley edge modes.

3-dB couplers, which are commonly used in photonic integrated circuits for on-chip information processing, precision measurement, and quantum computing, face challenges in achieving robust performance due to their limited 3-dB bandwidths and sensitivity to fabrication errors. To address this, we introduce topological physics to nanophotonics, developing a framework for topological 3-dB couplers. These couplers exhibit broad working wavelength range and robustness against fabrication dimensional errors. By leveraging valley-Hall topology and mirror symmetry, the photonic-crystal-slab couplers achieve ideal 3-dB splitting characterized by a wavelength-insensitive scattering matrix. Tolerance analysis confirms the superiority on broad bandwidth of 48 nm and robust splitting against dimensional errors of 20 nm. We further propose a topological interferometer for on-chip distance measurement, which also exhibits robustness against dimensional errors. This extension of topological principles to the fields of interferometers, may open up new possibilities for constructing robust wavelength division multiplexing, temperature-drift-insensitive sensing, and optical coherence tomography applications.

How the secrets behind photocurrents are revealed in Ag-TiO2 heterostructures-based plasmonic photoelectrochemical systems: A collaborative approach of EC-SERS and photoelectrochemical methods.

Plasmon-mediated chemical reactions (PMCR) have garnered growing interest as a promising concept for photocatalysis. However, in electrochemical systems at solid-liquid interfaces, the photo-induced charge transfer on the surface of metal-semiconductor heterostructures involves complex processes and mechanisms, which are still poorly understood. We explore the plasmon-mediated carrier transfer mechanism and the synergistic effect of light and electric fields on Ag-TiO2 heterostructures, through a combination of electrochemical surface-enhanced Raman spectroscopy and photoelectrochemical methods, with para-aminothiophenol (PATP) serving as a probe molecule. The results show that photocurrent responses are dependent on not only excitation wavelengths and applied potentials, but also the irreversibility of redox. The relationship between photocurrent responses and the chemical transformation between PATP and 4,4'-dimercaptoazobenzene is established, reflecting the photo-induced charge transfer of the heterostructures. The collaboration of spectroscopic and photoelectrochemical methods provide valuable insights into the chemical transformation and kinetic information of adsorbed molecules on the heterostructure during PMCR, offering opportunities for modulating of photocatalytic activities of hot carriers.

Case report: Sarcomatoid renal cell carcinoma masquerading as hydronephrosis.

Sarcomatoid renal cell carcinoma (SRCC), a manifestation of sarcomatoid dedifferentiation in renal cell carcinoma, is characterized by elevated invasiveness and a grim prognosis. Typically, SRCC patients present with advanced or metastatic conditions and survival rates rarely extend beyond one year. In this study, we describe a case of SRCC characterized by the patient exhibiting right flank pain without hematuria. Initially, imaging interpretations led to a diagnosis of severe hydronephrosis. Subsequently, an open right nephrectomy post-surgery confirmed the pathology of sarcomatoid renal cell carcinoma.

Fast Nano-IR Hyperspectral Imaging Empowered by Large-Dataset-Free Miniaturized Spatial-Spectral Network.

The emerging field of nanoscale infrared (nano-IR) offers label-free molecular contrast, yet its imaging speed is limited by point-by-point traverse acquisition of a three-dimensional (3D) data cube. Here, we develop a spatial-spectral network (SS-Net), a miniaturized deep-learning model, together with compressive sampling to accelerate the nano-IR imaging. The compressive sampling is performed in both the spatial and spectral domains to accelerate the imaging process. The SS-Net is trained to learn the mapping from small nano-IR image patches to the corresponding spectra. With this elaborated mapping strategy, the training can be finished quickly within several minutes using the subsampled data, eliminating the need for a large-labeled dataset of common deep learning methods. We also designed an efficient loss function, which incorporates the image and spectral similarity to enhance the training. We first validate the SS-Net on an open stimulated Raman-scattering dataset; the results exhibit the potential of 10-fold imaging speed improvement with state-of-the-art performance. We then demonstrate the versatility of this approach on atomic force microscopy infrared (AFM-IR) microscopy with 7-fold imaging speed improvement, even on nanoscale Fourier transform infrared (nano-FTIR) microscopy with up to 261.6 folds faster imaging speed. We further showcase the generalization of this method on AFM-force volume-based multiparametric nanoimaging. This method establishes a paradigm for rapid nano-IR imaging, opening new possibilities for cutting-edge research in materials, photonics, and beyond.

An Unexpected Synthesis of 2-Sulfonylquinolines via Deoxygenative C2-Sulfonylation of Quinoline N-Oxides with Sulfonyl Chlorides.

A mild, efficient and practical protocol for the preparation of 2-sulfonylquinolines through CS2/Et2NH-induced deoxygenative C2-H sulfonylation of quinoline N-oxides with readily available RSO2Cl was developed. The reaction proceeded well under transition-metal-free conditions and exhibited a wide substrate scope and functional group tolerance. The preliminary studies suggested that the nucleophilic sulfonyl sources were generated in situ via the reaction of CS2, Et2NH and sulfonyl chlorides.

An eco-friendly and high-yield extraction of rare earth from the leaching solution of ion adsorbed minerals.

Ion-adsorbed rare earth minerals are rich in medium and heavy rare earth (RE), which are important strategic resources. In this article, a novel approach for the extraction of RE from ion adsorbed minerals was developed. Through a comprehensive assessment of their extraction and separation performance, the hydrophobic deep eutectic solvents (HDES) with a composition of trioctylphosphine oxide (TOPO): dodecanol (LA): 2-thiophenoyltrifluoroacetone (HTTA) = 1:1:1 was determined as the optimal configuration. Under optimized conditions, only RE were extracted by the HDES, while Al, Ca, Mg were not extracted at all. The HDES based extraction obviated the need for diluent such as kerosene, eliminating the generation of impurity removal residues. The RE in the stripping solution could be successfully enriched by saponified lauric acid, achieving an impressive precipitation rate of 99.7%. The RE precipitate underwent further enrichment, resulting in a RE concentration of 176 g/L (REO = 210 g/L). Unlike industrial precipitants such as oxalic acid and ammonium bicarbonate, lauric acid can be effectively recycled, thereby avoiding a large amount of wastewater and carbon dioxide emissions. The obtained RE solution product exhibits high yield and purity, this study provides an eco-friendly and high-yield approach for extracting RE.