Highly Stable Lithium Metal Batteries Enabled by Tuning the Molecular Polarity of Diluents in Localized High-Concentration Electrolytes.

Electrolyte plays a crucial role in ensuring stable operation of lithium metal batteries (LMBs). Localized high-concentration electrolytes (LHCEs) have the potential to form a robust solid-electrolyte interphase (SEI) and mitigate Li dendrite growth, making them a highly promising electrolyte option. However, the principles governing the selection of diluents, a crucial component in LHCE, have not been clearly determined, hampering the advancement of such a type of electrolyte systems. Herein, the diluents from the perspective of molecular polarity are rationally designed and developed. A moderately fluorinated solvent, 1-(1,1,2,2-tetrafluoroethoxy)propane (TNE), is employed as a diluent to create a novel LHCE. The unique molecular structure of TNE enhances the intrinsic dipole moment, thereby altering solvent interactions and the coordination environment of Li-ions in LHCE. The achieved solvation structure not only enhances the bulk properties of LHCE, but also facilitates the formation of more stable anion-derived SEIs featured with a higher proportion of inorganic species. Consequently, the corresponding full cells of both Li||LiFePO4 and Li||LiNi0.8 Co0.1 Mn0.1 O2 cells utilizing Li thin-film anodes exhibit extended long-term stability with significantly improved average Coulombic efficiency. This work offers new insights into the functions of diluents in LHCEs and provides direction for further optimizing the LHCEs for LMBs.

Bacterial interactome disturbance in chronic obstructive pulmonary disease clinical stability and exacerbations.

RATIONALE: Our understanding of airway dysbiosis in chronic obstructive pulmonary disease (COPD) remains incomplete, which may be improved by unraveling the complexity in microbial interactome. OBJECTIVES: To characterize reproducible features of airway bacterial interactome in COPD at clinical stability and during exacerbation, and evaluate their associations with disease phenotypes. METHODS: We performed weighted ensemble-based co-occurrence network analysis of 1742 sputum microbiomes from published and new microbiome datasets, comprising two case-control studies of stable COPD versus healthy control, two studies of COPD stability versus exacerbation, and one study with exacerbation-recovery time series data. RESULTS: Patients with COPD had reproducibly lower degree of negative bacterial interactions, i.e. total number of negative interactions as a proportion of total interactions, in their airway microbiome compared with healthy controls. Evaluation of the Haemophilus interactome showed that the antagonistic interaction networks of this established pathogen rather than its abundance consistently changed in COPD. Interactome dynamic analysis revealed reproducibly reduced antagonistic interactions but not diversity loss during COPD exacerbation, which recovered after treatment. In phenotypic analysis, unsupervised network clustering showed that loss of antagonistic interactions was associated with worse clinical symptoms (dyspnea), poorer lung function, exaggerated neutrophilic inflammation, and higher exacerbation risk. Furthermore, the frequent exacerbators (≥ 2 exacerbations per year) had significantly reduced antagonistic bacterial interactions while exhibiting subtle compositional changes in their airway microbiota. CONCLUSIONS: Bacterial interactome disturbance characterized by reduced antagonistic interactions, rather than change in pathogen abundance or diversity, is a reproducible feature of airway dysbiosis in COPD clinical stability and exacerbations, which suggests that we may target interactome rather than pathogen alone for disease treatment.

Unraveling the Mechanism of Very Initial Dendritic Growth Under Lithium Ion Transport Control in Lithium Metal Anodes.

Lithium metal deposition is strongly affected by the intrinsic properties of the solid-electrolyte interphase (SEI) and working electrolyte, but a relevant understanding is far from complete. Here, by employing multiple electrochemical techniques and the design of SEI and electrolyte, we elucidate the electrochemistry of Li deposition under mass transport control. It is discovered that SEIs with a lower Li ion transference number and/or conductivity induce a distinctive current transition even under moderate potentiostatic polarization, which is associated with the control regime transition of Li ion transport from the SEI to the electrolyte. Furthermore, our findings help reveal the creation of a space-charge layer at the electrode/SEI interface due to the involvement of the diffusion process of Li ions through the SEI, which promotes the formation of dendrite embryos that develop and eventually trigger SEI breakage and the control regime transition of Li ion transport. Our insight into the very initial dendritic growth mechanism offers a bridge toward design and control for superior SEIs.

Application of machine learning in the preoperative radiomic diagnosis of ameloblastoma and odontogenic keratocyst based on cone-beam CT.

OBJECTIVES: Preoperative diagnosis of oral ameloblastoma (AME) and odontogenic keratocyst (OKC) has been a challenge in dentistry. This study uses radiomics approaches and machine learning (ML) algorithms to characterize cone-beam CT (CBCT) image features for the preoperative differential diagnosis of AME and OKC and compares ML algorithms to expert radiologists to validate performance. METHODS: We retrospectively collected the data of 326 patients with AME and OKC, where all diagnoses were confirmed by histopathologic tests. A total of 348 features were selected to train six ML models for differential diagnosis by a 5-fold cross-validation. We then compared the performance of ML-based diagnoses to those of radiologists. RESULTS: Among the six ML models, XGBoost was effective in distinguishing AME and OKC in CBCT images, with its classification performance outperforming the other models. The mean precision, recall, accuracy, F1-score, and area under the curve (AUC) were 0.900, 0.807, 0.843, 0.841, and 0.872, respectively. Compared to the diagnostics by radiologists, ML-based radiomic diagnostics performed better. CONCLUSIONS: Radiomic-based ML algorithms allow CBCT images of AME and OKC to be distinguished accurately, facilitating the preoperative differential diagnosis of AME and OKC. ADVANCES IN KNOWLEDGE: ML and radiomic approaches with high-resolution CBCT images provide new insights into the differential diagnosis of AME and OKC.

Morphology-Dictated Mechanism of Efficient Reaction Sites for Li2O2 Decomposition.

In the pursuit of a highly reversible lithium-oxygen (Li-O2) battery, control of reaction sites to maintain stable conversion between O2 and Li2O2 at the cathode side is imperatively desirable. However, the mechanism involving the reaction site during charging remains elusive, which, in turn, imposes challenges in recognition of the origin of overpotential. Herein, via combined investigations by in situ atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS), we propose a universal morphology-dictated mechanism of efficient reaction sites for Li2O2 decomposition. It is found that Li2O2 deposits with different morphologies share similar localized conductivities, much higher than that reported for bulk Li2O2, enabling the reaction site not only at the electrode/Li2O2/electrolyte interface but also at the Li2O2/electrolyte interface. However, while the mass transport process is more enhanced at the former, the charge-transfer resistance at the latter is sensitively related to the surface structure and thus the reactivity of the Li2O2 deposit. Consequently, for compact disk-like deposits, the electrode/Li2O2/electrolyte interface serves as the dominant decomposition site, which causes premature departure of Li2O2 and loss of reversibility; on the contrary, for porous flower-like and film-like Li2O2 deposits bearing a larger surface area and richer surface-active structures, both the interfaces are efficient for decomposition without premature departure of the deposit so that the overpotential arises primarily from the sluggish oxidation kinetics and the decomposition is more reversible. The present work provides instructive insights into the understanding of the mechanism of reaction sites during the charge process, which offers guidance for the design of reversible Li-O2 batteries.

Effectiveness and safety of opioids on breathlessness and exercise endurance in patients with chronic obstructive pulmonary disease: A systematic review and meta-analysis of randomised controlled trials.

BACKGROUND: Opioids are recommended to treat advanced refractory dyspnoea despite optimal therapy by the American Thoracic Society clinical practice guidelines, while newly published randomised controlled trials of opioids in chronic obstructive pulmonary disease yield conflicting results. AIM: This study aimed to evaluate the effectiveness and safety of opioids for patients with chronic obstructive pulmonary disease. DESIGN: Systematic review and meta-analysis (PROSPERO CRD42021272556). DATA SOURCES: Databases of PubMed, EMBASE and CENTRAL were searched from inception to 2022 for eligible randomised controlled trials. RESULTS: Twenty-four studies including 975 patients, were included. In cross-over studies, opioids improved breathlessness (standardised mean difference, -0.43; 95% CI, -0.55 to -0.30; I2 = 18%) and exercise endurance (standardised mean difference, 0.22; 95% CI, 0.02-0.41; I2 = 70%). However, opioids failed to improve dyspnoea (standardised mean difference, -0.02; 95% CI, -0.22 to 0.19; I2 = 39%) and exercise endurance (standardised mean difference, 0.00; 95% CI, -0.27 to 0.27; I2 = 0%) in parallel control studies that administered sustained-release opioids for more than 1 week. The opioids used in most crossover studies were short-acting and rarely associated with serious adverse effects. Only minor side effects such as dizziness, nausea, constipation and vomiting were identified for short-acting opioids. CONCLUSIONS: Sustained-release opioids did not improve dyspnoea and exercise endurance. Short-acting opioids appeared to be safe, have potential to lessen dyspnoea and improve exercise endurance, supporting benefit in managing episodes of breathlessness and providing prophylactic treatment for exertional dyspnoea.

Noninvasive Prediction of Ki-67 Expression in Hepatocellular Carcinoma Using Machine Learning-Based Ultrasomics: A Multicenter Study.

OBJECTIVES: To investigate the ability of ultrasomics to predict Ki-67 expression in hepatocellular carcinoma (HCC). METHODS: A total of 244 patients from three hospitals were retrospectively recruited (training dataset, n = 168; test dataset, n = 43; and validation dataset, n = 33). Lesion segmentation of the ultrasound images was performed manually by two radiologists. In total, 1409 ultrasomics features were extracted. Feature selection was conducted using the intra-class correlation coefficient, variance threshold, mutual information, and recursive feature elimination plus eXtreme Gradient Boosting. The support vector machine was combined with the learning curve and grid search parameter tuning to construct the clinical, ultrasomics, and combined models. The predictive performance of the models was assessed using the area under the receiver operating characteristic curve (AUC), sensitivity, specificity and accuracy. RESULTS: The ultrasomics model performed well on the training, test, and validation datasets. The AUC (95% confidence interval [CI]) for these datasets were 0.955 (0.912-0.981), 0.861 (0.721-0.947), and 0.665 (0.480-0.819), respectively. The combination of ultrasomics and clinical features significantly improved model performance on all three datasets. The AUC (95% CI), sensitivity, specificity, and accuracy were 0.986 (0.955-0.998), 0.973, 0.840, and 0.869 on the training dataset; 0.871 (0.734-0.954), 0.750, 0.829, and 0.814 on the test dataset; and 0.742 (0.560-0.878), 0.714, 0.808, and 0.788 on the validation dataset, respectively. CONCLUSIONS: Ultrasomics was proved to be a potential noninvasive method to predict Ki-67 expression in HCC.

Revealing the Interaction of Charge Carrier-Phonon Coupling by Quantification of Electronic Properties at the SrTiO3/TiO2 Heterointerface.

Oxide heterointerfaces with high carrier density can interact strongly with the lattice phonons, generating considerable plasmon-phonon coupling and thereby perturbing the fascinating optical and electronic properties, such as two-dimensional electron gas, ferromagnetism, and superconductivity. Here we use infrared-spectroscopic nanoimaging based on scattering-type scanning near-field optical microscopy (s-SNOM) to quantify the interaction of electron-phonon coupling and the spatial distribution of local charge carriers at the SrTiO3/TiO2 interface. We found an increased high-frequency dielectric constant (ε∞ = 7.1-9.0) and charge carrier density (n = 6.5 × 1019 to 1.5 × 1020 cm-3) near the heterointerface. Moreover, quantitative information between the charge carrier density and extension thickness across the heterointerface has been extracted by monochromatic near-field imaging. A direct evaluation of the relationship between the thickness and the interaction of charge carrier-phonon coupling of the heterointerface would provide valuable information for the development of oxide-based electronic devices.

The Role of Water Content of Deep Eutectic Solvent Ethaline in the Anodic Process of Gold Electrode.

Traditional coupling of ligands for gold wet etching makes large-scale applications problematic. Deep eutectic solvents (DESs) are a new class of environment-friendly solvents, which could possibly overcome the shortcomings. In this work, the effect of water content on the Au anodic process in DES ethaline was investigated by combining linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Meanwhile, we employed atomic force microscopy (AFM) to image the evolution of the surface morphology of the Au electrode during its dissolution and passivation process. The obtained AFM data help to explain the observations about the effect of water content on the Au anodic process from the microscopic perspective. High water contents make the occurrence of anodic dissolution of gold at higher potential, but enhances the rate of the electron transfer and gold dissolution. AFM results reveal the occurrence of massive exfoliation, which confirms that the gold dissolution reaction is more violent in ethaline with higher water contents. In addition, AFM results illustrate that the passive film and its average roughness could be tailored by changing the water content of ethaline.

Formation sequence of solid electrolyte interphases and impacts on lithium deposition and dissolution on copper: an in situ atomic force microscopic study.

Copper is the most widely used substrate for Li deposition and dissolution in lithium metal anodes, which is complicated by the formation of solid electrolyte interphases (SEIs), whose physical and chemical properties can affect Li deposition and dissolution significantly. However, initial Li nucleation and growth on bare Cu creates Li nuclei that only partially cover the Cu surface so that SEI formation could proceed not only on Li nuclei but also on the bare region of the Cu surface with different kinetics, which may affect the follow-up processes distinctively. In this paper, we employ in situ atomic force microscopy (AFM), together with X-ray photoelectron spectroscopy (XPS), to investigate how SEIs formed on a Cu surface, without Li participation, and on the surface of growing Li nuclei, with Li participation, affect the components and structures of the SEIs, and how the formation sequence of the two kinds of SEIs, along with Li deposition, affect subsequent dissolution and re-deposition processes in a pyrrolidinium-based ionic liquid electrolyte containing a small amount of water. Nanoscale in situ AFM observations show that sphere-like Li deposits may have differently conditioned SEI-shells, depending on whether Li nucleation is preceded by the formation of the SEI on Cu. Models of integrated-SEI shells and segmented-SEI shells are proposed to describe SEI shells formed on Li nuclei and SEI shells sequentially formed on Cu and then on Li nuclei, respectively. "Top-dissolution" is observed for both types of shelled Li deposits, but the integrated-SEI shells only show wrinkles, which can be recovered upon Li re-deposition, while the segmented-SEI shells are apparently top-opened due to mechanical stresses introduced at the junctions of the top regions and become "dead" SEIs, which forces subsequent Li nucleation and growth in the interstice of the dead SEIs. Our work provides insights into the impact mechanism of SEIs on the initial stage Li deposition and dissolution on foreign substrates, revealing that SEIs could be more influential on Li dissolution and that the spatial integration of SEI shells on Li deposits is important to improving the reversibility of deposition and dissolution cycling.

Clinical spectrum and genetic variations of LMNA-related muscular dystrophies in a large cohort of Chinese patients.

BACKGROUND: LMNA-related muscular dystrophy is caused by mutations in LMNA gene. We aimed to identify genetic variations and clinical features in a large cohort of Chinese patients with LMNA mutations in an attempt to establish genotype-phenotype correlation. METHODS: The clinical presentations of patients with LMNA-related muscular dystrophy were recorded using retrospective and prospective cohort study. LMNA mutation analysis was performed by Sanger sequencing or next-generation sequencing. Mosaicism was detected by personal genome machine amplicon deep sequencing for mosaicism. RESULTS: Eighty-four patients were identified to harbour LMNA mutations. Forty-one of those were diagnosed with LMNA-related congenital muscular dystrophy (L-CMD), 32 with Emery-Dreifuss muscular dystrophy (EDMD) and 11 with limb-girdle muscular dystrophy type 1B (LGMD1B). We identified 21 novel and 29 known LMNA mutations. Two frequent mutations were identified: c.745C>T and c.1357C>T. A correlation between the location of mutation and the clinical phenotype was observed: mutations affecting the head and coil 2A domains mainly occurred in L-CMD, while the coil 2B and Ig-like domains mainly related to EDMD and LGMD1B. We found somatic mosaicism in one parent of four probands. Muscle biopsies revealed 11 of 20 biopsied L-CMD exhibited inflammatory changes, and muscle cell ultrastructure showed abnormal nuclear morphology. CONCLUSIONS: Our detailed clinical and genetic analysis of 84 patients with LMNA-related muscular dystrophy expands clinical spectrum and broadens genetic variations caused by LMNA mutations. We identified 21 novel and 29 known LMNA mutations and found two frequent mutations. A correlation between the location of mutation and the clinical severity was observed. Preliminary data suggested that low-dose corticosteroid treatment may be effective.

Preoperative classification of primary and metastatic liver cancer via machine learning-based ultrasound radiomics.

OBJECTIVE: To investigate the application of machine learning-based ultrasound radiomics in preoperative classification of primary and metastatic liver cancer. METHODS: Data of 114 consecutive histopathologically confirmed patients with liver cancer from January 2018 to November 2019 were retrospectively analyzed. All patients underwent liver ultrasonography within 1 week before hepatectomy or fine-needle biopsy. The liver lesions were manually segmented by two experts using ITK-SNAP software. Seven categories of radiomics features, including first-order, two-dimensional shape, gray-level co-occurrence matrices, gray-level run-length matrix, gray-level size-zone matrix, neighboring gray tone difference matrix, and gray-level dependence matrix, were extracted on the Pyradiomics platform. Fourteen filters were applied to the original images, and derived images were obtained. Then, the dimensions of radiomics features were reduced by least absolute shrinkage and selection operator (Lasso) method. Finally, k-nearest neighbor (KNN), logistic regression (LR), multilayer perceptron (MLP), random forest (RF), and support vector machine (SVM) were employed to distinguish primary liver cancer from metastatic liver cancer by a fivefold cross-validation strategy. The performance of the established model was mainly evaluated by the area under the receiver operating characteristic (ROC) curve (AUC) and accuracy. RESULTS: One thousand four hundred nine radiomics features were extracted from the original images and/or derived images for each patient. The mentioned five machine learning classifiers were able to differentiate primary liver cancer from metastatic liver cancer. LR outperformed other classifiers, with the accuracy of 0.843 ± 0.078 (AUC, 0.816 ± 0.088; sensitivity, 0.768 ± 0.232; specificity, 0.880 ± 0.117). CONCLUSIONS: Machine learning-based ultrasound radiomics features are able to non-invasively distinguish primary liver tumors from metastatic liver tumors. KEY POINTS: • Ultrasound-based radiomics was initially used for preoperative classification of primary versus metastatic liver cancer. • Multiple machine learning-based algorithms with cross-validation strategy were applied to extract machine learning-based ultrasound radiomics features. • Distinction between primary and metastatic tumors was obtained with a sensitivity of 0.768 and a specificity of 0.880.

Gender difference in the association between cough severity and quality of life among patients with postinfectious cough.

BACKGROUND: Despite close link exists between cough severity and quality of life (QoL), whether gender difference is implied in the effect of cough on QoL has not been studied yet. This study primarily aims to investigate whether the association between cough severity and QoL is modified by gender in patients with postinfectious cough. METHODS: Secondary analyses were performed in 180 participants with postinfectious cough in a multisite randomized controlled trial. Baseline demographics, clinical characteristics and score of cough specific quality of life questionnaire (CQLQ) were collected. Linear regression analyses were conducted to examine gender difference in CQLQ score and the association between cough severity and CQLQ score. RESULTS: Difference between women and men was not significant in CQLQ total score in the unadjusted analysis (P = 0.077). Women had a 2.20-point higher CQLQ total score than men (95% confidence interval (CI) 0.11-4.30; P = 0.039), after adjusting for age, cough duration, cough severity, and clinical center. Gender significantly modified the association between cough severity and CQLQ total score (coefficient 1.80, 95% CI 0.29-3.30; P = 0.020), after adjusting for age, cough duration, and study center. An increase of 1-point in cough severity was associated with a 2.55-point (95% CI 1.16-3.95) increase in CQLQ total score in women versus a 1.26-point (95% CI 0.20-2.31) increase in men (P = 0.020). CONCLUSIONS: Female sex may be associated with worse QoL than men, and women's QoL may be more significantly impaired as cough symptom deteriorates. Gender difference should be taken into account in the clinical settings and research of cough and cough related QoL. TRIAL REGISTRATION: Chinese Clinical Trial Registry, ChiCTRTRC12002297. Registered 19 June 2012, http://www.chictr.org.cn/abouten.aspx .

Pneumonia Is Associated with Increased Mortality in Hospitalized COPD Patients: A Systematic Review and Meta-Analysis.

BACKGROUND: Patients with chronic obstructive pulmonary disease (COPD) are at a heightened risk of pneumonia. Whether coexisting community-acquired pneumonia (CAP) can predict increased mortality in hospitalized COPD patients is still controversial. OBJECTIVE: This systematic review and meta-analysis aims to assess the association between CAP and mortality and morbidity in COPD patients hospitalized for acute worsening of respiratory symptoms. METHODS: In this review, cohort studies and case-control studies investigating the impact of CAP in hospitalized COPD patients were retrieved from 4 electronic databases from inception until December 2019. Methodological quality of included studies was assessed using Newcastle-Ottawa Quality Assessment Scale. The primary outcome was mortality. The secondary outcomes included length of hospital stay, need for mechanical ventilation, intensive care unit (ICU) admission, length of ICU stay, and readmission rate. The Mantel-Haenszel method and inverse variance method were used to calculate pooled relative risk (RR) and mean difference (MD), respectively. RESULTS: A total of 18 studies were included. The presence of CAP was associated with higher mortality (RR = 1.85; 95% CI: 1.50-2.30; p < 0.00001), longer length of hospital stay (MD = 1.89; 95% CI: 1.19-2.59; p < 0.00001), more need for mechanical ventilation (RR = 1.48; 95% CI: 1.32-1.67; p < 0.00001), and more ICU admissions (RR = 1.58; 95% CI: 1.24-2.03; p = 0.0002) in hospitalized COPD patients. CAP was not associated with longer ICU stay (MD = 5.2; 95% CI: -2.35 to 12.74; p = 0.18) or higher readmission rate (RR = 1.02; 95% CI: 0.96-1.09; p = 0.47). CONCLUSION: Coexisting CAP may be associated with increased mortality and morbidity in hospitalized COPD patients, so radiological confirmation of CAP should be required and more attention should be paid to these patients.

Cardiac Phenotype-Genotype Associations in DMD/BMD: A Meta-Analysis and Systematic Review.

Cardiac involvement of Duchenne and Becker muscular dystrophies (DMD/BMD) is the most common cause of fatal outcomes. It is still unclear whether some DMD/BMD gene mutations might be predictive of cardiac involvement. In this study, we provide a comprehensive overview on genotypes of cardiac disease in DMD/BMD. We systematically searched the PubMed/Medline, EMBASE and Cochrane electronic databases. Search results were filtered to include only human studies, English language and all dates up to August 2019. We summarized and extensively reviewed all studies that passed the selection criteria and performed a meta-analysis on key genotype parameters of cardiac disease in DMD/BMD. Of 3450 articles scanned, we included 18 studies from 9 regions in the meta-analysis. The pooled studies included 2661 DMD/BMD patients and 1324 DMD/BMD patients with cardiac disease. The most common mutation type was exon deletion, with a pooled frequency of 90% (P < 0.01). In DMD/BMD patients with cardiac dysfunction, a higher frequency of involvement of exons 45 and 46 was found in DMD/BMD patients with cardiac dysfunction. This might be predictive of cardiac involvement in patients with DMD/BMD.

Revisiting the Atomistic Structures at the Interface of Au(111) Electrode-Sulfuric Acid Solution.

Knowledge of atomistic structures at solid/liquid interfaces is essential to elucidate interfacial processes in chemistry, physics, and materials sciences. The (√3 × âˆš7) structure associated with a pair of sharp reversible current spikes in the cyclic voltammogram on a Au(111) electrode in sulfuric acid solution represents one of the most classical ordered structures at electrode/electrolyte interfaces. Although more than 10 adsorption configurations have been proposed in the past four decades, the atomistic structure remains ambiguous and is consequently an open problem in electrochemistry and surface science. Herein, by combining high-resolution electrochemical scanning tuning microscopy, electrochemical infrared and Raman spectroscopies, and, in particular, the newly developed quantitative computational method for electrochemical infrared and Raman spectra, we unambiguously reveal that the adstructure is Au(111)(√3 × âˆš7)-(SO4···w2) with a sulfate anion (SO4*) and two structured water molecules (w2*) in a unit cell, and the crisscrossed [w···SO4···w]n and [w···w···]n hydrogen-bonding network comprises the symmetric adstructure. We further elucidate that the electrostatic potential energy dictates the proton affinity of sulfate anions, leading to the potential-tuned structural transformations. Our work enlightens the structural details of the inner Helmholtz plane and thus advances our fundamental understanding of the processes at electrochemical interfaces.

Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes.

An attractive field of plasmon-mediated chemical reactions (PMCRs) is developing rapidly, but there is still incomplete understanding of how to control the kinetics of such a reaction related to hot carriers. Here, we chose 8-bromoadenine (8BrAd) as a probe molecule of hot electrons to investigate the influence of the electrode potential, laser wavelength, and power on the PMCR kinetics on silver nanoparticle-modified silver electrodes. Plasmonic hot electron-mediated cleavage of the C-Br bond in 8BrAd has been investigated by combining in situ electrochemical surface-enhanced Raman spectroscopy and density functional theory calculations. The experimental and theoretical results reveal that the energy position of plasmon relaxation-generated hot electrons can be modulated conveniently by applied potentials and laser light. This allows the proposal of a mechanism of modulating the matching energy of the hot electron of plasmon relaxation to promote the efficiency of PMCRs in electrochemical interfaces. Our work will be helpful to design surface plasmon resonance photoelectrochemical reactions on metal electrode surfaces of nanostructures with higher efficiency.

SNHG17 upregulates WLS expression to accelerate lung adenocarcinoma progression by sponging miR-485-5p.

BACKGROUND: Long non-coding RNAs (lncRNAs) have been uncovered to be essential regulators in the biological processes of human cancers, including lung adenocarcinoma (LUAD). Recently, small nucleolar RNA host gene 17 (SNHG17) has been identified as one novel oncogenic lncRNA in gastric cancer. However, it remains unclear whether SNHG7 exert functions in LUAD progression. METHODS: The expression levels of SNHG17, miR-485-5p and Wnt ligand secretion mediator (WLS) in LUAD cells was evaluated by RT-qPCR. The effect of SNHG7 silencing on LUAD cell proliferation was assessed by colony formation and EdU assays. The apoptosis of LUAD cells was measured by flow cytometry analysis. Transwell assays were applied to detect cell migration and invasion. The relationship between SNHG17 and miR-485-5p was validated by RIP, RNA pull down and luciferase reporter assays. RESULTS: SNHG17 and WLS were up-regulated in LUAD cell lines. Down-regulation of SNHG17 curbed LUAD cell proliferation, migration and invasion but facilitated apoptosis. SNHG17 acted as miR-485-5p sponge to upregulate WLS expression. CONCLUSION: SNHG17 triggers the progression of LUAD via sponging miR-485-5p to upregulate WLS expression.

Preoperative prediction for pathological grade of hepatocellular carcinoma via machine learning-based radiomics.

OBJECTIVE: To investigate the efficacy of contrast-enhanced computed tomography (CECT)-based radiomics signatures for preoperative prediction of pathological grades of hepatocellular carcinoma (HCC) via machine learning. METHODS: In this single-center retrospective study, data collected from 297 consecutive subjects with HCC were allocated to training dataset (n = 237) and test dataset (n = 60). Manual segmentation of lesion sites was performed with ITK-SNAP, the radiomics features were extracted by the Pyradiomics, and radiomics signatures were synthesized using recursive feature elimination (RFE) method. The prediction models for pathological grading of HCC were established by using eXtreme Gradient Boosting (XGBoost). The performance of the models was evaluated using the AUC along with 95% confidence intervals (CIs) and standard deviation, sensitivity, specificity, and accuracy. RESULTS: The radiomics signatures were found highly efficient for machine learning to differentiate high-grade HCC from low-grade HCC. For the clinical factors, when they were merely applied to train a machine learning model, the model achieved an AUC of 0.6698, along with 95% CI and standard deviation of 0.5307-0.8089 and 0.0710, respectively (sensitivity, 0.6522; specificity, 0.4595; accuracy, 0.5333). Meanwhile, when the radiomics signatures were applied in association with clinical factors to train a machine learning model, the performance of the model remarkably increased with AUC of 0.8014, along with 95% CI and standard deviation of 0.6899-0.9129 and 0.0569, respectively (sensitivity, 0.6522; specificity, 0.7297; accuracy, 0.7000). CONCLUSIONS: The radiomics signatures could non-invasively explore the underlying association between CECT images and pathological grades of HCC. KEY POINTS: • The radiomics signatures may non-invasively explore the underlying association between CECT images and pathological grades of HCC via machine learning. • The radiomics signatures of CECT images may enhance the prediction performance of pathological grading of HCC, and further validation is required. • The features extracted from arterial phase CECT images may be more reliable than venous phase CECT images for predicting pathological grades of HCC.

Theoretical Insight into Coordination Chemistry of Am(VI) and Am(V) with Phenanthroline Ligand: Implications for High Oxidation State Based Minor Actinide Separation.

Despite continuing and burgeoning interest in americium (Am) coordination chemistry in recent years, investigations of the electronic structures and bonding chemistry of high oxidation state americium complexes and their implications for minor actinide separation remain relatively less explored to date. Here, we used density functional theory (DFT) to create high oxidation states of americium but experimentally feasible models of Am(V) and Am(VI) complexes of phenanthroline ligand (DAPhen) as [AmO2(L)]1+/2+ and [AmO3(L)]1+ (L = 2,9-bis[(N,N-dimethyl)-carbonyl]-1,10-phenanthroline (oxo-DAPhen, LO) and 2,9-bis[(N,N-dimethyl)-thio-carbonyl]-1,10-phenanthroline (thio-DAPhen, LS)), meanwhile comparing these with [UO2(L)]2+. On the basis of the calculations, the Am(V) and Am(VI) oxidation state are thermodynamically feasible and can be stabilized by DAPhen ligands. From a comparative study, the strength of thio-DAPhen in the separation of high oxidation state Am emerges better than does oxo-DAPhen, which relates to the nature, energy level, and spatial arrangement of their frontier orbitals. This study provides fundamental knowledge toward understanding the transuranic separations processes, which has implications in designing new, more selective extraction processes for the separation of Am from curium (Cm) as well as lanthanide.