Crystal epitaxy-confined Pd, Ti-bimetallic sites in the MFI zeolite for benzylalcohol oxidation.

A general strategy for confining Pd, Ti-bimetallic sites in the MFI zeolite by crystal epitaxy was developed. The tailored spatial intimacy of the bimetallic sites demonstrated distinct catalytic performance for the oxidation of benzylalcohol. The related mechanism was clarified and afforded a valuable pathway for rational catalyst design.

Microbial-mediated conversion of soil organic carbon co-regulates the evolution of antibiotic resistance.

The influence of organic carbon on the proliferation of antibiotic resistance genes (ARGs) in the soil has been widely documented. However, it is unclear how soil organic carbon (SOC) interacts with the evolution of antibiotic resistance in bacteria. Here, we examined the variations in ARGs abundance during SOC mineralization and explored the microbiological mechanisms and key metabolic pathways involved in their coevolution. The results showed that the SOC mineralization rate was closely correlated with ARGs abundance (p < 0.05). High organic carbon (OC) mineralization was conducive to the occurrence of multidrug resistance genes. For example, multidrug_transporter and mexB increased 2.26 and 7.83 times from the initial level. The competitor (stress) evolutionary strategy model revealed that higher OC inputs drive environmental microorganisms to evolve from stress tolerant to high resistance and strong adaptation. Meta-genomic and transcriptomic analyses revealed that the conversion process of pyruvate to acetyl-CoA to acetate was the critical metabolic pathway for the co-regulation of antibiotic resistance. Gene deletion validation trials have demonstrated that the key functional genes (ackA and pta) involved in this process can modulate the development of vancomycin and multidrug resistance. This outcome provides a preliminary framework for microbial mechanisms that target the co-regulation of microbial OC conversion and the evolution of antibiotic resistance.

Identification of fibronectin type III domain containing 3B as a potential prognostic and therapeutic target for pancreatic cancer: a preliminary analysis.

BACKGROUND: Fibronectin type III domain containing 3B (FNDC3B), a member of the fibronectin type III domain-containing protein family, has been indicated in various malignancies. However, the precise role of FNDC3B in the progression of pancreatic cancer (PC) still remains to be elucidated. METHODS: In this study, we integrated data from the National Center for Biotechnology Information, the Cancer Genome Atlas, Genotype-Tissue Expression database, and Gene Expression Omnibus datasets to analyze FNDC3B expression and its association with various clinicopathological parameters. Subsequently, Gene Ontology and Kyoto Encyclopedia of Genes and Genomes, along with Gene Set Enrichment Analysis (GSEA), single sample Gene Set Enrichment Analysis (ssGSEA) and estimate analysis were recruited to delve into the biological function and immune infiltration based on FNDC3B expression. Additionally, the prognostic estimation was conducted using Cox analysis and Kaplan-Meier analysis. Subsequently, a nomogram was constructed according to the result of Cox analysis to enhance the prognostic ability of FNDC3B. Finally, the preliminary biological function of FNDC3B in PC cells was explored. RESULTS: The study demonstrated a significantly higher expression of FNDC3B in tumor tissues compared to normal pancreatic tissues, and this expression was significantly associated with various clinicopathological parameters. GSEA revealed the involvement of FNDC3B in biological processes and signaling pathways related to integrin signaling pathway and cell adhesion. Additionally, ssGSEA analysis indicated a positive correlation between FNDC3B expression and infiltration of Th2 cells and neutrophils, while showing a negative correlation with plasmacytoid dendritic cells and Th17 cells infiltration. Kaplan-Meier analysis further supported that high FNDC3B expression in PC patients was linked to shorter overall survival, disease-specific survival, and progression-free interval. However, although univariate analysis demonstrated a significant correlation between FNDC3B expression and prognosis in PC patients, this association did not hold true in multivariate analysis. Finally, our findings highlight the crucial role of FNDC3B expression in regulating proliferation, migration, and invasion abilities of PC cells. CONCLUSION: Despite limitations, the findings of this study underscored the potential of FNDC3B as a prognostic biomarker and its pivotal role in driving the progression of PC, particularly in orchestrating immune responses.

Sarcopenia in peripheral arterial disease: Establishing and validating a predictive nomogram based on clinical and computed tomography angiography indicators.

Purpose: To establish, validate, and clinically evaluate a nomogram for predicting the risk of sarcopenia in patients with peripheral arterial disease (PAD) based on clinical and lower extremity computed tomography angiography (LE-CTA) imaging characteristics. Methods: Clinical data and CTA imaging features from 281 PAD patients treated between January 1, 2019, and May 1, 2023, at two hospitals were retrospectively analyzed using binary logistic regression to identify the independent risk factors for sarcopenia. These identified risk factors were used to develop a predictive nomogram. The nomogram's effectiveness was assessed through various metrics, including the receiver operating characteristic (ROC) curve, area under the curve (AUC), concordance index (C-index), Hosmer-Lemeshow (HL) test, and calibration curve. Its clinical utility was demonstrated using decision curve analysis (DCA). Results: Several key independent risk factors for sarcopenia in PAD patients were identified, namely age, body mass index (BMI), history of coronary heart disease (CHD), and white blood cell (WBC) count, as well as the severity of luminal stenosis (P < 0.05). The discriminative ability of the nomogram was supported by the C-index and an AUC of 0.810 (95% confidence interval: 0.757-0.862). A robust concordance between predicted and observed outcomes was reflected by the calibration curve. The HL test further affirmed the model's calibration with a P-value of 0.40. The DCA curve validated the nomogram's favorable clinical utility. Lastly, the model underwent internal validation. Conclusions: A simple nomogram based on five independent factors, namely age, BMI, history of CHD, WBC count, and the severity of luminal stenosis, was developed to assist clinicians in estimating sarcopenia risk among PAD patients. This tool boasts impressive predictive capabilities and broad utility, significantly aiding clinicians in identifying high-risk individuals and enhancing the prognosis of PAD patients.

Survival benefit of adjuvant chemotherapy in patients with resected gallbladder adenocarcinoma: An updated retrospective cohort analysis.

BACKGROUND: The rarity yet high malignancy of gallbladder adenocarcinoma (GBA) endows it with a distinctive nature. Radical resection remains the foremost therapeutic approach for GBA, while the impact of early recurrence and metastasis on patient prognosis necessitates the utilization of adjuvant chemotherapy (AC). Despite numerous previous studies on this topic, a consensus regarding the authentic efficacy of AC has yet to be reached. METHODS: We conducted an updated retrospective cohort analysis utilizing data from the Surveillance, Epidemiology, and End Results (SEER) database spanning from 2010 to 2020 to explore the association between AC and survival outcomes in patients with resected GBA. RESULTS: Our study included 2782 patients from the SEER database, with further evaluation of 843 patients in each cohort following meticulous execution of a 1:1 propensity score matching. Remarkably, the AC cohort exhibited a significant survival advantage when juxtaposed against the non-AC cohort. Multivariable Cox regression analysis identified age at diagnosis, year at diagnosis, grade, AJCC T stage, AJCC N stage as well as AC as independent prognostic factors. Furthermore, our findings unveiled that poor/undifferentiated tumor histology, pathological T2 or higher category and pathological N1 category were significantly associated with improved survival when treated with AC while simultaneously observing improved survival across all age categories. CONCLUSION: These results provide additional evidence supporting the survival benefits of AC and offer guidance for personalized therapy in patients with resected GBA.

OTUB1 Targets CHK1 for Deubiquitination and Stabilization to Facilitate Lung Cancer Progression and Radioresistance.

PURPOSE: Radioresistance of lung cancer poses a significant challenge when it comes to the treatment of advanced, recurrent, and metastatic cases. Ovarian tumor domain ubiquitin aldehyde binding 1 (OTUB1) is a key member of the deubiquitinase OTU superfamily. This protein is involved in various cellular functions, including cell proliferation, iron death, lipid metabolism, and cytokine secretion as well as immune response processes. However, its specific role and molecular mechanism in lung cancer radioresistance remain to be clarified. METHODS AND MATERIALS: The expression levels of OTUB1 in paired lung cancer tissues were determined by immunohistochemistry. In vitro and in vivo experiments were conducted to investigate the impact of OTUB1 on the growth and proliferation of lung cancer. Coimmunoprecipitation and Western blotting techniques were performed to examine the interaction between OTUB1 and CHK1. The DNA damage response was measured by comet tailing and immunofluorescence staining. KEGG pathways and Gene Ontology terms were analyzed based on RNA sequencing. RESULTS: Our findings reveal a high frequency of OTUB1 overexpression, which is associated with an unfavorable prognosis in patients with lung cancer. Through comprehensive investigations, we demonstrate that OTUB1 depletion impairs the process of DNA damage repair and overcomes radioresistance. In terms of the underlying mechanism, our study uncovers that OTUB1 deubiquitinates and stabilizes CHK1, which enhances CHK1 stability, thereby regulating DNA damage and repair. Additionally, we identify CHK1 as the primary downstream effector responsible for mediating the functional effects exerted by OTUB1 specifically in lung cancer. Importantly, OTUB1 has the potential to be a valuable marker for improving the efficacy of radiation therapy for lung adenocarcinoma. CONCLUSIONS: These findings unveil a novel role for OTUB1 in enhancing radioresistance by deubiquitination and stabilization of the expression of CHK1 in lung cancer and indicate that targeting OTUB1 holds great potential as an effective therapeutic approach for enhancing the efficacy of radiation therapy in lung cancer.

Extracellular Matrix Disorganization Caused by ADAMTS16 Deficiency Leads to Bicuspid Aortic Valve With Raphe Formation.

BACKGROUND: A better understanding of the molecular mechanism of aortic valve development and bicuspid aortic valve (BAV) formation would significantly improve and optimize the therapeutic strategy for BAV treatment. Over the past decade, the genes involved in aortic valve development and BAV formation have been increasingly recognized. On the other hand, ADAMTS (a disintegrin and metalloproteinase with thrombospondin motifs) gene family members have been reported to be able to modulate cardiovascular development and diseases. The present study aimed to further investigate the roles of ADAMTS family members in aortic valve development and BAV formation. METHODS: Morpholino-based ADAMTS family gene-targeted screening for zebrafish heart outflow tract phenotypes combined with DNA sequencing in a 304 cohort BAV patient registry study was initially carried out to identify potentially related genes. Both ADAMTS gene-specific fluorescence in situ hybridization assay and genetic tracing experiments were performed to evaluate the expression pattern in the aortic valve. Accordingly, related genetic mouse models (both knockout and knockin) were generated using the CRISPR/Cas9 (clustered regularly interspaced short palindromic repeats/clustered regularly interspaced short palindromic repeat-associated 9) method to further study the roles of ADAMTS family genes. The lineage-tracing technique was used again to evaluate how the cellular activity of specific progenitor cells was regulated by ADAMTS genes. Bulk RNA sequencing was used to investigate the signaling pathways involved. Inducible pluripotent stem cells derived from both BAV patients and genetic mouse tissue were used to study the molecular mechanism of ADAMTS. Immunohistochemistry was performed to examine the phenotype of cardiac valve anomalies, especially in the extracellular matrix components. RESULTS: ADAMTS genes targeting and phenotype screening in zebrafish and targeted DNA sequencing on a cohort of patients with BAV identified ADAMTS16 (a disintegrin and metalloproteinase with thrombospondin motifs 16) as a BAV-causing gene and found the ADAMTS16 p. H357Q variant in an inherited BAV family. Both in situ hybridization and genetic tracing studies described a unique spatiotemporal pattern of ADAMTS16 expression during aortic valve development. Adamts16+/- and Adamts16+/H355Q mouse models both exhibited a right coronary cusp-noncoronary cusp fusion-type BAV phenotype, with progressive aortic valve thickening associated with raphe formation (fusion of the commissure). Further, ADAMTS16 deficiency in Tie2 lineage cells recapitulated the BAV phenotype. This was confirmed in lineage-tracing mouse models in which Adamts16 deficiency affected endothelial and second heart field cells, not the neural crest cells. Accordingly, the changes were mainly detected in the noncoronary and right coronary leaflets. Bulk RNA sequencing using inducible pluripotent stem cells-derived endothelial cells and genetic mouse embryonic heart tissue unveiled enhanced FAK (focal adhesion kinase) signaling, which was accompanied by elevated fibronectin levels. Both in vitro inducible pluripotent stem cells-derived endothelial cells culture and ex vivo embryonic outflow tract explant studies validated the altered FAK signaling. CONCLUSIONS: Our present study identified a novel BAV-causing ADAMTS16 p. H357Q variant. ADAMTS16 deficiency led to BAV formation.

Association between the sarcopenia index and abnormal liver function in the adult population in the United States: a cross-sectional study.

Background: The objective of this study was to explore the association between the sarcopenia index and abnormal liver function in adult individuals in the United States. Methodology: This study employed a rigorous cross-sectional analysis of data derived from the National Health and Nutrition Examination Survey (NHANES) conducted between 2017 and 2018. The primary objective was to investigate the correlation between the sarcopenia index and abnormal liver function. To achieve this, an advanced multivariate regression model was utilized, allowing for comprehensive analysis and meticulous adjustment of relevant variables. To ensure the robustness of the findings, a visually appealing smooth curve was constructed, and a two-stage regression model was applied for validation. Additionally, a detailed gender-stratified analysis was conducted to further explore the association between the sarcopenia index and abnormal liver function within distinct subgroups. Results: Through our rigorous participant selection process, a total of 1756 individuals were included in the study. The meticulously adjusted multivariate regression model revealed a significant negative association between the sarcopenia index and abnormal liver function, with an adjusted odds ratio (OR) of 0.73 and a 95% confidence interval (CI) ranging from 0.63 to 0.86. The robustness of this association was further supported by the visually appealing smooth curve plot. Moreover, in the gender-stratified subgroup analysis, after meticulous adjustment for confounding factors, notable differences in this association emerged (males: OR = 0.8, 95% CI: 0.66-0.98; females: OR = 0.61, 95% CI: 0.47-0.79). Conclusion: This cross-sectional study yields robust evidence indicating a negative correlation between the sarcopenia index and abnormal liver function, predominantly observed among females.

Engineering a Cl- -Modulated Light-Driven Na+ Pump.

Microbial Na+ -pumping rhodopsin (NaR) is a promising optogenetic tool due to its unique ability to transport Na+ . Like most rhodopsin-based tools, NaR is limited to light-based control. In this study, our objective was to develop a novel mode of modulation for NaR beyond light control. By introducing a potential Cl- binding site near the putative Na+ release cavity, we engineered Nonlabens dokdonensis rhodopsin 2 (NdR2) to be modulated by Cl- , an essential chemical in organisms. The engineered NdR2 demonstrated an approximately two-fold increase in Na+ pump activity in the presence of 100 mM Cl- compared to Cl- -free solution. Increasing Cl- concentration decreased the lifetimes of the M and O intermediates accordingly. The analysis of competitive ion uptake suggested the bound Cl- may increase the Na+ affinity and selectivity. This chemical modulation allows for more diverse and precise control over cellular processes, advancing the development of next-generation optogenetic tools. Notably, our Cl- -modulated NdR2 establishes an innovative mechanism for linking Cl- to Na+ -related processes, with potential applications in optogenetic therapies for related diseases.

K+-Dependent Photocycle and Photocurrent Reveal the Uptake of K+ in Light-Driven Sodium Pump.

Engineering light-controlled K+ pumps from Na+-pumping rhodopsins (NaR) greatly expands the scope of optogenetic applications. However, the limited knowledge regarding the kinetic and selective mechanism of K+ uptake has significantly impeded the modification and design of light-controlled K+ pumps, as well as their practical applications in various fields, including neuroscience. In this study, we presented K+-dependent photocycle kinetics and photocurrent of a light-driven Na+ pump called Nonlabens dokdonensis rhodopsin 2 (NdR2). As the concentration of K+ increased, we observed the accelerated decay of M intermediate in the wild type (WT) through flash photolysis. In 100 mM KCl, the lifetime of the M decay was approximately 1.0 s, which shortened to around 0.6 s in 1 M KCl. Additionally, the K+-dependent M decay kinetics were also observed in the G263W/N61P mutant, which transports K+. In 100 mM KCl, the lifetime of the M decay was approximately 2.5 s, which shortened to around 0.2 s in 1 M KCl. According to the competitive model, in high KCl, K+ may be taken up from the cytoplasmic surface, competing with Na+ or H+ during M decay. This was further confirmed by the K+-dependent photocurrent of WT liposome. As the concentration of K+ increased to 500 mM, the amplitude of peak current significantly dropped to approximately ~60%. Titration experiments revealed that the ratio of the rate constant of H+ uptake (kH) to that of K+ uptake (kK) is >108. Compared to the WT, the G263W/N61P mutant exhibited a decrease of approximately 40-fold in kH/kK. Previous studies focused on transforming NaR into K+ pumps have primarily targeted the intracellular ion uptake region of Krokinobacter eikastus rhodopsin 2 (KR2) to enhance K+ uptake. However, our results demonstrate that the naturally occurring WT NdR2 is capable of intracellular K+ uptake without requiring structural modifications on the intracellular region. This discovery provides diverse options for future K+ pump designs. Furthermore, we propose a novel photocurrent-based approach to evaluate K+ uptake, which can serve as a reference for similar studies on other ion pumps. In conclusion, our research not only provides new insights into the mechanism of K+ uptake but also offers a valuable point of reference for the development of optogenetic tools and other applications in this field.

Na+ Binding and Transport: Insights from Light-Driven Na+-Pumping Rhodopsin.

Na+ plays a vital role in numerous physiological processes across humans and animals, necessitating a comprehensive understanding of Na+ transmembrane transport. Among the various Na+ pumps and channels, light-driven Na+-pumping rhodopsin (NaR) has emerged as a noteworthy model in this field. This review offers a concise overview of the structural and functional studies conducted on NaR, encompassing ground/intermediate-state structures and photocycle kinetics. The primary focus lies in addressing key inquiries: (1) unraveling the translocation pathway of Na+; (2) examining the role of structural changes within the photocycle, particularly in the O state, in facilitating Na+ transport; and (3) investigating the timing of Na+ uptake/release. By delving into these unresolved issues and existing debates, this review aims to shed light on the future direction of Na+ pump research.

Long-distance migration law of radon in overburden of abandoned goaf during coal spontaneous combustion.

The surface isotope radon measurement method (SIRMM) is widely used in fire source detection in abandoned mines. However, studies on the long-distance migration of radon during coal spontaneous combustion are lacking, which hinders the further popularization of this technology in coal fire prevention and control. For this reason, the migration law of radon in overlying strata in fire areas was studied through experiments and numerical simulation. The radon exhalation concentration of coal was found to increase at first and then decrease in the range of 30-350 °C through experiments. The radon concentration reaches the maximum value (557.1 Bq/m3) at 150 °C, which is 6.3 times higher than that at 30 °C. Based on the radon source term obtained by fitting the experimental data, the radon migration model of coal spontaneous combustion in abandoned goaf was constructed, and the dynamic distribution characteristics of the airflow, temperature, and radon concentration fields in the overlying strata area were analyzed. The internal relationship between surface radon and underground fire source was discussed. The simulation results revealed the sharp change in the porosity of the overlying rock causes radon concentration at the interface between the caving and fissure zones to increase continually with the process of spontaneous combustion, providing material and energy support for the long-distance radon migration. When the maximum temperature of the coal pile reaches 70 °C, the concentration of radon released from the coal pile increases rapidly to 13696 Bq/m3, and the radon from the underground space appears on the surface at this temperature. In the range of 70-150 °C, with rapid increase in radon released from coal piles, the surface concentration of radon also increased rapidly to 225 Bq/m3. At the high-temperature stage exceeding 150 °C, the concentration of radon released from coal piles exhibited a downward trend, resulting in a decrease in the rate of increase of radon concentration on the surface. A close relationship between the surface radon concentration and underground fire source temperature in the process of coal spontaneous combustion was observed. In the spatial position, the peak position of radon on the surface was highly consistent with that of the fire source longitudinally, which ensures the accuracy of the SIRMM to determine the location of the hidden fire source. This suggests that the SIRMM can accurately evaluate the fire source's temperature and fire area's development trend.

The potent BECN2-ATG14 coiled-coil interaction is selectively critical for endolysosomal degradation of GPRASP1/GASP1-associated GPCRs.

ABBREVIATIONS: AMBRA1 autophagy and beclin 1 regulator 1; ATG14 autophagy related 14; ATG5 autophagy related 5; ATG7 autophagy related 7; BECN1 beclin 1; BECN2 beclin 2; CC coiled-coil; CQ chloroquine CNR1/CB1R cannabinoid receptor 1 DAPI 4',6-diamidino-2-phenylindole; dCCD delete CCD; DRD2/D2R dopamine receptor D2 GPRASP1/GASP1 G protein-coupled receptor associated sorting protein 1 GPCR G-protein coupled receptor; ITC isothermal titration calorimetry; IP immunoprecipitation; KD knockdown; KO knockout; MAP1LC3/LC3 microtubule associated protein 1 light chain 3; NRBF2 nuclear receptor binding factor 2; OPRD1/DOR opioid receptor delta 1 PIK3C3/VPS34 phosphatidylinositol 3-kinase catalytic subunit type 3; PIK3R4/VPS15 phosphoinositide-3-kinase regulatory subunit 4; PtdIns3K class III phosphatidylinositol 3-kinase; PtdIns3P phosphatidylinositol-3-phosphate; RUBCN rubicon autophagy regulator; SQSTM1/p62 sequestosome 1; UVRAG UV radiation resistance associated; VPS vacuolar protein sorting; WT wild type.

A Nomogram-Based Model for Predicting the Risk of Severe Acute Cholangitis Occurrence.

Background: Acute cholangitis is a severe inflammatory disease associated with an infection of the biliary system, which can lead to complications and adverse outcomes. The existing nomogram-based risk assessment methods largely rely on a limited set of clinical features and laboratory indicators, and are mostly constructed using univariable models, which have limitations in predicting the severity. This study aims to develop a nomogram-based model that integrates multiple variables to improve risk prediction for acute cholangitis. Methods: Data were retrospectively collected from 152 patients with acute cholangitis who attended the People's Hospital of Jiangsu University between January 2019 and March 2022, and were graded as having mild to moderate versus severe cholangitis according to the 2018 Tokyo guidelines. Univariate and multivariate analyses were employed to discern independent risk factors associated with severe acute cholangitis, which were subsequently integrated into a nomogram model. The efficacy of the model was appraised by leveraging Receiver Operating Characteristic (ROC) curves, calibration curves, and Decision Curve Analysis (DCA). Results: Aspartate to alanine transaminase ratio (Transaminase ratio or TR), Neutrophil-lymphocyte ratio (NLR), C-reactive protein (CRP), and D-dimer (DD) levels were independent risk factors for severe acute cholangitis. A nomogram model was constructed based on these 4 risk factors. ROC and calibration curves were well differentiated and calibrated. DCA had a high net gain in the range of 7% to 83%. The above model was tested internally. According to the nomogram model when patients using characteristic curve critical values were divided into a low-risk group and a high-risk group, the incidence in the high-risk group was significantly higher than in the low-risk group. Conclusion: This nomogram model may provide clinicians with an effective tool to predict the potential risk of severe acute cholangitis in patients and guide informed intervention measures and treatment decisions.

Discovery of novel TRPV1 modulators through machine learning-based molecular docking and molecular similarity searching.

The transient receptor potential vanilloid 1 (TRPV1) channel belongs to the transient receptor potential channel superfamily and participates in many physiological processes. TRPV1 modulators (both agonists and antagonists) can effectively inhibit pain caused by various factors and have curative effects in various diseases, such as itch, cancer, and cardiovascular diseases. Therefore, the development of TRPV1 channel modulators is of great importance. In this study, the structure-based virtual screening and ligand-based virtual screening methods were used to screen compound databases respectively. In the structure-based virtual screening route, a full-length human TRPV1 protein was first constructed, three molecular docking methods with different precisions were performed based on the hTRPV1 structure, and a machine learning-based rescoring model by the XGBoost algorithm was constructed to enrich active compounds. In the ligand-based virtual screening route, the ROCS program was used for 3D shape similarity searching and the EON program was used for electrostatic similarity searching. Final 77 compounds were selected from two routes for in vitro assays. The results showed that 8 of them were identified as active compounds, including three hits with IC50 values close to capsazepine. In addition, one hit is a partial agonist with both agonistic and antagonistic activity. The mechanisms of some active compounds were investigated by molecular dynamics simulation, which explained their agonism or antagonism.

Research on Electric Field-Induced Catalysis Using Single-Molecule Electrical Measurement.

The role of catalysis in controlling chemical reactions is crucial. As an important external stimulus regulatory tool, electric field (EF) catalysis enables further possibilities for chemical reaction regulation. To date, the regulation mechanism of electric fields and electrons on chemical reactions has been modeled. The electric field at the single-molecule electronic scale provides a powerful theoretical weapon to explore the dynamics of individual chemical reactions. The combination of electric fields and single-molecule electronic techniques not only uncovers new principles but also results in the regulation of chemical reactions at the single-molecule scale. This perspective focuses on the recent electric field-catalyzed, single-molecule chemical reactions and assembly, and highlights promising outlooks for future work in single-molecule catalysis.

New Halide-Based Sodium-Ion Conductors Na3Y2Cl9 Inversely Designed by Building Block Construction.

Due to the excellent ionic conductivity and compatibility with high-voltage cathodes, halide-based superionic conductors as promising electrolytes have received widespread attention. A series of halide-based conductors, including Na3YCl6, are investigated aiming to find new solid electrolytes for sodium-ion batteries. However, Na3YCl6 with high ionic conductivity is meta-stable in thermostability while the stable phase exhibits poor ionic transport properties. In this work, we find that the coplanar formed anionic group (Y2Cl9)3- is the result of a combination of the structural features of the fast ion phase and stable phase of Na3YCl6 by systematic analysis of crystal structures. Aiming to find fast sodium-ion conductors, the three-step structure construction method using functional (Y2Cl9)3- groups as building blocks is proposed, and three new crystal structures in the composition of Na3Y2Cl9 with the space group of P63, Cc, and R32 are obtained. Na+ transport properties, thermostability, and electrochemical window of these structures with various symmetries are investigated by first-principles calculation methods. The results show that the principle to inverse design crystal structures of halides by basic blocks, e.g., anion groups and mobile cations, is proven to be effective and successful. For P63-Na3Y2Cl9 with outstanding transport properties, the simulation results indicate that its superionic behavior is attributed to the coherent diffusion connecting two directions. The synchronization of the migration pathways along the ab plane and the migration pathways along the c direction promotes the Na ion conductivity in Na3Y2Cl9. Our research will promote the understanding of the transport mechanism in halide-based electrolytes, and the structure construction method based on functional basic building blocks and special stacking modes will accelerate the inverse design of inorganic crystal structures.

Quantum decoherence of dark pulses in optical microresonators.

Quantum fluctuations disrupt the cyclic motions of dissipative Kerr solitons (DKSs) in nonlinear optical microresonators and consequently cause timing jitter of the emitted pulse trains. This problem is translated to the performance of several applications that employ DKSs as compact frequency comb sources. Recently, device manufacturing and noise reduction technologies have advanced to unveil the quantum properties of DKSs. Here we investigate the quantum decoherence of DKSs existing in normal-dispersion microresonators known as dark pulses. By virtue of the very large material nonlinearity, we directly observe the quantum decoherence of dark pulses in an AlGaAs-on-insulator microresonator, and the underlying dynamical processes are resolved by injecting stochastic photons into the microresonators. Moreover, phase correlation measurements show that the uniformity of comb spacing of quantum-limited dark pulses is better than 1.2 × 10-16 and 2.5 × 10-13 when normalized to the optical carrier frequencies and repetition frequencies, respectively. Comparing DKSs generated in different material platforms explicitly confirms the advantages of dark pulses over bright solitons in terms of quantum-limited coherence. Our work establishes a critical performance assessment of DKSs, providing guidelines for coherence engineering of chip-scale optical frequency combs.

A Study of the Mechanisms and Characteristics of Fluorescence Enhancement for the Detection of Formononetin and Ononin.

In this work, the origins for the spectral difference between two isoflavones, formononetin (F) and ononin (FG), are revealed via a comparison study of the fluorescence molecular structure. The fluorescence enhancement of FG in hot alkaline conditions is reported for the first time. For F, there is almost no fluorescence under acidic conditions, but when the pH is >4.8, its fluorescence begins to increase due to the deprotonation of 7-OH. Under a pH between 9.3 and 12.0, the anionic form of F produces a strong and stable fluorescence. The fluorescence quantum yield (Yf) of F is measured to be 0.042. FG shows only weak fluorescence in aqueous solutions under a wide range of pH until it is placed in hot alkaline solutions, which is attributed to the cleavage reaction of the γ-pyrone ring in FG. The Yf of FG is determined to be 0.020. Based on the fluorescence sensitization methods of F and FG, the quantitative analysis and detection of two substances can be realized. The limit of the detections for F and FG are 2.60 ng·mL-1 and 9.30 ng·mL-1, respectively. The linear detection ranges of F and FG are 11.7~1860 ng·mL-1 and 14.6~2920 ng·mL-1, respectively. Although the structural relationship between F and FG is glycoside and aglycone, under hot alkaline conditions, the final products after the cleavage and hydrolysis reactions are essentially different. The different fluorescence characteristics between F and FG pave a way for further identification and a quantitative analysis of the corresponding components in Chinese herbal medicine.

Difference Between Screw Cement Filling and Adequate Osteotomy With Thick Liner for Primary Total Knee Arthroplasty in Patients With Rand IIb Tibial Defects.

BACKGROUND: The effectiveness of 2 treatment options, screw-cement fill, and adequate osteotomy with a thick liner, in treating patients with Rand IIb tibial defects (tibial plateau defects to a depth of 5 to 10 millimeters) in primary total knee arthroplasty (TKA) has not yet been demonstrated. Therefore, we performed a retrospective study to evaluate the differences between these 2 treatments. METHODS: We retrospectively analyzed patients who underwent primary TKA for Rand IIb tibial plateau defects from 2015 to 2020 from a department database. Patients were categorized into the screw-cement and thick liner groups based on the different options used to repair tibial defects. We evaluated Knee Society Score, range of motion (ROM), Insall-Salvati index (ISI), and Forgotten Joint Score (FJS) in both groups. We also compared differences in prosthesis survival, stiffness, myasthenia, and joint clicking between the 2 groups at mean 2 years postoperatively (range, 2 to 2.3). A power analysis was performed on the number of cases in the cohort. RESULTS: Postoperative femur-tibia mechanical axis (FTMA) correction was significantly higher in the screw-cement group than in the thick-liner group: 18.8 (±5.6°) versus 15.4 (±5.9°) (P < .01); At mean 2 years after surgery, the American Knee Society Functional Score improvement values were higher in the thick-liner group than in the screw-cement group: 36.3 (±12.4) versus 42.4 (±16.4) (P = .05). Postoperative ISI scores were 0.95 (±0.12) points in the screw-cement group and 0.89 (±0.13) points in the-thick liner group (P = .03). There were no statistically significant differences in the Knee Society Clinical Score, ROM, FJS, stiffness, myasthenia, joint clicking, and revision rate. CONCLUSION: The results of this study showed no significant difference in clinical outcomes between the 2 reconstruction strategies of the screw cement fill technique and the adequate osteotomy and thick liner technique for Rand IIb tibial plateau defects. However, in patients who have FTMA deformities greater than 20° or in younger patients who need to preserve bone volume, we recommend the screw cement filling technique to ensure stable postoperative results and to prepare these patients for possible later surgery.