Hydrogen-Bonded Mesoporous Frameworks with Tunable Pore Sizes and Architectures from Nanocluster Assembly Units.

Construction of mesoporous frameworks by noncovalent bonding still remains a great challenge. Here, we report a micelle-directed nanocluster modular self-assembly approach to synthesize a novel type of two-dimensional (2-D) hydrogen-bonded mesoporous frameworks (HMFs) for the first time based on nanoscale cluster units (1.0-3.

Solvent-Free Synthesis Enables Encapsulation of Subnanometric FeO Clusters in Pure Siliceous Zeolites for Efficient Catalytic Oxidation Reactions.

Metal/metal oxide clusters possess a higher count of unsaturated coordination sites than nanoparticles, providing multiatomic sites that single atoms do not. Encapsulating metal/metal oxide clusters within zeolites is a promising approach for synthesizing and stabilizing these clusters. The unique feature endows the metal clusters with an exceptional catalytic performance in a broad range of catalytic reactions.

Silver and Copper Dual Single Atoms Boosting Direct Oxidation of Methane to Methanol via Synergistic Catalysis.

Rationally constructing atom-precise active sites is highly important to promote their catalytic performance but still challenging. Herein, this work designs and constructs ZSM-5 supported Cu and Ag dual single atoms as a proof-of-concept catalyst (Ag -Cu /ZSM-5 hetero-SAC (single-atom catalyst)) to boost direct oxidation of methane (DOM) by H O . The Ag -Cu /ZSM-5 hetero-SAC synthesized via a modified co-adsorption strategy yields a methanol productivity of 20,115 µmol g with 81% selectivity at 70 °C within 30 min, which surpasses most of the state-of-the-art noble metal catalysts.

Neglected acidity pitfall: boric acid-anchoring hole-selective contact for perovskite solar cells.

The spontaneous formation of self-assembly monolayer (SAM) on various substrates represents an effective strategy for interfacial engineering of optoelectronic devices. Hole-selective SAM is becoming popular among high-performance inverted perovskite solar cells (PSCs), but the presence of strong acidic anchors (such as -POH) in state-of-the-art SAM is detrimental to device stability. Herein, we report for the first time that acidity-weakened boric acid can function as an alternative anchor to construct efficient SAM-based hole-selective contact (HSC) for PSCs.

Atomic Insights into the Cu Species Supported on Zeolite for Direct Oxidation of Methane to Methanol via Low-Damage HAADF-STEM.

Precise determination of the structure-property relationship of zeolite-based metal catalysts is critical for the development toward practical applications. However, the scarcity of real-space imaging of zeolite-based low-atomic-number (LAN) metal materials due to the electron-beam sensitivity of zeolites has led to continuous debates regarding the exact LAN metal configurations. Here, a low-damage high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging technique is employed for direct visualization and determination of LAN metal (Cu) species in ZSM-5 zeolite frameworks.

Identification of SOX6 and SOX12 as Prognostic Biomarkers for Clear Cell Renal Cell Carcinoma: A Retrospective Study Based on TCGA Database.

Background: The SOX gene family has been proven to display regulatory effects on numerous diseases, particularly in the malignant progression of neoplasms. However, the molecular functions and action mechanisms of SOX genes have not been clearly elucidated in clear cell renal cell carcinoma (ccRCC). We aimed to explore the expression status, prognostic values, clinical significances, and regulatory actions of SOX genes in ccRCC.

Accelerating Metadynamics-Based Free-Energy Calculations with Adaptive Machine Learning Potentials.

There is an increasing demand for free-energy calculations using ab initio molecular dynamics these days. Metadynamics (MetaD) is frequently utilized to reconstruct the free-energy surface, but it is often computationally intractable for the first-principles calculations. Machine learning potentials (MLPs) have become popular alternatives.

Perspective on computational reaction prediction using machine learning methods in heterogeneous catalysis.

Heterogeneous catalysis plays a significant role in the modern chemical industry. Towards the rational design of novel catalysts, understanding reactions over surfaces is the most essential aspect. Typical industrial catalytic processes such as syngas conversion and methane utilisation can generate a large reaction network comprising thousands of intermediates and reaction pairs.

A fast species redistribution approach to accelerate the kinetic Monte Carlo simulation for heterogeneous catalysis.

The first-principles kinetic Monte Carlo (kMC) simulation has been demonstrated as a reliable multiscale modeling approach in silico to disclose the interplay among all the elementary steps in a complex reaction network for heterogeneous catalysis. Heterogeneous catalytic systems frequently contain fast surface diffusion processes of some adsorbates while the elementary steps in it would be much slower than those in fast diffusion. Consequently, the kMC simulation for these systems is easily trapped in the sub-basins of a super basin on a potential energy surface due to the continuous and repeated sampling of these fast processes, which would significantly increase the total accessible simulation time and even make it impossible to get the reasonable simulation results using the kMC simulation.

Autografts vs Synthetics for Cruciate Ligament Reconstruction: A Systematic Review and Meta-Analysis.

To describe the outcomes of autografts and synthetics in anterior cruciate ligament (ACL) and posterior cruciate ligament (PCL) reconstruction with respect to instrumented laxity measurements, patient-reported outcome scores, complications, and graft failure risk. We searched PubMed, Cochrane Library, and EMBASE for published randomized controlled trials (RCT) and case controlled trials (CCTs) to compare the outcomes of the autografts versus synthetics after cruciate ligament reconstruction. Data analyses were performed using Cochrane Collaboration RevMan 5.

Structural characterization of self-assembled chain like Fe-FeOx Core shell nanostructure.

One of the big challenge of studying the core-shell iron nanostructures is to know the nature of oxide shell, i.e., whether it is γ-FeO (Maghemite), FeO (Magnetite), α-FeO (Hematite), or FeO (Wustite).

Interface-tuned selective reductive coupling of nitroarenes to aromatic azo and azoxy: a first-principles-based microkinetics study.

It is of great importance to regulate a catalyst to control its selectivity. In general, the Pt catalyzed hydrogenation of nitrobenzene (PhNO) would produce aniline. Yet, when KOH is added, the more value-added N-N coupling products such as aromatic azoxy and azo exhibit better selectivity.

Pumping a Ring-Sliding Molecular Motion by a Light-Powered Molecular Motor.

Designing artificial molecular machines to execute complex mechanical tasks, like coupling rotation and translation to accomplish transmission of motion, continues to provide important challenges. Herein, we demonstrated a novel molecular machine comprising a second-generation light-driven molecular motor and a bistable [1]rotaxane unit. The molecular motor can rotate successfully even in an interlocked [1]rotaxane system through a photoinduced cis-to -trans isomerization and a thermal helix inversion, resulting in concomitant transitional motion of the [1]rotaxane.

Role of miR-337-3p and its target Rap1A in modulating proliferation, invasion, migration and apoptosis of cervical cancer cells.

Objective: To investigate the role of miR-337-3p targeting Rap1A in modulating proliferation, invasion, migration and apoptosis of cervical cancer cells.

Methods: The expression levels of miR-337-3p and Rap1A in cervical cancer tissues and normal tissues were evaluated through quantitative Real-time PCR (qRT-PCR) and Western blotting; and correlations of miR-337-3p with clinicopathological characteristics and prognosis of patients were also analyzed. Besides, human cervical cancer cell line HeLa cells were randomly divided into five groups (Mock, NC, miR-337-3p mimic, Rap1A, and miR-337-3p mimic + Rap1A groups).

Contribution of IL-1β, 6 and TNF-α to the form of post-traumatic osteoarthritis induced by "idealized" anterior cruciate ligament reconstruction in a porcine model.

Background: It has been noted that anterior cruciate ligament (ACL) injury-induced cartilage degeneration is the key risk factor for post-traumatic osteoarthritis (PTOA). However, whether the cartilage degeneration after ACL injury is caused by inflammation, abnormal biomechanics or both remains largely unknown, as there has been no animal model for separating the two factors so far.

Methods: Eighteen-month-old female mini-pigs were divided into an "idealized" anterior cruciate ligament reconstruction (IACLR) group and a control group (n = 16 limbs per group).

White-light emission from a single organic compound with unique self-folded conformation and multistimuli responsiveness.

White-light emitting organic materials attract broad attention which are ascribed to their potential for applications in lighting devices and display media. Most reported organic white-light emitters rely on the combination of several components that emit different colors of light (red/green/blue or orange/blue), which may cause problems to stability, reproducibility and device fabrication. By contrast, white-light emission from single-molecule systems offers opportunities to overcome these disadvantages, meanwhile engendering white-light with high quality.

A tritopic carbanionic N-heterocyclic dicarbene and its homo- and heterometallic coinage metal complexes.

Homo (Au3)- and heterotrinuclear coinage metal complexes (Au2Ag and Au2Cu) ligated by the first tritopic carbanionic N-heterocyclic carbene (NHC) have been prepared by deprotonation of ditopic NHC digold complexes and structurally characterized by single-crystal X-ray diffraction.

Simple Cadmium Sulfide Compound with Stable 95 % Selectivity for Carbon Dioxide Electroreduction in Aqueous Medium.

A simple cadmium sulfide nanomaterial is found to be an efficient and stable electrocatalyst for CO reduction in aqueous medium for more than 40 h with a steady CO faradaic efficiency of approximately 95 %. Moreover, it can realize a current density of -10 mA cm at an overpotential of -0.55 V on a porous substrate with similar selectivity.

Amorphous Metal-Free Room-Temperature Phosphorescent Small Molecules with Multicolor Photoluminescence via a Host-Guest and Dual-Emission Strategy.

Metal-free room-temperature phosphorescence (RTP) materials offer unprecedented potentials for photoelectric and biochemical materials due to their unique advantages of long lifetime and low toxicity. However, the achievements of phosphorescence at ambient condition so far have been mainly focused on ordered crystal lattice or on embedding into rigid matrices, where the preparation process might bring out poor repeatability and limited application. In this research, a series of amorphous organic small molecular compounds were developed with efficient RTP emission through conveniently modifying phosphor moieties to β-cyclodextrin (β-CD).

Visible-Light-Driven Valorization of Biomass Intermediates Integrated with H Production Catalyzed by Ultrathin Ni/CdS Nanosheets.

Photocatalytic upgrading of crucial biomass-derived intermediate chemicals (i.e., furfural alcohol, 5-hydroxymethylfurfural (HMF)) to value-added products (aldehydes and acids) was carried out on ultrathin CdS nanosheets (thickness ∼1 nm) decorated with nickel (Ni/CdS).

Enhancing Metal-Support Interactions by Molybdenum Carbide: An Efficient Strategy toward the Chemoselective Hydrogenation of α,β-Unsaturated Aldehydes.

Metal-support interactions are desired to optimize the catalytic turnover on metals. Herein, the enhanced interactions by using a Mo2C nanowires support were utilized to modify the charge density of an Ir surface, accomplishing the selective hydrogenation of α,β-unsaturated aldehydes on negatively charged Ir(δ-) species. The combined experimental and theoretical investigations showed that the Ir(δ-) species derive from the higher work function of Ir (vs.

Highly selective detection of carbon monoxide in living cells by palladacycle carbonylation-based surface enhanced Raman spectroscopy nanosensors.

A novel nanosensor was explored for the highly selective detection of intracellular carbon monoxide (CO) by surface enhanced Raman spectroscopy (SERS) on the basis of palladacycle carbonylation. By assembling new synthesized palladacycles (PC) on the surface of gold nanoparticles (AuNPs), SERS nanosensors (AuNP/PC) were prepared with good SERS activity and reactivity with CO. When the AuNP/PC nanosensors were incubated with a CO-containing system, carbonylation of the PC assembled on AuNPs was initiated, and the corresponding SERS spectra of AuNP/PC changed significantly, which allowed the carbonylation reaction to be directly observed in situ.

Bridge- and solvent-mediated intramolecular electronic communications in ubiquinone-based biomolecular wires.

Intramolecular electronic communications of molecular wires play a crucial role for developing molecular devices. In the present work, we describe different degrees of intramolecular electronic communications in the redox processes of three ubiquinone-based biomolecular wires (Bis-CoQ0s) evaluated by electrochemistry and Density Functional Theory (DFT) methods in different solvents. We found that the bridges linkers have a significant effect on the electronic communications between the two peripheral ubiquinone moieties and solvents effects are limited and mostly depend on the nature of solvents.

Ultralow-temperature CO oxidation on an In2O3-Co3O4 catalyst: a strategy to tune CO adsorption strength and oxygen activation simultaneously.

Highly efficient In2O3-Co3O4 catalysts were prepared for ultralow-temperature CO oxidation by simultaneously tuning the CO adsorption strength and oxygen activation over a Co3O4 surface, which could completely convert CO to CO2 at temperatures as low as -105 °C compared to -40 °C over pure Co3O4, with enhanced stability.

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution.

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent.