Scanning Tunneling Spectroscopy Investigation of Au-bis-acetylide Networks on Au(111): The Influence of Metal-Organic Hybridization.

Graphdiyne (GDY) is an appealing two-dimensional carbon material, but the on-surface synthesis of a single layer remains challenging. Demetalation of well-crystalline metal acetylide networks, though in its infancy, provides a new avenue to on-surface synthesized GDY substructures. In spite of the synthetic efforts and theoretical concerns, there are few reports steeped in elaborate characterization of the electronic influence of metalation. In this context, we focused on the surface supported Au-bis-acetylide network, which underwent demetalation after further annealing to form hydrogen-substituted GDY. We made a comprehensive study on the geometric structure and electronic structure and the corresponding demetalized structure on Au(111) through STM, noncontact atomic force microscopy (nc-AFM), scanning tunneling spectroscopy (STS), and density functional theory (DFT) simulations. The bandgap of the Au-bis-acetylide network on Au(111) is measured to be 2.7 eV, while the bandgap of a fully demetalized Au-bis-acetylide network is estimated to be about 4.1 eV. Our findings reveal that the intercalated Au adatoms are positioned closer to the metal surface compared with the organic skeletons, facilitating electronic hybridization between the surface state and unoccupied frontier molecular orbitals of organic components. This leads to an extended conjugation through Au-bis-acetylene bonds, resulting in a reduced bandgap.

Applicability of VGGish embedding in bee colony monitoring: comparison with MFCC in colony sound classification.

Background: Bee colony sound is a continuous, low-frequency buzzing sound that varies with the environment or the colony's behavior and is considered meaningful. Bees use sounds to communicate within the hive, and bee colony sounds investigation can reveal helpful information about the circumstances in the colony. Therefore, one crucial step in analyzing bee colony sounds is to extract appropriate acoustic feature. Methods: This article uses VGGish (a visual geometry group-like audio classification model) embedding and Mel-frequency Cepstral Coefficient (MFCC) generated from three bee colony sound datasets, to train four machine learning algorithms to determine which acoustic feature performs better in bee colony sound recognition. Results: The results showed that VGGish embedding performs better than or on par with MFCC in all three datasets.

Highly Selective On-Surface [2 + 2] Cycloaddition Induced by Hierarchical Metal-Organic Hybrids.

On-surface synthesis of phenylenes is a promising strategy to form extended π-conjugated frameworks but normally lacks selectivity in achieving uniform products. Herein we demonstrate that the debromination reaction of 2,3-dibromophenazine (DBPZ) on Au(111) and Ag(111) surfaces can vary significantly considering the involvement of metal-organic hybrids (MOHs). On Au(111), [2 + 2] and [2 + 2 + 2] cycloadditions facilitate instantaneously upon the debromination occurring, while on Ag(111), several MOHs have been observed under sequential thermal annealing, leading to finally the uniform [2 + 2] cycloaddition product exclusively. By means of scanning tunneling microscopy (STM) and bond-resolved atomic force microscopy (BR-AFM), we have unambiguously depicted the chemical structure of related reaction intermediates and unraveled the undocumented role of hierarchical evolution of MOHs in steering the chemical selectivity.

Anchoring and Reacting On-Surface to Achieve Programmability.

On-surface synthesis has developed into a modern method to fabricate low-dimensional molecular nanostructures with atomic precision. It impresses the chemistry community mostly via its simplicity, selectivity, and programmability during the synthesis. However, an insufficient mechanistic understanding of on-surface reactions and the discriminations in methodologies block it out from the conventional cognition of reaction and catalysis, which inhibits the extensive implication of on-surface synthesis. In this Perspective, we summarize the empirical paradigms of conceptually appealing programmability in on-surface synthesis. We endeavor to deliver the message that the impressive programmability is related to chemical heterogeneity which can also be coded at the molecular level and deciphered by the catalytic surfaces in varying chemical environments as specific chemical selectivity. With the assistance of structure-sensitive techniques, it is possible to recognize the chemical heterogeneity on surfaces to provide insight into the programmable on-surface construction of molecular nanoarchitectures and to reshape the correlation between the mechanistic understanding in on-surface synthesis and conventional chemistry.

Fine Particulate Matter Induces Childhood Asthma Attacks via Extracellular Vesicle-Packaged Let-7i-5p-Mediated Modulation of the MAPK Signaling Pathway.

Fine particulate matter less than 2.5 µm in diameter (PM2.5 ) is a major risk factor for acute asthma attacks in children. However, the biological mechanism underlying this association remains unclear. In the present study, PM2.5 -treated HBE cells-secreted extracellular vesicles (PM2.5 -EVs) caused cytotoxicity in "horizontal" HBE cells and increased the contractility of "longitudinal" sensitive human bronchial smooth muscle cells (HBSMCs). RNA sequencing showed that let-7i-5p is significantly overexpressed in PM2.5 -EVs and asthmatic plasma; additionally, its level is correlated with PM2.5 exposure in children with asthma. The combination of EV-packaged let-7i-5p and the traditional clinical biomarker IgE exhibits the best diagnostic performance (area under the curve [AUC] = 0.855, 95% CI = 0.786-0.923). Mechanistically, let-7i-5p is packaged into PM2.5 -EVs by interacting with ELAVL1 and internalized by both "horizontal" recipient HBE cells and "longitudinal" recipient-sensitive HBSMCs, with subsequent activation of the MAPK signaling pathway via suppression of its target DUSP1. Furthermore, an injection of EV-packaged let-7i-5p into PM2.5 -treated juvenile mice aggravated asthma symptoms. This comprehensive study deciphered the remodeling of the extracellular environment mediated by the secretion of let-7i-5p-enriched EVs during PM2.5 -induced asthma attacks and identified plasma EV-packaged let-7i-5p as a novel predictor of childhood asthma.

Solid-liquid interface reconstruction for sandwich structure metal plate via laser-ultrasonic techniques.

A laser-ultrasonic testing system was built for the purpose of liquid core detection of a moving and inaccessible continuous casting slab. Reflected waves from different solid-liquid interfaces are studied using the simulation model established with the finite element method. The solid-liquid interfaces of a sandwich structure aluminum plate were preliminarily detected and reconstructed using the time of flight data of ultrasound propagated between layers. Multiple equal-interval ultrasonic echoes were detected and analyzed according to the reflection and transmission of elastic waves in the solid-liquid interface. A B-scan map for the sandwich structure sample was obtained to show the difference between echoes reflected from each interface. Interfaces of different samples were used to calculate the interface position with relative error no more than 1.3%.

2D Molecular Sheets of Hydrogen-Bonded Organic Frameworks for Ultrastable Sodium-Ion Storage.

There has been growing research interest in hydrogen bonded organic frameworks (HOFs) by virtue of their great structural crystallinity, large surface areas and porosity. Their potential in electrochemical applications, unfortunately, remains elusive because weak hydrogen bonds would dissociate in solution that eventually compromises the structural integrity. Herein, it is demonstrated that this issue may be overcome by designing and introducing multisite hydrogen bonding within HOFs. 2D molecular sheets are prepared using diaminotriazole as the linkers for the first time. In spite of the molecular thickness (≈1 nm), they are chemically stable and mechanically robust, and have diminished solubility in most polar or nonpolar organic solvents. This solution-stable HOF exhibits an excellent electrochemical performance for Na+ ion storage. In particular, it enables an exceptional cycle life of >10 000 cycles at 1 A g-1 , which is far superior to most other organic electrode materials. Theoretical simulations indicate that the activation barrier for the intralayer or interlayer diffusion of Na+ ions within the organic frameworks is small.