Unlocking the Nitrogen Reduction Electrocatalyst with a Dual-Metal-Boron System: From High-Throughput Screening to Machine Learning.

Recently, dual-metal catalysts have attracted much attention due to their abundant active sites and tunable chemical properties. On the other hand, metal borides have been widely applied in splitting the inert chemical bonds in small molecules (such as N) because of their excellent catalytic performances. As a combination of the above two systems, in this work, 11 kinds of transition metal atoms (TM = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and W) were selected to embed in boron-doped graphene (BG) to construct 66 dual-metal-boron systems, and their performances toward the N reduction reaction (NRR) were examined using first-principles simulations.

Triel Bonds with Methyl Groups as Electron Donors. A Pentacoordinate Carbon Atom.

The triel bond (TrB) formed between Be(CH)/Mg(CH) and TrX (Tr=B, Al, and Ga; X=H, F, Cl, Br, and I) is investigated via the MP2/aug-cc-pVTZ(PP) quantum chemical protocol. The C atoms of the methyl groups in M(CH) are characterized by a negative electrostatic potential and act as an electron donor in a triel bond with the π-hole above the Tr atom of planar TrX. The interaction energy spans a wide range between -2 and -69 kcal/mol.

Clinical Predilection Features of Middle Ear Adenomatous Neuroendocrine Tumors: A Review of 10 Patients and a Special Case Is Attached.

Middle ear adenomatous neuroendocrine tumors (MEANTs) are rare middle ear lesions characterized by nonspecific symptoms, signs, and imaging findings. Diagnosis typically relies on postoperative pathological assessment. This study investigated the diagnostic utility of the predilection sites and clinical characteristics of MEANTs.

Dirhodium(II) complex catalyzed dehydrosilylation of styrenes: theoretical investigations on the mechanism, selectivity, and ligand effects.

The dirhodium(II) complexes with bridging phosphine and OAc ligands showed high reactivity and selectivities in olefin dehydrosilylation. In order to determine the structure of the actual catalyst which cannot be determined experimentally, the geometries of the dirhodium catalyst, the detailed catalytic mechanism, and the stereo- and chemo-selectivities of the title reaction were studied using DFT calculations. The results showed that one OAc group is monodentate and the other is bidentate in the dirhodium catalyst C'.

Strong Triel Bonds with Be as Electron Donor.

A systematic theoretical study was conducted on the triel bonds (TrBs) within the TrX···Be(CO) complexes (Tr = B, Al, Ga, In, Tl; X = H, F, Cl, Br, I). The interaction energies of these systems range between 4 and 38 kcal/mol. The TrB weakens as X becomes more electronegative in the B and Al systems, while the opposite pattern of stronger bonds is observed in the In and Tl analogues.

Triel Bonds between BH/CHBX and M(MDA) (X = H, CN, F, CH, NH; M = Ni, Pd, Pt, MDA = Enolated Malondialdehyde) and Group 10 Transition Metal Electron Donors.

A systematic theoretical study was conducted on the triel bonds (TrB) within the BH∙∙∙M(MDA) and CHBX∙∙∙M(MDA) (M = Ni, Pd, Pt, X = H, CN, F, CH, NH, MDA = enolated malondialdehyde) complexes, with BH and CHBX acting as the electron acceptors and the square-coordinated M(MDA) acting as the electron donor. The interaction energies of these systems range between -4.71 and -33.

Altered Fhod3 expression involved in progressive high-frequency hearing loss via dysregulation of actin polymerization stoichiometry in the cuticular plate.

Age-related hearing loss (ARHL) is a common sensory impairment with complex underlying mechanisms. In our previous study, we performed a meta-analysis of genome-wide association studies (GWAS) in mice and identified a novel locus on chromosome 18 associated with ARHL specifically linked to a 32 kHz tone burst stimulus. Consequently, we investigated the role of Formin Homology 2 Domain Containing 3 (Fhod3), a newly discovered candidate gene for ARHL based on the GWAS results.

Hydrogen-triggered metal filament rupture in Cu-based resistance switches.

Cation-based resistance switches have been considered as promising candidates for memory cells and other novel devices. So far, the most accepted switching processes of such devices are based on the formation/rupture of metallic filaments between two electrodes. Although many recent studies have identified the existence of HO (and resulting -OH groups) in such devices, their effects on the switching process are still unclear.

A Novel Multi-Functional Fluorescence Probe for the Detection of Al/Zn/Cd and its Practical Applications.

A novel multi-functional fluorescence probe HMIC based on hydrazide Schiff base has been successfully synthesized and characterized. It can distinguish Al/Zn/Cd in ethanol, in which fluorescence emission with different colors (blue for Al, orange for Zn, and green for Cd) were presented. The limits of detection of HMIC towards three ions were calculated from the titration curve as 7.

Search for Osme Bonds with π Systems as Electron Donors.

The Osme bond is defined as pairing a Group 8 metal atom as an electron acceptor in a noncovalent interaction with a nucleophile. DFT calculations with the ωB97XD functional consider MO (M = Ru, Os) as the Lewis acid, paired with a series of π electron donors CH, CH, CH, CHN, CHO, and CHS. The calculations establish interaction energies in the range between 9.

Mechanistic insights into photoinduced energy and charge transfer dynamics between magnesium-centered tetrapyrroles and carbon nanotubes.

Functionalizing single-walled carbon nanotubes (SWNTs) with light-harvesting molecules is a facile way to construct donor-acceptor nanoarchitectures with intriguing optoelectronic properties. Magnesium-centered bacteriochlorin (MgBC), chlorin (MgC), and porphyrin (MgP) are a series of tetrapyrrole macrocycles comprising a central metal and four coordinated aromatic or antiaromatic five-membered rings linked by methine units, which show excellent visible light absorption. To delineate the effects of the aromaticity of coordinated rings on the optoelectronic properties of the nanocomposites, the photoinduced energy and charge transfer dynamics between Mg-centered tetrapyrroles and SWNTs are explored.

Near-Infrared Dual-Emission of a Thiolate-Protected Au Nanocluster: Excited States, Nonradiative Rates, and Mechanism.

Both DFT and TD-DFT methods are used to elaborate on the excited-state properties and dual-emission mechanism of a thiolate-protected Au42 nanocluster. A three-state model (S, S, and T) is proposed with respect to the results. The intersystem crossing (ISC) process from S to T benefits from a small reorganization energy due to the similar geometric structures of S and T.

The Tetrel Bonds of Hypervalent Halogen Compounds.

The tetrel bond between PhXFY(TF) (T = C and Si; X = Cl, Br, and I; Y = F and Cl) and the electron donor MCN (M = Li and Na) was investigated at the M06-2X/aug-cc-pVDZ level of theory. As the electronegativity of the halogen atom X increases, the strength of the tetrel bond also increases, but as the electronegativity of the halogen atom Y increases, the strength of the tetrel bond decreases. The magnitude of the interaction energy in most -CF complexes was found to be less than 10 kcal/mol, but to exceed 11 kcal/mol for PhClFCl(CF)⋯NCNa.

Cooperativity between H-bonds and tetrel bonds. Transformation of a noncovalent C⋯N tetrel bond to a covalent bond.

The dimers and trimers formed by imidazole (IM) and FTO (T = C, Si, Ge) are studied by calculations. IM can engage in either a NH⋯O H-bond with FTO or a T⋯N tetrel bond (TB) with the π-hole above the T atom. The latter is a true noncovalent TB for T = C but is a much shorter and stronger covalent bond with FSiO or FGeO.

Metal-Doped CB Monolayer as the Promising Electrocatalyst for Hydrogen/Oxygen Evolution Reaction: A Combined Density Functional Theory and Machine Learning Study.

The development of high-efficiency electrocatalysts for hydrogen evolution reduction (HER)/oxygen evolution reduction (OER) is highly desirable. In particular, metal borides have attracted much attention because of their excellent performances. In this study, we designed a series of metal borides by doping of a transition metal (TM) in a CB monolayer and further explored their potential applications for HER/OER via density functional theory (DFT) calculations and machine learning (ML) analysis.

C∙∙∙O and Si∙∙∙O Tetrel Bonds: Substituent Effects and Transfer of the SiF Group.

The tetrel bond (TB) between 1,2-benzisothiazol-3-one-2-TF-1,1-dioxide (T = C, Si) and the O atom of pyridine-1-oxide (PO) and its derivatives (PO-X, X = H, NO, CN, F, CH, OH, OCH, NH, and Li) is examined by quantum chemical means. The Si∙∙∙O TB is quite strong, with interaction energies approaching a maximum of nearly 70 kcal/mol, while the C∙∙∙O TB is an order of magnitude weaker, with interaction energies between 2.0 and 2.

scMCs: a framework for single-cell multi-omics data integration and multiple clusterings.

Motivation: The integration of single-cell multi-omics data can uncover the underlying regulatory basis of diverse cell types and states. However, contemporary methods disregard the omics individuality, and the high noise, sparsity, and heterogeneity of single-cell data also impact the fusion effect. Furthermore, available single-cell clustering methods only focus on the cell type clustering, which cannot mine the alternative clustering to comprehensively analyze cells.

Social distancing cut down the prevalence of acute otitis media in children.

Objectives: To evaluate the additional, unintended benefits of social distancing in cutting down the prevalence of acute otitis media (AOM) in children, especially during coronavirus disease 2019 (COVID-19) periods.

Methods: The daily outpatient attendance of AOM for childhood (from 6 months to 12 years) was compared in the tertiary hospital in Shanghai during pre-COVID-19 and COVID-19 year.

Results: A total of 24,543 AOM cases were included from 2015 to 2020.

Motion coordination and dexterous manipulation for underwater vehicle-manipulator systems.

This paper addresses the redundancy resolution problem for underwater vehicle-manipulator systems (UVMSs). More specifically, a new redundancy resolution approach with motion coordination and dexterous manipulation is presented to guarantee the tracking accuracy of the end-effector while avoiding singular configurations of the manipulator. The task-priority redundancy resolution framework is adopted to achieve an effective coordinated motion of the vehicle and manipulator while exploiting the redundant degrees of freedom available.

Abnormalities of the Halogen Bonds in the Complexes between YCTe (Y = H, F, CH) and XF (X = F, Cl, Br, I).

In this work, the hydrogen bonds and halogen bonds in the complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I) have been studied by quantum chemical calculations. We found three interesting abnormalities regarding the interactions. Firstly, the strength of halogen bonds increases in the order of IF < BrF < ClF < F2.

Triel Bonds with Au Atoms as Electron Donors.

The novel triel bonds of BX (X=H, F, Cl, Br, and I) and C H B as electron acceptors and AuR (R=Cl and CH ) as an electron donor were explored. The triel bond is a primary driving force for most complexes, while the contribution from a halogen-chlorine interaction in BX -AuCl (X=Cl, Br, and I) and an iodine-Au interaction in BI -Au(CH ) is also very important. Interestingly, the positively charged Au atom of AuCl can attractively bind with the holes of BX and C H B.

Enhancing Interfacial and Electromagnetic Interference Shielding Properties of Carbon Fiber Composites via the Hierarchical Assembly of the MWNT/MOF Interphase.

A metal-organic framework (MOF) based on a conjugated organic ligand and a transition-metal ion was designed and used to construct a novel multiwalled carbon nanotube (MWNT)/MOF interphase via hierarchical assembly on the carbon fiber (CF) surface and was compared to various interphases established by MWNT and MOF. An intertwined MWNT and MOF "jujube core" was randomly dispersed on MWNT@CF and MOF@CF surfaces, while interpenetrating structures with the MWNT network and MOF jujube core were simultaneously observed on MWNT/MOF@CF due to coordination bonds and π-π conjugation effects, which were derived from the MWNT template with carboxyl groups and sp-hybridized domains as well as the secondary growth of MOF to promote self-assembly and the connection of MOF. The transverse fiber bundle test (TFBT) strength and interfacial shear strength (IFSS) of the MWNT/MOF@CF composite were 36.