Photocatalytic Oxidative Coupling of Methane to Ethane Using CO2 as a Soft Oxidant Over the Au/TiO2-Vo Nanosheets.

Herein, we first report a photocatalytic OCM using CO2 as a soft oxidant for C2H6 production under mild conditions, where an efficient photocatalyst with unique interface sites is constructed to facilitate CO2 adsorption and activation, while concurrently boosting CH4 dissociation. As a prototype, the Au quantum dots anchored on oxygen-deficient TiO2 nanosheets are fabricated, where the Au-Vo-Ti interface sites for CO2 adsorption and activation are collectively disclosed by in situ Kelvin probe force microscopy, quasi in situ X-ray photoelectron spectroscopy and theoretical calculations. Compared with single metal site, the Au-Vo-Ti interface sites exhibit the lower CO2 adsorption energy and decrease the energy barrier of the *CO2 hydrogenation step from 1.

Electrochemical synthesis of nitrosation compounds using CHNO as a nitroso reagent.

An electrochemical synthesis of various nitroso organic compounds (NOCs) from secondary amines was developed under metal-free and oxidant-free conditions. This method used commercially available nitromethane as the nitrosation reagent to provide various NOCs in good to excellent yields. Furthermore, the valuable drug molecule form desloratadine can be prepared by this method easily.

High-resolution anionic velocity map imaging apparatus for dissociative electron attachment dynamics study.

Dissociative electron attachment (DEA) of a molecular target XY, e- + XY → XY- → X + Y-, is an important process in plasma, atmosphere, interstellar space, and ionizing radiation. DEA dynamics, i.e.

Unexpected and divergent mechanosynthesis of furanoid-bridged fullerene dimers CO and CO.

An unexpected, divergent and efficient approach toward furanoid-bridged fullerene dimers CO and CO was established under different solvent-free ball-milling conditions by simply using pristine C as the starting material, water as the oxygen source and FeCl as the mediator. The structures of CO and CO were unambiguously established by single-crystal X-ray crystallography. A plausible reaction mechanism is proposed on the basis of control experiments.

Technologies for investigating single-molecule chemical reactions.

Single molecules, the smallest independently stable units in the material world, serve as the fundamental building blocks of matter. Among different branches of single-molecule sciences, single-molecule chemical reactions, by revealing the behavior and properties of individual molecules at the molecular scale, are particularly attractive because they can advance the understanding of chemical reaction mechanisms and help to address key scientific problems in broad fields such as physics, chemistry, biology and materials science. This review provides a timely, comprehensive overview of single-molecule chemical reactions based on various technical platforms such as scanning probe microscopy, single-molecule junction, single-molecule nanostructure, single-molecule fluorescence detection and crossed molecular beam.

First-principles studies of gas molecule adsorption on a LaB(100) surface.

First-principles calculations were employed to study the molecular and dissociative adsorption of CO, HO, O and N on a LaB(100) surface. The adsorption energy calculation results indicate that these gas molecules can form thermodynamically stable adsorption structures. Dissociative adsorption is always accompanied by more electron transfer compared to molecular adsorption, which is one of the necessary conditions for dissociation to occur.

Targeting myeloid-derived suppressor cells promotes antiparasitic T-cell immunity and enhances the efficacy of PD-1 blockade (15 words).

Immune exhaustion corresponds to a loss of effector function of T cells that associates with cancer or chronic infection. Here, our objective was to decipher the mechanisms involved in the immune suppression of myeloid-derived suppressor cells (MDSCs) and to explore the potential to target these cells for immunotherapy to enhance checkpoint blockade efficacy in a chronic parasite infection. We demonstrated that programmed cell-death-1 (PD-1) expression was significantly upregulated and associated with T-cell dysfunction in advanced alveolar echinococcosis (AE) patients and in Echinococcus multilocularis-infected mice.

Photothermal CO conversion to ethanol through photothermal heterojunction-nanosheet arrays.

Photothermal CO conversion to ethanol offers a sustainable solution for achieving net-zero carbon management. However, serious carrier recombination and high C-C coupling energy barrier cause poor performance in ethanol generation. Here, we report a Cu/CuSe-CuO heterojunction-nanosheet array, showcasing a good ethanol yield under visible-near-infrared light without external heating.

From 2e- to 4e- pathway in the alkaline oxygen reduction reaction on Au(100): Kinetic circumvention of the volcano curve.

We report the free energy barriers for the elementary reactions in the 2e- and 4e- oxygen reduction reaction (ORR) steps on Au(100) in an alkaline solution. Due to the weak adsorption energy of O2 on Au(100), the barrier for the association channel is very low, and the 2e- pathway is clearly favored, while the barrier for the O-O dissociation channel is significantly higher at 0.5 eV.

Synthesis and Photophysical Properties of a Chiral Carbon Nanoring Containing Rubicene.

Herein we report the construction of an inherently chiral carbon nanoring, cyclo[7]paraphenylene-2,9-rubicene (), by combining rubicene with a C-shaped synthon through the Suzuki-Miyaura coupling reaction. The structure was fully confirmed by high-resolution mass spectroscopies (HR-MS) and various NMR techniques. The photophysical properties were investigated by UV-vis absorption and fluorescence spectroscopy as well as the time-resolved fluorescence decay.

Unraveling the Unique Strong Metal-Support Interaction in Titanium Dioxide Supported Platinum Clusters for the Hydrogen Evolution Reaction.

Strong metal-support interaction (SMSI) is crucial to modulating the nature of metal species, yet the SMSI behaviors of sub-nanometer metal clusters remain unknown due to the difficulties in constructing SMSI at cluster scale. Herein, we achieve the successful construction of the SMSI between Pt clusters and amorphous TiO nanosheets by vacuum annealing, which requires a relatively low temperature that avoids the aggregation of small clusters. In situ scanning transmission electron microscopy observation is employed to explore the SMSI behaviors, and the results reveal the dynamic rearrangement of Pt atoms upon annealing for the first time.

Metallic Ru─Ru Interaction in Ruthenium Oxide Enabling Durable Proton Exchange Membrane Water Electrolysis.

Developing efficient and robust electrocatalysts toward the oxygen evolution reaction (OER) is critical for proton exchange membrane water electrolysis (PEMWE). RuO possesses intrinsically high OER activity, but the concurrent electrochemical dissolution leads to rapid deactivation. Here a unique RuO catalyst containing metallic Ru─Ru interactions (m-RuO) is reported, which maintains stability in practical PEMWE for 100 h at 60 °C and 1 A cm.

Breaking the Activity-Selectivity Trade-off for CH-to-CH Photoconversion.

Photocatalytic conversion of methane (CH) to ethane (CH) has attracted extensive attention from academia and industry. Typically, the traditional oxidative coupling of CH (OCM) reaches a high CH productivity, yet the inevitable overoxidation limits the target product selectivity. Although the traditional nonoxidative coupling of CH (NOCM) can improve the product selectivity, it still encounters unsatisfied activity, arising from being thermodynamically unfavorable.

A copper-catalyzed asymmetric Friedel-Crafts hydroxyalkylation of pyrazole-4,5-diones with 5-aminoisoxazoles.

An asymmetric Friedel-Crafts hydroxyalkylation reaction of 5-aminoisoxazoles with pyrazole-4,5-diones was developed under the catalysis of 5% chiral copper complexes. This reaction exhibits functional group tolerance and excellent enantioselectivity. Moreover, the reaction can be scaled up and its mechanism was studied.

Breaking the Scaling Relationship in C-N Coupling via the Doping Effects for Efficient Urea Electrosynthesis.

Electrochemical C-N coupling reaction based on carbon dioxide and nitrate have been emerged as a new "green synthetic strategy" for the synthesis of urea, but the catalytic efficiency is seriously restricted by the inherent scaling relations of adsorption energies of the active sites, the improvement of catalytic activity is frequently accompanied by the decrease in selectivity. Herein, a doping engineering strategy was proposed to break the scaling relationship of intermediate binding and minimize the kinetic barrier of C-N coupling. A thus designed SrCoRuO catalyst achieves a urea yield rate of 1522 μg h mg and faradic efficiency of 34.

Nitrogen Doping-Roused Synergistic Active Sites in Perovskite Enabling Highly Selective CO Photoreduction into CH.

The intricate protonation process in carbon dioxide reduction usually makes the product unpredictable. Thus, it is significant to control the reactive intermediates to manipulate the reaction steps. Here, we propose that the synergistic La-Ti active sites in the N-LaTiO nanosheets enable the highly selective carbon dioxide photoreduction into methane.

Rovibrational Energies of CO Determined with Kilohertz Accuracy.

Accurate spectroscopic data of carbon dioxide are widely used in many important applications, such as carbon monitoring missions. Here, we present comb-locked cavity ring-down saturation spectroscopy of the second most abundant isotopologue of CO, CO. We determined the positions of 88 lines in three vibrational bands in the 1.

Clinical immunotherapy in pancreatic cancer.

Pancreatic cancer remains a challenging disease with limited treatment options, resulting in high mortality rates. The predominant approach to managing pancreatic cancer patients continues to be systemic cytotoxic chemotherapy. Despite substantial advancements in immunotherapy strategies for various cancers, their clinical utility in pancreatic cancer has proven less effective and durable.

Blockade of CD300A enhances the ability of human NK cells to lyse hematologic malignancies.

Objective: The human cluster of differentiation (CD)300A, a type-I transmembrane protein with immunoreceptor tyrosine-based inhibitory motifs, was investigated as a potential immune checkpoint for human natural killer (NK) cells targeting hematologic malignancies (HMs).

Methods: We implemented a stimulation system involving the CD300A ligand, phosphatidylserine (PS), exposed to the outer surface of malignant cells. Additionally, we utilized CD300A overexpression, a CD300A blocking system, and a xenotransplantation model to evaluate the impact of CD300A on NK cell efficacy against HMs in and settings.

A non-metal single atom nanozyme for cutting off the energy and reducing power of tumors.

Enzymes are considered safe and effective therapeutic tools for various diseases. With the increasing integration of biomedicine and nanotechnology, artificial nanozymes offer advanced controllability and functionality in medical design. However, several notable gaps, such as catalytic diversity, specificity and biosafety, still exist between nanozymes and their native counterparts.

Tandem Dual-Site PbCu Electrocatalyst for High-Rate and Selective Glycine Synthesis at Industrial Current Densities.

Direct electrosynthesis of high-value amino acids from carbon and nitrogen monomers remains a challenge. Here, we design a tandem dual-site PbCu electrocatalyst for efficient amino acid electrosynthesis. Using oxalic acid (HCO) and hydroxylamine (NHOH) as the raw reactants, for the first time, we have realized the flow-electrosynthesis of glycine at the industrial current density of 200 mA cm with Faradaic efficiency over 78%.

Light-Driven C-C Coupling for Targeted Synthesis of CH COOH with Nearly 100 % Selectivity from CO.

Targeted synthesis of acetic acid (CH COOH) from CO photoreduction under mild conditions mainly limits by the kinetic challenge of the C-C coupling. Herein, we utilized doping engineering to build charge-asymmetrical metal pair sites for boosted C-C coupling, enhancing the activity and selectivity of CO photoreduction towards CH COOH. As a prototype, the Pd doped Co O atomic layers are synthesized, where the established charge-asymmetrical cobalt pair sites are verified by X-ray photoelectron spectroscopy and X-ray absorption near edge spectroscopy spectra.