Modulator-assisted solvent-free synthesis of amorphous zirconium terephthalate catalyst for efficient oxidative desulfurization.

Oxidative desulfurization (ODS) emerges as a critical player in enhancing efficient fuel desulfurization and promoting sustainable clean energy. Metal-organic frameworks (MOFs) show great potential as ODS catalysts because of their exceptional porosity and versatility. This study explores the use of amorphous metal-organic frameworks (aMOFs), which combine MOFs' structural advantages with unique properties of amorphous materials, to enhance catalytic efficiency in ODS. Traditional methods for synthesizing MOFs rely on solvent-thermal or solvent-free methods, each with limitations in environmental impact or scalability. To address this, we introduce a novel strategy utilizing a small quantity of benzoic acid (BA) modifier to facilitate the solvent-free, one-pot, mechanical synthesis of amorphous zirconium terephthalate (GU-2BA-3h). The resulting GU-2BA-3h demonstrates exceptional ODS performance, efficiently removing 1000 ppm of dibenzothiophene (DBT) in just 6 min at 60 °C. Amorphous GU-2BA-3h features an expanded external surface area, increased acidic sites, and exceptional stability, resulting in a high turnover frequency (19.6 h-1) and outstanding catalytic activity (53.2 mmol g-1 h-1), establishing it as a highly efficient ODS catalyst. This remarkable performance arises from the formation of dangling carboxyl groups and active metal sites due to the competitive coordination of benzoic acid with the linker. Experimental evidence confirms that these carboxyl groups and exposed Zr-OH sites interact with oxidants, generating hydroxyl radicals that effectively eliminate sulfur-containing compounds. Furthermore, the methodology exhibits universality in constructing amorphous Zr-based MOFs, and provides an eco-friendly, cost-effective route for efficient ODS catalyst production.

Sequential co-reduction of nitrate and carbon dioxide enables selective urea electrosynthesis.

Despite the recent achievements in urea electrosynthesis from co-reduction of nitrogen wastes (such as NO3-) and CO2, the product selectivity remains fairly mediocre due to the competing nature of the two parallel reduction reactions. Here we report a catalyst design that affords high selectivity to urea by sequentially reducing NO3- and CO2 at a dynamic catalytic centre, which not only alleviates the competition issue but also facilitates C-N coupling. We exemplify this strategy on a nitrogen-doped carbon catalyst, where a spontaneous switch between NO3- and CO2 reduction paths is enabled by reversible hydrogenation on the nitrogen functional groups. A high urea yield rate of 596.1 µg mg-1 h-1 with a promising Faradaic efficiency of 62% is obtained. These findings, rationalized by in situ spectroscopic techniques and theoretical calculations, are rooted in the proton-involved dynamic catalyst evolution that mitigates overwhelming reduction of reactants and thereby minimizes the formation of side products.

Multi-Stream Fusion Network for Skeleton-Based Construction Worker Action Recognition.

The global concern regarding the monitoring of construction workers' activities necessitates an efficient means of continuous monitoring for timely action recognition at construction sites. This paper introduces a novel approach-the multi-scale graph strategy-to enhance feature extraction in complex networks. At the core of this strategy lies the multi-feature fusion network (MF-Net), which employs multiple scale graphs in distinct network streams to capture both local and global features of crucial joints. This approach extends beyond local relationships to encompass broader connections, including those between the head and foot, as well as interactions like those involving the head and neck. By integrating diverse scale graphs into distinct network streams, we effectively incorporate physically unrelated information, aiding in the extraction of vital local joint contour features. Furthermore, we introduce velocity and acceleration as temporal features, fusing them with spatial features to enhance informational efficacy and the model's performance. Finally, efficiency-enhancing measures, such as a bottleneck structure and a branch-wise attention block, are implemented to optimize computational resources while enhancing feature discriminability. The significance of this paper lies in improving the management model of the construction industry, ultimately aiming to enhance the health and work efficiency of workers.

The substrate selectivity of papain-like proteases from human-infecting coronaviruses correlates with innate immune suppression.

Coronaviruses that can infect humans can cause either common colds (HCoV-NL63, HCoV-229E, HCoV-HKU1, and HCoV-OC43) or severe respiratory symptoms (SARS-CoV-2, SARS-CoV, and MERS-CoV). The papain-like proteases (PLPs) of SARS-CoV, SARS-CoV-2, MERS-CoV, and HCoV-NL63 function in viral innate immune evasion and have deubiquitinating (DUB) and deISGylating activities. We identified the PLPs of HCoV-229E, HCoV-HKU1, and HCoV-OC43 and found that their enzymatic properties correlated with their ability to suppress innate immune responses. A conserved noncatalytic aspartic acid residue was critical for both DUB and deISGylating activities, but the PLPs had differing ubiquitin (Ub) chain cleavage selectivities and binding affinities for Ub, K48-linked diUb, and interferon-stimulated gene 15 (ISG15) substrates. The crystal structure of HKU1-PLP2 in complex with Ub revealed binding interfaces that accounted for the unusually high binding affinity between this PLP and Ub. In cellular assays, the PLPs from the severe disease-causing coronaviruses strongly suppressed innate immune IFN-I and NF-κB signaling and stimulated autophagy, whereas the PLPs from the mild disease-causing coronaviruses generally showed weaker effects on immune suppression and autophagy induction. In addition, a PLP from a SARS-CoV-2 variant of concern showed increased suppression of innate immune signaling pathways. Overall, these results demonstrated that the DUB and deISGylating activities and substrate selectivities of these PLPs differentially contribute to viral innate immune evasion and may affect viral pathogenicity.

Construction of C(CO)-C(CO) Bond via NHC-Catalyzed Radical Cross-Coupling Reaction.

A C(sp2)-C(sp2) bond can be constructed via a photoredox/N-heterocyclic carbene (NHC)-cocatalyzed radical cross-coupling reaction, which provides a complementary strategy to classic electron pair processes. The present protocol represents the first example of an NHC-catalyzed two-component radical cross-coupling reaction involving C(sp2)-centered radical species. The decarboxylative acylation of oxamic acid with acyl fluoride was conducted under mild conditions and allowed the preparation of a variety of useful α-keto amides, including sterically congested ones.

Interaction between DLC-1 and SAO-1 facilitates CED-4 translocation during apoptosis in the Caenorhabditis elegans germline.

Apoptosis is one of the major forms of programmed cell death, and it serves vital biological functions in multicellular animal and plant cells. The core mechanism of apoptosis is highly conserved in metazoans, where the translocation of CED-4/Apaf-1 from mitochondria to the nuclear membrane is required to initiate and execute apoptosis. However, the underlying molecular mechanisms of this translocation are poorly understood. In this study, we showed that SAO-1 binds DLC-1 and prevents its degradation to promote apoptosis in C. elegans germ cells. We demonstrated that SAO-1 and DLC-1 regulate CED-4/Apaf-1 nuclear membrane accumulation during apoptosis. Isothermal titration calorimetry-based assay and high-resolution crystal structure analysis further revealed that SAO-1 interacted with DLC-1 to form a 2:4 complex: each of the two ß-sheets in the SAO-1 peptide interacted with two DLC-1 dimers. Point mutations at the SAO-1-DLC-1 binding interface significantly inhibited apoptotic corpse formation and CED-4 nuclear membrane accumulation within C. elegans germ cells. In conclusion, our study provides a new perspective on the regulation of CED-4-mediated apoptosis.

Homogenization of an acoustic coating with a steel backing subject to an obliquely incident sound.

An effective homogenization model for the acoustic coating of underwater structures is important for reducing the complexity of acoustic scattering computation, which arises from the huge difference in scale between the integral structure and the inhomogeneous microstructure of the coating. The main difficulty of this homogenization arises from the oblique-incidence effect of external sound waves and the interface effect between the coating and backing. In this work, a hybrid method, combining the Bloch wave analysis and retrieval technique, is proposed to characterize the acoustic behavior of the voided coating backed with a steel plate under the action of external sound waves with an arbitrary incident angle. The effectiveness of this method is validated by numerical simulations and comparison with the Bloch wave method and the traditional retrieval method. The influence of the shear-wave effect under obliquely incident sound waves and the coupling effect between the coating and the backing on the homogenization model is investigated in detail, providing a comprehensive understanding of the effective acoustic behavior of the coating.

Recent Progress on Photoelectrochemical Water Splitting of Graphitic Carbon Nitride (g-CN) Electrodes.

Graphitic carbon nitride (g-CN), a promising visible-light-responsive semiconductor material, is regarded as a fascinating photocatalyst and heterogeneous catalyst for various reactions due to its non-toxicity, high thermal durability and chemical durability, and "earth-abundant" nature. However, practical applications of g-CN in photoelectrochemical (PEC) and photoelectronic devices are still in the early stages of development due to the difficulties in fabricating high-quality g-CN layers on substrates, wide band gaps, high charge-recombination rates, and low electronic conductivity. Various fabrication and modification strategies of g-CN-based films have been reported. This review summarizes the latest progress related to the growth and modification of high-quality g-CN-based films. Furthermore, (1) the classification of synthetic pathways for the preparation of g-CN films, (2) functionalization of g-CN films at an atomic level (elemental doping) and molecular level (copolymerization), (3) modification of g-CN films with a co-catalyst, and (4) composite films fabricating, will be discussed in detail. Last but not least, this review will conclude with a summary and some invigorating viewpoints on the key challenges and future developments.

Comparison of perioperative indicators, treatment efficacy, and postoperative complications between tonsillotomy and tonsillectomy for children with obstructive sleep apnea hypopnea syndrome.

OBJECTIVE: This study aimed to compare the perioperative indicators, treatment efficacy, and postoperative complications between tonsillotomy and tonsillectomy for children with obstructive sleep apnea hypopnea syndrome. METHODS: A total of 134 children with obstructive sleep apnea hypopnea syndrome were divided into tonsillotomy group (n=66) and tonsillectomy group (n=68). The tonsillotomy group received tonsillotomy treatment with a power cutter, while the tonsillectomy group received tonsillectomy treatment. The perioperative indicators, treatment efficacy, and postoperative complications were compared between the two groups. RESULTS: There was no significant difference in operative time between the two groups (p>0.05), with significant difference in amount of blood loss, postoperative Visual Analogue Scale score, food intake amount, and general diet-taking starting time between the two groups (p<0.05). The total effective rate of treatment had no significant difference between the two groups (p>0.05). There was significant difference in postoperative bleeding, upper respiratory tract infection, and pharyngeal scar grade between the two groups (p<0.05). CONCLUSIONS: Compared with tonsillectomy treatment for children with obstructive sleep apnea hypopnea syndrome, tonsillotomy treatment is more beneficial to optimize the perioperative indicators, relieve the postoperative pain, facilitate the postoperative recovery, and reduce the postoperative complications, which is worthy of clinical promotion.

Comparison of perioperative indicators, treatment efficacy, and postoperative complications between tonsillotomy and tonsillectomy for children with obstructive sleep apnea hypopnea syndrome

SUMMARY OBJECTIVE: This study aimed to compare the perioperative indicators, treatment efficacy, and postoperative complications between tonsillotomy and tonsillectomy for children with obstructive sleep apnea hypopnea syndrome. METHODS: A total of 134 children with obstructive sleep apnea hypopnea syndrome were divided into tonsillotomy group (n=66) and tonsillectomy group (n=68). The tonsillotomy group received tonsillotomy treatment with a power cutter, while the tonsillectomy group received tonsillectomy treatment. The perioperative indicators, treatment efficacy, and postoperative complications were compared between the two groups. RESULTS: There was no significant difference in operative time between the two groups (p>0.05), with significant difference in amount of blood loss, postoperative Visual Analogue Scale score, food intake amount, and general diet-taking starting time between the two groups (p<0.05). The total effective rate of treatment had no significant difference between the two groups (p>0.05). There was significant difference in postoperative bleeding, upper respiratory tract infection, and pharyngeal scar grade between the two groups (p<0.05). CONCLUSIONS: Compared with tonsillectomy treatment for children with obstructive sleep apnea hypopnea syndrome, tonsillotomy treatment is more beneficial to optimize the perioperative indicators, relieve the postoperative pain, facilitate the postoperative recovery, and reduce the postoperative complications, which is worthy of clinical promotion.

Highly efficient catalytic reduction of 4-nitrophenol and organic dyes by ultrafine palladium nanoparticles anchored on CeO2 nanorods.

Uniformly dispersed Pd nanoparticles on certain supports exhibit exceptional catalytic performance toward various environmental applications. In this work, ultrafine Pd nanoparticles anchored on CeO2 nanorods were synthesized via an absorption-in situ reduction method. The activity of the CeO2/Pd nanocomposites was systematically investigated toward reduction of 4-nitrophenol (4-NP) and organic dyes including methyl blue, rhodamine B, methyl orange, and Congo red. The results indicated that the CeO2/Pd nanocomposites with different weight ratios of Pd nanoparticles (10.23 wt%, 11.01 wt%, and 14.27 wt%) can almost completely reduce 4-NP with a rate constant of 3.31×10-1, 3.22×10-1, and 2.23×10-1 min-1. Besides, the 10.23 wt% CeO2/Pd nanocomposites exhibit remarkable enhanced catalytic activity toward reduction of organic dyes. The catalysts display ideal stability after being used for three times for the reduction of 4-NP. We believe that our strategy demonstrated here offers insights into the design and fabrication of novel Pd-based nanocomposites for various heterogeneous catalysis applications.

A Genetically Encoded Bioluminescent System for Fast and Highly Sensitive Detection of Antibodies with a Bright Green Fluorescent Protein.

A method for fast and highly sensitive detection of antibodies in serum would greatly facilitate the early diagnosis of disease and infection and dose optimization of therapeutic antibody. Bioluminescence detection with LUMABS (renamed mNeonG-LUMABS, where mNeonG is short for mNeonGreen) sensors based on bioluminescence resonance energy transfer (BRET) between blue-emitting luciferase Nluc and green fluorescent protein (FP) mNeonGreen has been demonstrated to enable fast detection of antibodies directly in serum with reasonable sensitivity. However, some mNeonG-LUMABS sensors exhibit low sensitivity, and thus, sensitivity improvement remains imperative. Here, we report a bright green FP, Clover4, obtained by structure-guided mutagenesis of green FP Clover. Despite similar brightness and fluorescence spectra of Clover and mNeonGreen, Clover4-LUMABS sensors exhibit a largely increased dynamic range (maximum 20-fold) and much lower limit of detection (LOD) (maximum 5.6-fold), most likely because Clover4 is positioned in a more parallel orientation to Nluc in LUMABS. Due to modular design, Clover4-LUMABS offers a general BRET system for fast and highly sensitive antibody detection in serum.

Fabrication of Porous Lead Bromide Films by Introducing Indium Tribromide for Efficient Inorganic CsPbBr3 Perovskite Solar Cells.

In the process of preparing CsPbBr3 films by two-step or multi-step methods, due to the low solubility of CsBr in organic solvents, the prepared perovskite films often have a large number of holes, which is definitely not conducive to the performance of CsPbBr3 perovskite solar cells (PSCs). In response to this problem, this article proposed a method of introducing InBr3 into the PbBr2 precursor to prepare a porous PbBr2 film to increase the reaction efficiency between CsBr and PbBr2 and achieve the purpose of In (Ⅲ) incorporation, which not only optimized the morphology of the produced CsPbBr3 film but also enhanced the charge extraction and transport capabilities, which was ascribed to the reduction of the trap state density and impurity phases in the perovskite films, improving the performance of CsPbBr3 PSCs. At the optimal InBr3 concentration of 0.21 M, the InBr3:CsPbBr3 perovskite solar cell exhibited a power conversion efficiency of 6.48%, which was significantly higher than that of the pristine device.

Complex structures of Rsu1 and PINCH1 reveal a regulatory mechanism of the ILK/PINCH/Parvin complex for F-actin dynamics.

Communications between actin filaments and integrin-mediated focal adhesion (FA) are crucial for cell adhesion and migration. As a core platform to organize FA proteins, the tripartite ILK/PINCH/Parvin (IPP) complex interacts with actin filaments to regulate the cytoskeleton-FA crosstalk. Rsu1, a Ras suppressor, is enriched in FA through PINCH1 and plays important roles in regulating F-actin structures. Here, we solved crystal structures of the Rsu1/PINCH1 complex, in which the leucine-rich-repeats of Rsu1 form a solenoid structure to tightly associate with the C-terminal region of PINCH1. Further structural analysis uncovered that the interaction between Rsu1 and PINCH1 blocks the IPP-mediated F-actin bundling by disrupting the binding of PINCH1 to actin. Consistently, overexpressing Rsu1 in HeLa cells impairs stress fiber formation and cell spreading. Together, our findings demonstrated that Rsu1 is critical for tuning the communication between F-actin and FA by interacting with the IPP complex and negatively modulating the F-actin bundling.

C-C Bond Acylation of Oxime Ethers via NHC Catalysis.

An N-heterocyclic carbene (NHC)-catalyzed strategy has been developed to address the issue of using toxic transitional metals in the field of C-C bond activation. The novel reaction mode enables an efficient docking between the cyanoalkyl from the cycloketone oxime derivative and the acyl group from the aldehyde, affording ketonitrile in moderate to good yields, which is one kind of useful building block for synthesizing nitrogen-containing pharmacophores.

Au/CdS Core-Shell Sensitized Actinomorphic Flower-Like ZnO Nanorods for Enhanced Photocatalytic Water Splitting Performance.

Herein, a novel actinomorphic flower-like ZnO/Au/CdS nanorods ternary composite photocatalyst is prepared to extend the light-responsive range, reduce the photogenerated charge carriers recombination, and ultimately improve the water splitting performance. Flower-like ZnO nanorods are synthesized by a chemical bath method and the CdS nanoparticles are sensitized by successive ionic layer adsorption and reaction method. Then the Au nanoparticles as co-catalysts are introduced by the photodeposition method to modify the interface of ZnO/CdS for reducing the photogenerated electron recombination rate and further improving the performance of water splitting. Detailed characterizations and measurements are employed to analyse the crystallinity, morphology, composition, and optical properties of the flower-like ZnO/Au/CdS nanorods samples. As a result, the flower-like ZnO/Au/CdS nanorod samples present significantly enhanced water splitting performance with a high gas evolution rate of 502.2 µmol/g/h, which is about 22.5 and 1.5 times higher than that of the pure ZnO sample and ZnO/CdS sample. The results demonstrate that the flower-like ZnO/Au/CdS nanorods ternary composite materials have great application potential in photocatalytic water splitting for the hydrogen evolution field.

Synthesis of amino-diamondoid pharmacophores via photocatalytic C-H aminoalkylation.

We report a direct C-H aminoalkylation reaction using two light-activated H-atom transfer catalyst systems that enable the introduction of protected amines to native adamantane scaffolds with C-C bond formation. The scope of adamantane and imine reaction partners is broad and deprotection provides versatile amine and amino acid building blocks. Using readily available chiral imines, the enantioselective synthesis of the saxagliptin core and rimantadine derivatives is also described.

Interfacial Modification of Mesoporous TiO2 Films with PbI2-Ethanolamine-Dimethyl Sulfoxide Solution for CsPbIBr2 Perovskite Solar Cells.

As one of the most frequently-used electron-transporting materials, the mesoporous titanium dioxide (m-TiO2) film used in mesoporous structured perovskite solar cells (PSCs) can be employed for the scaffold of the perovskite film and as a pathway for electron transport, and the contact area between the perovskite and m-TiO2 directly determines the comprehensive performance of the PSCs. Because of the substandard interface combining quality between the all-inorganic perovskite CsPbIBr2 and m-TiO2, the development of the mesoporous structured CsPbIBr2 PSCs synthesized by the one-step method is severely limited. Here, we used a solution containing PbI2, monoethanolamine (EA) and dimethyl sulfoxide (DMSO) (PED) as the interfacial modifier to enhance the contact area and modify the m-TiO2/CsPbIBr2 contact characteristics. Comparatively, the performance of the solar device based on the PED-modified m-TiO2 layer has improved considerably, and its power conversion efficiency is up to 6.39%.

Modular synthesis of α-aryl ß-perfluoroalkyl ketones via N-heterocyclic carbene catalysis.

A new general de novo synthesis of pharmaceutically important α-aryl ß-perfluoroalkyl ketones has been disclosed. Compared with trifluoromethylation-initiated radical 1,2-aryl migration of α,α-diaryl allylic alcohols, this protocol employs a new strategy of biomimetic carbene catalysis to assemble alkene, aldehyde and perfluoroalkyl reagents, providing access to products with excellent flexibility of the aryl unit and perfluoroalkyl group. This method also demonstrates excellent functional group compatibility, including some Grignard reagent sensitive groups.

Incorporation of Nickel Ions to Enhance Integrity and Stability of Perovskite Crystal Lattice for High-Performance Planar Heterojunction Solar Cells.

Enhancement of integrity and stability of crystal lattice are highly challenging for polycrystalline perovskite films. In this work, a strategy of incorporation of nickel (Ni) ions is presented to modulate the crystal structure of the CH3NH3PbI3 perovskite film. A broad range of experimental characterizations reveal that the incorporation of Ni ions can substantially eliminate the intrinsic halide vacancy defects, since Ni ions have a strong preference for octahedral coordination with halide ions, resulting in significantly improved integrity and short-range order of crystal lattice. Moreover, it is also demonstrated that the stronger chemical bonding interaction between Ni ions and halide ions as well as organic group can improve the stability of the perovskite material. Simultaneously, the surface morphology of the perovskite thin film is also improved by the incorporation of nickel ions. As a result, a planar heterojunction perovskite solar cell incorporated with 1.5% Ni exhibits a power conversion efficiency of 18.82%, which is improved by 25% compared with 14.92% for the pristine device. Simultaneously, the device formed incorpration of 1.5% Ni shows remarkable stability with 90% of the initial efficiency after storage in an air environment for 800 h. The studies provide a new insight into metal-incorporated perovskite materials for various optoelectronic applications.