Electrochemically Enable N-Sulfenylation/Phosphinylation of Sulfoximines via Oxidative Dehydrocoupling Reaction.

An electrochemical oxidative cross-coupling strategy for the synthesis of N-sulfenylsulfoximines from sulfoximines and thiols was accomplished, giving diverse N-sulfenylsulfoximines in moderate to good yields. Moreover, this strategy can be extended to construct the N-P bond of N-phosphinylated sulfoximines. With electrons as reagents, the oxidative dehydrogenation cross-coupling reaction proceeds smoothly in the absence of traditional redox reagents.

Electrochemical Benzylic C(sp3)-H Imidation Enabled by Benzoic Acid Derived Radicals.

We developed an electrochemical approach for benzylic C(sp3)-H imidation by virtue of the in situ generated oxygen-centered radicals (OCRs). The electrochemical imidation provides a complementary approach to giving distinct imide products compared with previous acyloxylation products. This protocol exhibits good site selectivity and broad substrate generality. Moreover, the utility of the OCR-mediated protocol was extended to the electrochemical oxidation of silane, and its robustness was also highlighted by the imidation of complex substrates, which would otherwise be inaccessible for previous approaches. A plausible reaction mechanism was proposed to rationalize the experimental observations.

Caffeic-Acid-Functionalized MWCNTs and PEDOT:PSS Formed Composite Flexible Films with "Reinforced Concrete" Structure for Electrical Heating and EMI Shielding.

Nowadays, flexible multifunctional composites are attracting much attention and are practically being used in various emerging electronic devices. However, most composites suffer from the disadvantages of high loadings of conductive fillers, complicated preparation processes, and low energy conversion efficiency. In this article, Caffeic acid-modified multiwalled carbon nanotubes (C-MWCNTs)/poly(3,4-ethylene dioxythiophene):polystyrene sulfonic acid (PEDOT:PSS)/polyimide (PI) composite films (CPFs) were prepared using a simple layer-by-layer deposition method. The "reinforced concrete" structure of the C-MWCNTs/PEDOT:PSS layer ensures high electrical conductivity of the film, while the PI layer provides excellent mechanical properties (72.69 MPa). The composite film exhibits excellent electrothermal response and thermal stability up to approximately 125 °C at 5 V. In addition, the good conductivity of the film provides its electromagnetic shielding effectiveness (32.69 dB). With these advantages, we expect that flexible CPFs will be widely utilized in wearable devices, electromagnetic interference (EMI) shielding applications, and thermal management of personal or electronic devices.

Electrocatalytic C-H/S-H Coupling of Amino Pyrazoles and Thiophenols: Synthesis of Amino Pyrazole Thioether Derivatives.

A mild method for the C-H/S-H coupling of pyrazol-5-amines and thiophenols was developed via electrochemistry, giving diverse amino pyrazole thioether derivatives in 37-98% yields. This electrochemical reaction is sustainable and an atom-efficient approach with good functional group tolerance and scalability by avoiding metal and external chemical oxidants.

MXene and AgNW based flexible transparent conductive films with sandwich structure for high-performance EMI shielding and electrical heaters.

With the popularization of 5G technology and the development of science and technology, flexible and transparent conductive films (TCF) are increasingly used in the preparation of optoelectronic devices such as electromagnetic shielding devices, transparent flexible heaters, and solar cells. Silver nanowires (AgNW) are considered the best material for replacing indium tin oxide to prepare TCFs due to their excellent comprehensive properties. However, the loose overlap between AgNWs is a significant reason for the high resistance. This article investigates a sandwich structured conductive network composed of AgNW and Ti3C2Tx MXene for high-performance EMI shielding and transparent electrical heaters. Polyethylene pyrrolidone (PVP) solution was used to hydrophilic modify PET substrate, and then MXene, AgNW, and MXene were assembled layer by layer using spin coating method to form a TCF with a sandwich structure. One-dimensional AgNW is used to provide electron transfer channels and improve light penetration, while two-dimensional MXene nanosheets are used for welding AgNWs and adding additional conductive channels. The flexible TCF has excellent transmittance (85.1 % at 550 nm) and EMI shielding efficiency (27.1 dB). At the voltage of 5 V, the TCF used as a heater can reach 85.6 °C. This work offers an innovative approach to creating TCFs for the future generation.

Characteristics and Influence Factors of Pb(II) Adsorption by Graphene Oxide-Montmorillonite Composite.

This study presents the fabrication of a novel porous composite of graphene oxide-montmorillonite (GO-MMT) through the modification of montmorillonite using the freeze-drying method for the purpose of Pb removal. The characterization of the GO-MMT composite was conducted using scanning electron microscopy, Fourier transform infrared spectrometry, and X-ray diffraction. The results from batch adsorption experiments revealed that the GO-MMT composite exhibited a superior capacity for Pb removal compared to MMT. Furthermore, a single factor experiment confirmed that the dosage of the GO-MMT composite or GO, pH, temperature, and reaction time all significantly influenced the adsorption of Pb by the GO-MMT composite, MMT, or GO. This superiority can be attributed to the presence of oxygen-containing functional groups, the site-blocking effect, and the ion exchange mechanism exhibited by the GO-MMT composite.

Circ_0004872 deficiency attenuates ox-LDL-induced vascular smooth muscle cell dysfunction by miR-424-5p-dependent regulation of FRS2.

Atherosclerosis (AS) is a pivotal pathological basis of cardiovascular and cerebrovascular diseases, and circular RNAs (circRNAs) has been disclosed to exert a vital part in the progression of AS. However, the functions of circ_0004872 in the progression of AS is indistinct. In this context, we aimed to elucidate the role of circ_0004872 and the potential mechanism in AS. The level of circ_0004872, miR-424-5p and fibroblast growth factor receptor substrate 2 (FRS2) was detected using quantitative real-time polymerase chain reaction (qRT-PCR). Cell proliferation was monitored by Cell Counting Kit-8 and 5-ethynyl-2'-deoxyuridine (EDU) assays. The invasion and migration capabilities of VSMCs were tested by transwell assays and wound-healing assay, respectively. Western blot was adopted to check the protein levels of CyclinD1, Vimentin and FRS2. Dual-luciferase reporter and RNA immunoprecipitation assay were executed to manifest the interaction between miR-424-5p and circ_0004872 or FRS2. The level of circ_0004872 was increased in the serum samples of AS patients and ox-LDL-exposed VSMCs. Ox-LDL exposure triggered cell proliferation, invasion and migration ability of VSMCs. depletion of circ_0004872 partly weakened ox-LDL-mediated effects in VSMCs. Mechanistically, circ_0004872 functioned as a sponge of miR-424-5p, and miR-424-5p inhibition partly alleviated circ_0004872 deficiency-mediated influences in VSMCs. Additionally, miR-424-5p interacted with FRS2, and miR-424-5p constrained dysfunction in ox-LDL-stimulated VSMCs via reducing FRS2 level. Notably, circ_0004872 functioned as a sponge of miR-424-5p to elevate FRS2 expression. Circ_0004872 accelerated ox-LDL-induced damage via mediating miR-424-5p/FRS2 axis.

Crohn's disease as the intestinal manifestation of pan-lymphatic dysfunction: An exploratory proposal based on basic and clinical data.

Crohn's disease (CD) is caused by immune, environmental, and genetic factors. It can involve the entire gastrointestinal tract, and although its prevalence is rapidly increasing its etiology remains unclear. Emerging biological and small-molecule drugs have advanced the treatment of CD; however, a considerable proportion of patients are non-responsive to all known drugs. To achieve a breakthrough in this field, innovations that could guide the further development of effective therapies are of utmost urgency. In this review, we first propose the innovative concept of pan-lymphatic dysfunction for the general distribution of lymphatic dysfunction in various diseases, and suggest that CD is the intestinal manifestation of pan-lymphatic dysfunction based on basic and clinical preliminary data. The supporting evidence is fully summarized, including the existence of lymphatic system dysfunction, recognition of the inside-out model, disorders of immune cells, changes in cell plasticity, partial overlap of the underlying mechanisms, and common gut-derived fatty and bile acid metabolism. Another benefit of this novel concept is that it proposes adopting the zebrafish model for studying intestinal diseases, especially CD, as this model is good at presenting and mimicking lymphatic dysfunction. More importantly, the ensuing focus on improving lymphatic function may lead to novel and promising therapeutic strategies for CD.

Ir/Zn-cocatalyzed chemo- and atroposelective [2+2+2] cycloaddition for construction of C─N axially chiral indoles and pyrroles.

Here, an Ir/Zn-cocatalyzed atroposelective [2+2+2] cycloaddition of 1,6-diynes and ynamines was developed, forging various functionalized C─N axially chiral indoles and pyrroles in generally good to excellent yields (up to 99%), excellent chemoselectivities, and high enantioselectivities (up to 98% enantiomeric excess) with wide substrate scope. This cocatalyzed strategy not only provided an alternative promising and reliable way for asymmetric alkyne [2+2+2] cyclotrimerization in an easy handle but also settled the issues of previous [Rh(COD)2]BF4-catalyzed system on the construction of C─N axial chirality such as complex operations, limited substrate scope, and low efficiency. In addition, control experiments and theoretical calculations disclosed that Zn(OTf)2 markedly reduced the barrier of migration insertion to significantly increase reaction efficiency, which was distinctly different from previous work on the Lewis acid for improving reaction yield through accelerating oxidative addition and reductive elimination.

Copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones with vinyl cations.

The enantioselective transformation of easily accessible 1,2-diketones represents a quick pathway towards enantioenriched molecules. Herein, we disclose a copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones with vinyl cations, enabling the efficient and atom-economical construction of axially chiral arylpyrroles bearing 1,3-dioxole moieties with good to excellent enantioselectivities under mild reaction conditions. Importantly, this methodology constitutes the first enantioselective formal [4+1] annulation of 1,2-diketones.

Ruthenium-Catalyzed 1,6-Hydroalkylation of para-Quinone Methides with Ketones via the in Situ Activation of C(sp3)-H Bonds.

A simple and efficient method for the ruthenium-catalyzed 1,6-hydroalkylation of para-quinone methides (p-QMs) with ketones via the in situ activation of C(sp3)-H bonds has been disclosed. Without the need for preactivation of the substrates and oxidant, a broad range of p-QMs and ketones are well tolerated, producing the expected 1,6-hydroalkylation products with moderate to good yields. Step-by-step control experiments and DFT calculation were conducted systematically to gain insights for the plausible reaction mechanism. This finding may have potential application in the selective diarylmethylation of ketones at the α-C position in organic synthesis.

Left epigastric isolated tumor fed by the inferior phrenic artery diagnosed as ectopic hepatocellular carcinoma: A case report.

BACKGROUND: Hepatocellular carcinoma (HCC) is one of the most frequent cancers and the main cause of cancer-related death worldwide. Ectopic HCC, an extremely rare type of HCC, exhibits a wide range of clinical signs and radiographic features, making preoperative identification challenging. CASE SUMMARY: A 47-year-old man underwent routine abdominal color ultrasonography, which identified an asymptomatic tumor in the left upper abdomen. The patient had no history of hepatitis, did not drink alcohol, and had no family history of cancer. Abdominal contrast-enhanced computed tomography (CT) revealed a heterogeneously enhanced lesion between the spleen and stomach that had invaded the diaphragm, with blood supplied by the left inferior phrenic artery. The patient underwent laparoscopic surgery, and HCC was identified by postoperative pathology. Additionally, specific immunohistochemical staining was performed to assess the molecular biological characteristics of the HCC. The patient underwent two rounds of hepatic arterial interventional chemotherapy after surgery. Abdominal plain and enhanced magnetic resonance imaging and lung CT 3 mo postoperatively revealed no signs of local recurrence or distant metastasis. CONCLUSION: This asymptomatic ectopic HCC case described achieved an excellent result due to early detection, radical resection, and systematic surveillance.

Copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles.

One-carbon homologation reactions based on one-carbon insertion into the N-O bond of heterocycles have received tremendous interest over the past decades. However, these protocols have to rely on the use of hazardous and not easily accessible diazo compounds as precursors, and examples of the relevant asymmetric catalysis have not been reported. Here we show that a copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles involving one-carbon insertion into the heterocyclic N-O bond via non-diazo approach. This method enables practical and atom-economic synthesis of valuable pyrrole-substituted oxadiazines in generally moderate to good yields under mild reaction conditions. In addition, the possibility of such an asymmetric formal (5 + 1) annulation also emerges.

Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles.

A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis-Arbuzov rearrangement for the synthesis of ß-ketophosphine oxides, ß-ketophosphinates, and ß-ketophosphonates is reported. The present reaction could be conducted effectively without the use of a ligand and a base. Various kinds of aryl acrylic acids and P(III)-nucleophiles are tolerated in the transformation, generating the desired ß-keto-organophosphorus compounds as a valuable class of phosphorus-containing intermediates with good to excellent yields. In addition, the possible mechanism and kinetic studies for the reaction have been explored by step-by-step control experiments and competitive experiments, and the results proved that this transformation may follow second-order chemical kinetics as well as involve a radical process.

Generating Topologically Consistent BIM Models of Utility Tunnels from Point Clouds.

The development and utilization of urban underground space is an important way to solve the "great urban disease". As one of the most important types of urban underground foundations, utility tunnels have become increasingly popular in municipal construction. The investigation of utility tunnels is a general task and three-dimensional laser scanning technology has played a significant role in surveying and data acquisition. However, three-dimensional laser scanning technology suffers from noise and occlusion in narrow congested utility tunnel spaces, and the acquired point clouds are imperfect; hence, errors and redundancies are introduced in the extracted geometric elements. The topology of reconstructed BIM objects cannot be ensured. Therefore, in this study, a hierarchical segmentation method for point clouds and a topology reconstruction method for building information model (BIM) objects in utility tunnels are proposed. The point cloud is segmented into facades, planes, and pipelines hierarchically. An improved mean-shift algorithm is proposed to extract wall line features and a local symmetry-based medial axis extraction algorithm is proposed to extract pipelines from point clouds. A topology reconstruction method that searches for the neighbor information of wall and pipeline centerlines and establishes collinear, perpendicular, and intersecting situations is used to reconstruct a topologically consistent 3D model of a utility tunnel. An experiment on the Guangzhou's Nansha District dataset successfully reconstructed 24 BIM wall objects and 12 pipelines within the utility tunnel, verifying the efficiency of the method.

The Influence of Heat and Cryogenic Treatment on Microstructure Evolution and Mechanical Properties of Laser-Welded AZ31B.

The pores and coarse lamellar Mg17Al12 that inevitably occur in the weld zone are the major challenge for laser-welded magnesium (Mg) alloys including AZ31B. In order to improve microstructure uniformity and eliminate welding defects, a new process assisted with combination of heat and cryogenic treatment was applied in this study. The results showed that after solution treatment, the number and size of precipitates decreased and the uniformity of the microstructure improved. After cryogenic treatment, the lamellar Mg17Al12 was cracked into particles, and the grain size was refined. After solution + cryogenic treatment, Al8Mn5 substituted the lamellar Mg17Al12. Through studying the changes in microhardness, precipitates, and microstructure under different treatments, it was found that the conversation of Mg17Al12 from lamellar state into particle-like state as well as the appearance of dispersed Al8Mn5 particles played a second-phase strengthening role in improving the mechanical properties of Mg alloy laser-welded joint, and the tensile strength (258.60 MPa) and elongation (10.90%) of the sample were 4.4% and 32.6% higher than those of the as-welded joint.

A two-stage segmentation of sublingual veins based on compact fully convolutional networks for Traditional Chinese Medicine images.

As one of the key methods of Traditional Chinese Medicine inspection, tongue diagnosis manifests the advantages of simplicity and directness. Sublingual veins can provide essential information about human health. In order to automate tongue diagnosis, sublingual veins segmentation has become one important issue in the field of Chinese medicine medical image processing. At present, the primary methods for sublingual veins segmentation are traditional feature engineering methods and the feature representation methods represented by deep learning. The former, which mainly based on colour space, belongs to unsupervised classification method. The latter, which includes U-Net and other deep neural network models, belongs to supervised classification method. Current feature engineering methods can only capture low dimensional information, which makes it difficult to extract efficient features for sublingual veins. On the other hand, current deep learning methods use down-sampling structures, which manifest weak robustness and low accuracy. So, it is difficult for current segmentation approaches to recognize tiny branches of sublingual veins. To overcome the above limits, this paper proposes a novel two-stage semantic segmentation method for sublingual veins. In the first stage, a fully convolutional network without down-sampling is used to realize the accurate segmentation of the tongue that includes the sublingual veins to be segmented in the next stage. During the tongue segmentation, the proposed networks can effectively reduce the loss of medical images spatial feature information. At the same time, in order to expand the receptive field, the dilated convolution has been introduced to the proposed networks, which can capture multi-scale information of segmentation images. In the second stage, another fully convolutional network has been used to segment the sublingual veins on the base of the results from the first stage. In this model, proper dilated convolutional rates have been selected to avoid gridding issue. In order to keep the quality of the images to be segmented, several particular data pre-processing and post-processing have been used, which includes specular highlight removal, data augmentation, erosion and dilation. Finally, in order to evaluate the performance of the proposed model, segmentation results have been compared with the state-of-the-art methods on the base of the dataset from Shanghai University of Traditional Chinese Medicine. The effectiveness of sublingual veins segmentation has been proved.

Flexible Wearable Electronic Fabrics with Dual Functions of Efficient EMI Shielding and Electric Heating for Triboelectric Nanogenerators.

Traditional conductive fabrics are prepared by the synthesis of conductive polymers and the coating modification of metals or carbon black conductive materials. However, the conductive fabrics cause a significant decline in performance after washing or mechanical wear, which limits their application. Moreover, the single function of the traditional conductive fabric is also the reason that limits its wide application. In order to prepare a wearable, stable, high-performance, washable, multifunctional conductive fabric, we have carried out related research. In this work, polydopamine was used as a bonding layer, an adsorption reduction layer, and a protective layer to improve the bonding between silver nanoparticles and carbon nanotubes (CNTs) on the polyester fabric surface so as to prepare a multifunctional conductive fabric with a high-stability "sandwich" structure, in which a Ag-NPS@CNT structure acting as an intermediate conductive layer formed on the inner layer PDA@CNT by electroless silver plating and the outermost layer PDA@CNT coated on the surface of the intermediate conductive layer by the impregnation-drying method. The sheet resistance of an E-Fabric can reach 2.11 Ω/□ due to the uniform and dense conductive path formed by the special structure Ag-NPs@CNT. At a low voltage of 1.5 V, the E-Fabric can reach 117 °C in 50 s and remain stable. The electrical conductivity and current heating properties of the E-Fabric remain good even after multiple washing or bending tests. Due to its stable and outstanding electrical conductivity, the E-Fabric has an electromagnetic shielding efficiency (SET) of 35.3 dB in the X-band (8.2-12.4 GHz). In addition, E-Fabric-based spin-coated poly(methyl methacrylate) or polydimethylsiloxane electrodes exhibit excellent performance in nanogenerators. Through the low-frequency friction of the human body, transient voltages up to 4 V can be generated from a 2 cm × 2 cm electrode sample. The output power of a single generator can reach about 12 nW/cm2. Therefore, an E-Fabric is considered to have great potential in the fields of electric heating, electromagnetic shielding, and smart wearable devices.

Brønsted acid-catalyzed asymmetric dearomatization for synthesis of chiral fused polycyclic enone and indoline scaffolds.

In the past two decades, substantial advances have been made on the asymmetric alkyne functionalization by the activation of inert alkynes. However, these asymmetric transformations have so far been mostly limited to transition metal catalysis, and chiral Brønsted acid-catalyzed examples are rarely explored. Here, we report a chiral Brønsted acid-catalyzed dearomatization reaction of phenol- and indole-tethered homopropargyl amines, allowing the practical and atom-economical synthesis of a diverse array of valuable fused polycyclic enones and indolines bearing a chiral quaternary carbon stereocenter and two contiguous stereogenic centers in moderate to good yields with excellent diastereoselectivities and generally excellent enantioselectivities (up to >99% enantiomeric excess). This protocol demonstrates Brønsted acid-catalyzed asymmetric dearomatizations via vinylidene-quinone methides.

Copper-Catalyzed Tandem Cyclization/Direct C(sp2)-H Annulation of Azide-Ynamides via α-Imino Copper Carbenes: Access to Azepino[2,3-b:4,5-b']diindoles.

A novel copper-catalyzed tandem cyclization/direct C(sp2)-H annulation of phenyl azide-ynamides via α-imino copper carbenes has been developed, which provides a concise and flexible approach for the construction of a range of valuable azepino[2,3-b:4,5-b']diindoles in mostly good to excellent yields with high chemoselectivities. This tandem reaction also exhibits a broad substrate scope, excellent functional group tolerance, simple operation, and mild reaction conditions.