The task of UAV-based maritime rescue object detection faces two significant challenges: accuracy and real-time performance. The YOLO series models, known for their streamlined and fast performance, offer promising solutions for this task. However, existing YOLO-based UAV maritime rescue object detection methods tend to prioritize high accuracy, often at the expense of real-time performance and ease of implementation and expansion.
View Article and Find Full Text PDFIn the realm of organic synthesis, the catalytic and stereoselective formation of C-glycosidic bonds is a pivotal process, bridging carbohydrates with aglycones. However, the inherent chirality of the saccharide scaffold often has a substantial impact on the stereoinduction imposed by a chiral ligand. In this study, we have established an unprecedented zirconaaziridine-mediated asymmetric nickel catalysis, enabling the diastereoselective coupling of bench-stable glycosyl phosphates with a range of (hetero)aromatic and glycal iodides as feasible coupling electrophiles.
View Article and Find Full Text PDFThe specificity of scenarios and tasks in Unmanned Aerial Vehicles (UAV)-based maritime rescue poses challenges for detecting targets within images captured by drones in such environments. This study focuses on leveraging heuristic methods to extract data features from specific UAV maritime rescue images to optimize the generation of anchor boxes in detection models. Experiments conducted on the large-scale SeaDronesSee maritime rescue dataset, using the MMDetection object detection framework, demonstrated that the optimized anchor boxes, improved model performance by 48.
View Article and Find Full Text PDFIn contrast with the well-established C(sp )-SCF cross-coupling to forge the Ar-SCF bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp )-SCF bond has remained largely unexplored. We herein disclose a copper-catalyzed enantioselective radical C(sp )-SCF coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me N)SCF reagent. The key to the success lies in the utilization of chiral phosphino-oxazoline-derived anionic N,N,P-ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity.
View Article and Find Full Text PDFBioengineering (Basel)
December 2023
Diagnostic errors represent a critical issue in clinical diagnosis and treatment. In China, the rate of misdiagnosis in clinical diagnostics is approximately 27.8%.
View Article and Find Full Text PDFThe rate constants () have been determined at 27 °C for H· (D·) transfer from CpCr(CO)H(D) to the C=C bonds of various enamides. This process leads to the formation of α-amino radicals. Vinyl enamides with -alkyl and -phenyl substituents have proven to be good H· acceptors, with rate constants close to those of styrene and methyl methacrylate.
View Article and Find Full Text PDFAlthough α-chiral C(sp)-S bonds are of enormous importance in organic synthesis and related areas, the transition-metal-catalysed enantioselective C(sp)-S bond construction still represents an underdeveloped domain probably due to the difficult heterolytic metal-sulfur bond cleavage and notorious catalyst-poisoning capability of sulfur nucleophiles. Here we demonstrate the use of chiral tridentate anionic ligands in combination with Cu(I) catalysts to enable a biomimetic enantioconvergent radical C(sp)-S cross-coupling reaction of both racemic secondary and tertiary alkyl halides with highly transformable sulfur nucleophiles. This protocol not only exhibits a broad substrate scope with high enantioselectivity but also provides universal access to a range of useful α-chiral alkyl organosulfur compounds with different sulfur oxidation states, thus providing a complementary approach to known asymmetric C(sp)-S bond formation methods.
View Article and Find Full Text PDFChiral amines are commonly used in the pharmaceutical and agrochemical industries. The strong demand for unnatural chiral amines has driven the development of catalytic asymmetric methods. Although the N-alkylation of aliphatic amines with alkyl halides has been widely adopted for over 100 years, catalyst poisoning and unfettered reactivity have been preventing the development of a catalyst-controlled enantioselective version.
View Article and Find Full Text PDFTransition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemo- and stereocontrol challenging. Herein, we describe Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling of acyl radicals. This reaction is compatible with (hetero)aryl and alkyl aldehydes and, more importantly, displays a very broad scope of challenging alcohol substrates, such as 2,2-disubstituted 1,3-diols, 2-substituted-2-chloro-1,3-diols, 2-substituted 1,2,3-triols, 2-substituted serinols, and meso primary 1,4-diols, providing enantioenriched esters characterized by challenging acyclic tetrasubstituted carbon stereocenters.
View Article and Find Full Text PDFAs a typical knowledge-intensive industry, the medical field uses knowledge graph technology to construct causal inference calculations, such as "symptom-disease", "laboratory examination/imaging examination-disease", and "disease-treatment method". The continuous expansion of large electronic clinical records provides an opportunity to learn medical knowledge by machine learning. In this process, how to extract entities with a medical logic structure and how to make entity extraction more consistent with the logic of the text content in electronic clinical records are two issues that have become key in building a high-quality, medical knowledge graph.
View Article and Find Full Text PDFA cobalt-catalyzed multipositional isomerization of conjugated dienes has been reported for the first time using an 8-oxazoline iminoquinoline ligand. This reaction is operationally simple and atom-economical using readily available starting materials with an mixture to access disubstituted 1,3-dienes with excellent yields and good , stereoselectivity. The mechanism via alkene insertion of cobalt hydride species and β-H elimination of a π-allyl cobalt intermediate is proposed on the basis of deuterium labeling and control experiments and density functional theory calculations.
View Article and Find Full Text PDFIn contrast with the well-established enantioconvergent radical C(sp)-C cross-coupling of racemic secondary alkyl electrophiles, the corresponding coupling of tertiary electrophiles to forge all-carbon quaternary stereocentres remains underexplored. The major challenge arises from the steric hindrance and the difficult enantio-differentiation of three distinct carbon substituents of prochiral tertiary radicals. Here we demonstrate a general copper-catalysed enantioconvergent C(sp)-C(sp) cross-coupling of diverse racemic tertiary alkyl halides with terminal alkynes (87 examples).
View Article and Find Full Text PDFThe enantioconvergent radical C(sp)-C(sp) cross-coupling of alkyl halides with alkenylboronate esters is an appealing tool in the assembly of synthetically valuable enantioenriched alkenes owing to the ready availability, low toxicity, and air/moisture stability of alkenylboronate esters. Here, we report a copper/chiral N,N,N-ligand catalytic system for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters (>80 examples) with good functional group tolerance. The key to the success is the rational design of hemilabile N,N,N-ligands by mounting steric hindrance at the ortho position of one coordinating quinoline ring.
View Article and Find Full Text PDFThe Carothers equation is often used to predict the utility of a small molecule reaction in a polymerization. In this study, we present the mechanistic study of Pd/Ag cocatalyzed cross dehydrogenative coupling (CDC) polymerization to synthesize a donor-acceptor (D-A) polymer of 3,3'-dihexyl-2,2'-bithiophene and 2,2',3,3',5,5',6,6'-octafluorobiphenyl, which go counter to the Carothers equation. It is uncovered that the second chain extension cross-coupling proceeds much more efficiently than the first cross-coupling and the homocoupling side reaction (at least 1 order of magnitude faster) leading to unexpectedly low homocoupling defects and high molecular weight polymers.
View Article and Find Full Text PDFChiral Brønsted acid-catalysed asymmetric synthesis has received tremendous interest over the past decades, and numerous efficient synthetic methods have been developed based on this approach. However, the use of chiral Brønsted acids in these reactions is mostly limited to the activation of imine and carbonyl moieties, and the direct activation of carbon-carbon triple bonds has so far not been invoked. Here we show that chiral Brønsted acids enable the catalytic asymmetric dearomatization reactions of naphthol-, phenol- and pyrrole-ynamides by the direct activation of alkynes.
View Article and Find Full Text PDFCombined computational and experimental studies elucidated the distinctive mechanistic features of electrochemical cobalt-catalyzed C-H oxygenation. A sequential electrochemical-chemical (EC) process was identified for the formation of an amidylcobalt(iii) intermediate. The synthesis, characterization, cyclic voltammetry studies, and stoichiometric reactions of the related amidylcobalt(iii) intermediate suggested that a second on-cycle electro-oxidation occurs on the amidylcobalt(iii) species, which leads to a formal Co(iv) intermediate.
View Article and Find Full Text PDFSubtle changes in white matter (WM) microstructure have been associated with normal aging and neurodegeneration. To study these associations in more detail, it is highly important that the WM tracts can be accurately and reproducibly characterized from brain diffusion MRI. In addition, to enable analysis of WM tracts in large datasets and in clinical practice it is essential to have methodology that is fast and easy to apply.
View Article and Find Full Text PDFJ Xray Sci Technol
April 2021
Background: Breast cancer is a common disease in women. Early detection and early treatment can reduce breast cancer mortality. Studies have shown that breast cancer microcalcifications is one of the important clinical manifestations of early breast cancer, and sometimes even the only manifestation.
View Article and Find Full Text PDFJ Xray Sci Technol
May 2021
Background: Breast cancer is one of the most important malignant tumors among women causing a serious impact on women's lives and mammography is one the most important methods for breast examination. When diagnosing the breast disease, radiologists sometimes may consult some previous diagnosis cases as a reference. But there are many previous cases and it is important to find which cases are the similar cases, which is a big project costing lots of time.
View Article and Find Full Text PDFBy taking advantage of a newly developed self-assembly approach based on oxime condensation, we successfully obtained a tetracationic macrocycle bearing two diquats in acidic aqueous media in a high yield. The ring is able to accommodate HPO42- and HCO3- in pure water.
View Article and Find Full Text PDFWe discovered a cooperative gold/silver catalysis mechanism in the oxidative cross-coupling reaction between 1,2,4,5-tetrafluorobenzene and N-TIPS-indole, using DFT calculations. A silver(I)-catalyzed CMD mechanism is responsible for the C-H activation of 1,2,4,5-tetrafluorobenzene, and C-H acidity determines the chemoselectivity. A gold(III)-catalyzed S2Ar mechanism is responsible for the C3-H activation of N-TIPS-indole, and arene nucleophilicity determines the chemo- and regioselectivity.
View Article and Find Full Text PDFAn asymmetric intermolecular, three-component radical-initiated dicarbofunctionalization of 1,1-diarylalkenes with diverse carbon-centered radical precursors and electron-rich heteroaromatics by a copper(I) and chiral phosphoric acid cooperative catalysis strategy has been developed, providing straightforward access to chiral triarylmethanes bearing quaternary all-carbon stereocenters with high efficiency as well as excellent chemo- and enantioselectivity. The key to success is not only the introduction of a sterically demanding chiral phosphoric acid to favor radical difunctionalization over the otherwise remarkable side reactions but also the in situ generation of carbocation intermediates from benzylic radical to realize asymmetric induction with the aid of a removable hydroxy directing group via cooperative interactions with chiral phosphate. Density functional theory calculations elucidated the critical chiral environment created by the hydrogen-bonding and ion-pair interactions between the chiral phosphoric acid catalyst and substrates, which leads to the enantioselective C-C bond formation.
View Article and Find Full Text PDFChem Commun (Camb)
March 2018
Using a novel dynamic covalent approach relying on reversible hydrazone formation, a purely organic 3-dimensional prismatic cage was developed in water at elevated temperatures. By lowering the temperature, the hydrazone bond becomes kinetically inert. This self-assembled cage acts as an effective receptor for donor-acceptor pairs, whose interactions are weak in the absence of the cage.
View Article and Find Full Text PDFThe quantitative analysis of the airway tree is of critical importance in the CT-based diagnosis and treatment of popular pulmonary diseases. The extraction of airway centerline is a precursor to identify airway hierarchical structure, measure geometrical parameters, and guide visualized detection. Traditional methods suffer from extra branches and circles due to incomplete segmentation results, which induce false analysis in applications.
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