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1.
Chem Sci ; 14(31): 8315-8320, 2023 Aug 09.
Article in English | MEDLINE | ID: mdl-37564412

ABSTRACT

A bimetallic tandem catalysis-enabled enantioselective cycloisomerization/carbonyl-ene reaction was developed. The reaction proceeded well with a broad range of N-propargylamides and acylsilanes, affording the target chiral 5-oxazoylmethyl α-silyl alcohols in up to 95% yield and 99% ee under mild conditions. Importantly, this facile protocol was available for the late-stage modification of several bioactive molecules. Based on the mechanistic study and control experiments, a possible catalytic cycle and transition state are proposed to elucidate the reaction process and enantioinduction.

2.
IEEE Trans Med Imaging ; 42(6): 1696-1706, 2023 06.
Article in English | MEDLINE | ID: mdl-37018705

ABSTRACT

Ultrasonography is an important routine examination for breast cancer diagnosis, due to its non-invasive, radiation-free and low-cost properties. However, the diagnostic accuracy of breast cancer is still limited due to its inherent limitations. Then, a precise diagnose using breast ultrasound (BUS) image would be significant useful. Many learning-based computer-aided diagnostic methods have been proposed to achieve breast cancer diagnosis/lesion classification. However, most of them require a pre-define region of interest (ROI) and then classify the lesion inside the ROI. Conventional classification backbones, such as VGG16 and ResNet50, can achieve promising classification results with no ROI requirement. But these models lack interpretability, thus restricting their use in clinical practice. In this study, we propose a novel ROI-free model for breast cancer diagnosis in ultrasound images with interpretable feature representations. We leverage the anatomical prior knowledge that malignant and benign tumors have different spatial relationships between different tissue layers, and propose a HoVer-Transformer to formulate this prior knowledge. The proposed HoVer-Trans block extracts the inter- and intra-layer spatial information horizontally and vertically. We conduct and release an open dataset GDPH&SYSUCC for breast cancer diagnosis in BUS. The proposed model is evaluated in three datasets by comparing with four CNN-based models and three vision transformer models via five-fold cross validation. It achieves state-of-the-art classification performance (GDPH&SYSUCC AUC: 0.924, ACC: 0.893, Spec: 0.836, Sens: 0.926) with the best model interpretability. In the meanwhile, our proposed model outperforms two senior sonographers on the breast cancer diagnosis when only one BUS image is given (GDPH&SYSUCC-AUC ours: 0.924 vs. reader1: 0.825 vs. reader2: 0.820).


Subject(s)
Breast Neoplasms , Female , Humans , Breast Neoplasms/diagnostic imaging , Ultrasonography , Ultrasonography, Mammary , Diagnosis, Computer-Assisted/methods
3.
Front Cardiovasc Med ; 9: 1002030, 2022.
Article in English | MEDLINE | ID: mdl-36158820

ABSTRACT

Background: The triglyceride-glucose (TyG) index is a novel marker representing the degree of insulin resistance (IR) and is closely related to cardiovascular diseases. However, the association between the TyG index and vascular function in patients with acute ST-elevation myocardial infarction (STEMI) after percutaneous coronary intervention (PCI) remains unknown. Materials and methods: This study was a post hoc analysis of a multicenter, prospective cohort study. In this study, patients with STEMI who underwent PCI were included, and coronary angiography data were analyzed by Quantitative coronary angiography (QCA) and quantitative flow ratio (QFR). In addition, the TyG index was calculated as follows: Ln [fasting triglyceride (mg/dl) × fasting blood glucose (mg/dl) × 1/2]. According to the post-PCI QFR, patients were divided into two groups: post-PCI QFR ≤ 0.92 group and post-PCI QFR > 0.92 group. Construction of logistic regression model to explore the relationship between the TyG index and post-PCI QFR. Results: A total of 241 STEMI patients were included in this study. Compared with patients in the post-PCI QFR > 0.92 group, the TyG index was higher in the post-PCI QFR ≤ 0.92 group. Logistic regression model showed that after adjusting for other confounding factors, the TyG index was positively correlated with the risk of post-PCI QFR ≤ 0.92 (OR = 1.697, 95% CI 1.171-2.460, P = 0.005). Restricted cubic splines showed the cutoff value of TyG index associated with post-PCI QFR ≤ 0.92 risk was 9.75. Conclusion: The TyG index was associated with the risk of post-PCI QFR ≤ 0.92 in STEMI patients. The risk of post-PCI QFR ≤ 0.92 increased when the TyG index exceeded 9.75.

4.
Org Lett ; 22(3): 1034-1039, 2020 Feb 07.
Article in English | MEDLINE | ID: mdl-31951145

ABSTRACT

An asymmetric tandem cycloisomerization and intermolecular [5+2] cycloaddition reaction of 2-ethynylphenyl-substituted nitrones with methyleneindolinones was realized. The process includes the palladium(II)-promoted in situ formation of azomethine ylide and the following chiral N,N'-dioxide-Co(II) complex-catalyzed regio-, diastereo-, and enantioselective [5+2] cycloaddition reaction. The desired spiro-tropanyl oxindoles were obtained in good yields with excellent dr and ee values. On the basis of the determination of the catalyst structure, a possible transition state model was proposed.

5.
Chem Sci ; 12(8): 2940-2947, 2020 Dec 27.
Article in English | MEDLINE | ID: mdl-34164061

ABSTRACT

New types of C 2-symmetric chiral macrodiolides are readily obtained via chiral N,N'-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel-Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.

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