Cyclic (Alkyl)(Amino)Carbene-Iminoboryl Compounds with Three Formal Oxidation States.

BN/CC isosterism is an effective strategy to build hybrid functional molecules with unique properties. In contrast to the alkynyl iminium salts derived from cyclic (alkyl)(amino)carbenes (CAACs) that feature only one reversible reduction wave, the isoelectronic cationic CAAC-iminoboryl adducts could be singly and doubly reduced smoothly. Both the resultant neutral radical and anionic azaborataallenes bear NBC-mixed allenic structures. The former radical has a high spin-density of 0.55e at CCAAC carbon, yet exhibits formal boron-centered radical reactivity. The latter azaborataallenes feature the nucleophilic CCAAC center and polar N(δ-)═B(δ+)═C(δ-) unit, and readily undergo nucleophilic substitution, isocyanide insertion, dipolar addition and cycloaddition reactions etc. The N-substituents have been shown to have a significant influence on the solid-state structure, thermal stability, and reactivity of azaborataallenes. This work showcases the allenic BN-unsaturated species as versatile building blocks in organic synthesis.

Catalyst-Free Regioselective Diborylation of Aryllithium with Tetra(o-tolyl)diborane(4).

A catalyst-free 1,2-diborylation of aryllithium with tetra(o-tolyl)diborane(4) has been achieved, giving a series of 1,2-diborylaryl lithium species in excellent yields under mild reaction conditions, which leads to 1,2-di(tolyl)borylarenes in 60-91 % yields upon treatment with the hydride-abstracting reagent. In these transformations, one sp2 C-H of arene is activated and both boryl units are utilized to build two new (sp2 )C-B bonds. This represents a new strategy for selective arene diborylation. Density functional theory (DFT) calculations suggest that an aromatic nucleophilic substitution is a key step in the formation of the products.

Cu-Catalyzed Cascade Annulation of Alkynols with 2-Azidobenzaldehydes: Access to 6H-Isochromeno[4,3-c]quinoline.

A copper-catalyzed cascade reaction of alkynols and 2-azidobenzaldehydes has been achieved, giving 6H-isochromeno[4,3-c]quinoline in yields of 40-81%. This reaction provides a novel, concise strategy for rapidly constructing compounds with fused N- and O-containing heterocycles. In contrast to previously reported reactions of alkynols in which the first step is intramolecular cycloisomerization, the first step in this novel reaction of alkynols is entropically unfavorable intermolecular addition. The resulting hemiacetal intermediate then undergoes intramolecular cyclization and aromatization to afford the product.

Enhancing Few-Shot CLIP With Semantic-Aware Fine-Tuning.

Learning generalized representations from limited training samples is crucial for applying deep neural networks in low-resource scenarios. Recently, methods based on contrastive language-image pretraining (CLIP) have exhibited promising performance in few-shot adaptation tasks. To avoid catastrophic forgetting and overfitting caused by few-shot fine-tuning, existing works usually freeze the parameters of CLIP pretrained on large-scale datasets, overlooking the possibility that some parameters might not be suitable for downstream tasks. To this end, we revisit CLIP's visual encoder with a specific focus on its distinctive attention pooling layer, which performs a spatial weighted-sum of the dense feature maps. Given that dense feature maps contain meaningful semantic information, and different semantics hold varying importance for diverse downstream tasks (such as prioritizing semantics like ears and eyes in pet classification tasks rather than side mirrors), using the same weighted-sum operation for dense features across different few-shot tasks might not be appropriate. Hence, we propose fine-tuning the parameters of the attention pooling layer during the training process to encourage the model to focus on task-specific semantics. In the inference process, we perform residual blending between the features pooled by the fine-tuned and the original attention pooling layers to incorporate both the few-shot knowledge and the pretrained CLIP's prior knowledge. We term this method as semantic-aware fine-tuning (). is effective in enhancing the conventional few-shot CLIP and is compatible with the existing adapter approach (termed ). Extensive experiments on 11 benchmarks demonstrate that both and significantly outperform the second-best method by + 1.51 % and + 2.38 % in the one-shot setting and by + 0.48 % and + 1.37 % in the four-shot setting, respectively.

Decreased free fatty acid levels associated with adverse clinical outcomes in coronary artery disease patients with type 2 diabetes: findings from the PRACTICE study.

AIMS: Increased free fatty acid (FFA) levels are known to be strongly associated with mortality in coronary artery disease (CAD) patients and the development of type 2 diabetes (T2DM). However, few studies have been large enough to accurately examine the relationship between FFA levels and mortality in CAD patients with T2DM. METHODS AND RESULTS: From December 2016 to October 2021, 10 395 CAD patients enrolled in PRACTICE, a prospective cohort study in China, were divided into four groups according to baseline FFA concentration. We investigated mortality, including all-cause mortality (ACM) and cardiac mortality (CM), as the primary endpoint. The secondary endpoints were major adverse cardiovascular and cerebrovascular events (MACCEs) and major adverse cardiovascular events (MACEs). The median follow-up time was 24 months. In the total cohort, there were 222 ACMs, 164 CMs, 718 MACEs, and 803 MACCEs recorded. After controlling for baseline variables, the association between FFA levels and the risk of mortality presented a non-linear U-shaped curve, with the lowest risk at 310 µmol/L. We also identified a non-linear U-shaped relationship for ischaemic events (MACE or MACCE) with the lowest risk at 500 µmol/L. Subgroup analysis showed that a U-shaped relationship between FFA and mortality or ischaemic events was observed only in individuals with T2DM but not in non-diabetic CAD patients. CONCLUSIONS: A non-linear U-shaped association was identified between baseline FFA levels and mortality or ischaemic events in CAD patients with T2DM.

From December 2016 to October 2021, 10 395 coronary artery disease (CAD) patients enrolled in PRACTICE, a prospective cohort study in China, were divided into four groups according to baseline free fatty acid (FFA) concentration. We investigated mortality, including all-cause mortality (ACM), and cardiac mortality (CM), as the primary endpoints. The secondary endpoints were major adverse cardiovascular and cerebrovascular events (MACCEs) and major adverse cardiovascular events (MACEs). The median follow-up time was 24 months. Finally, we were surprised to find that high and low FFA levels were associated with a higher risk of mortality and ischaemic events in CAD patients with T2DM. Baseline plasma FFA levels may be a more powerful, effective, and easily detectable biomarker of adverse outcomes in CAD patients with T2DM. As the FFA increases, a U-shaped curve appears in the poor long-term prognosis.

A (µ-hydrido)diborane(4) anion and its coordination chemistry with coinage metals.

A tetra(o-tolyl) (µ-hydrido)diborane(4) anion 1, an analogue of [B2H5]- species, was facilely prepared through the reaction of tetra(o-tolyl)diborane(4) with sodium hydride. Unlike common sp2-sp3 diborane species, 1 exhibited a σ-B-B bond nucleophilicity towards NHC-coordinated transition-metal (Cu, Ag, and Au) halides, resulting in the formation of η2-B-B bonded complexes 2 as confirmed by single-crystal X-ray analyses. Compared with 1, the structural data of 2 imply significant elongations of B-B bonds, following the order Au > Cu > Ag. DFT studies show that the diboron ligand interacts with the coinage metal through a three-center-two-electron B-M-B bonding mode. The fact that the B-B bond of the gold complex is much prolonged than the related Cu and Ag compounds might be ascribed to the superior electrophilicity of the gold atom.

Fine-Grained Fashion Similarity Prediction by Attribute-Specific Embedding Learning.

This paper strives to predict fine-grained fashion similarity. In this similarity paradigm, one should pay more attention to the similarity in terms of a specific design/attribute between fashion items. For example, whether the collar designs of the two clothes are similar. It has potential value in many fashion related applications, such as fashion copyright protection. To this end, we propose an Attribute-Specific Embedding Network (ASEN) to jointly learn multiple attribute-specific embeddings, thus measure the fine-grained similarity in the corresponding space. The proposed ASEN is comprised of a global branch and a local branch. The global branch takes the whole image as input to extract features from a global perspective, while the local branch takes as input the zoomed-in region-of-interest (RoI) w.r.t. the specified attribute thus able to extract more fine-grained features. As the global branch and the local branch extract the features from different perspectives, they are complementary to each other. Additionally, in each branch, two attention modules, i.e., Attribute-aware Spatial Attention and Attribute-aware Channel Attention, are integrated to make ASEN be able to locate the related regions and capture the essential patterns under the guidance of the specified attribute, thus make the learned attribute-specific embeddings better reflect the fine-grained similarity. Extensive experiments on three fashion-related datasets, i.e., FashionAI, DARN, and DeepFashion, show the effectiveness of ASEN for fine-grained fashion similarity prediction and its potential for fashion reranking. Code and data are available at https://github.com/maryeon/asenpp.

The Fibrinogen-to-Albumin Ratio Is Associated With Outcomes in Patients With Coronary Artery Disease Who Underwent Percutaneous Coronary Intervention.

Coronary artery disease (CAD) is a systemic chronic inflammatory disease, and serum fibrinogen and albumin are 2 important factors in systemic inflammation. We aimed to investigate the relationship between the fibrinogen-albumin ratio (FAR) and outcomes in patients with CAD who underwent percutaneous coronary intervention (PCI). All patients were from the Clinical Outcomes and Risk Factors of Patients with Coronary Heart Disease after PCI (CORFCHD-PCI) study, which is a retrospective cohort study (Identifier: ChiCTR-ORC-16010153) that includes a total of 6050 patients with CAD after PCI from January 2008 to December 2016. A total of 5829 patients with CAD after PCI were recruited in the present study. They were divided into 2 groups according to the FAR cutoff value, which was calculated using a receiver operating characteristic curve, a low group (FAR < 0.095, n = 3811), and a high group (FAR ≥ 0.095, n = 2018). The average follow-up time was 35.9 ± 22.6 months. The multivariate Cox proportional hazards model showed that FAR was independently correlated with all-cause mortality (adjusted hazard ratio [HR] = 1.432 [1.134-1.808], P = .003), cardiac mortality (adjusted HR = 1.579 [1.218-2.047], P = .001), major adverse cardiac and cerebrovascular events (adjusted HR = 1.296 [1.125-1.494], P < .001), major adverse cardiac events (adjusted HR = 1.357 [1.170-1.572], P < .001), and heart failure (adjusted HR = 1.540 [1.135-2.091], P = .006). The present study indicated that the FAR was associated with adverse outcomes in patients with CAD who underwent PCI.

Cascade reaction of alkynols with 1-(2-aminophenyl)prop-2-ynols to form a fused 5,5,6-tricyclic system: formation of four bonds in a single reaction.

A novel cascade reaction of internal alkynols with 1-(2-aminophenyl)prop-2-ynols has been developed to form a new N,O-containing fused 5,5,6-tricyclic skeleton. Mechanistic studies indicate that this reaction proceeds via alkynol cycloisomerization, intermolecular substitution with 1-(2-aminophenyl)prop-2-ynols, and intermolecular addition with alkynols and consequent cyclizations. In this way, two C-C bonds, one C-O bond and one C-N bond form to give a tricyclic skeleton in a single reaction.