CHoose nickel: The nickel‐catalyzed oxidative arylation of C(sp3)H bonds has been achieved. Several substituted arylboronic acids and various C(sp3)H bonds were found to be suitable substrates for ...this novel transformation, which is likely to proceed through a radical pathway. This method allows the introduction of simple ether derivatives to construct α‐arylated ethers. FG=functional group.
Enantiopure vicinal amino alcohols and derivatives are essential structural motifs in natural products and pharmaceutically active molecules, and serve as main chiral sources in asymmetric synthesis. ...Currently known asymmetric catalytic protocols for this class of compounds are still rare and often suffer from limited scope of substrates, relatively low regio- or stereoselectivities, thus prompting the development of more effective methodologies. Herein we report a dual catalytic strategy for the convergent enantioselective synthesis of vicinal amino alcohols. The method features a radical-type Zimmerman-Traxler transition state formed from a rare earth metal with a nitrone and an aromatic ketyl radical in the presence of chiral N,N'-dioxide ligands. In addition to high level of enantio- and diastereoselectivities, our synthetic protocol affords advantages of simple operation, mild conditions, high-yielding, and a broad scope of substrates. Furthermore, this protocol has been successfully applied to the concise synthesis of pharmaceutically valuable compounds (e.g., ephedrine and selegiline).
Hyperspectral unmixing is an important processing step for many hyperspectral applications, mainly including: 1) estimation of pure spectral signatures (endmembers) and 2) estimation of the abundance ...of each endmember in each pixel of the image. In recent years, nonnegative matrix factorization (NMF) has been highly attractive for this purpose due to the nonnegativity constraint that is often imposed in the abundance estimation step. However, most of the existing NMF-based methods only consider the information in a single layer while neglecting the hierarchical features with hidden information. To alleviate such limitation, in this paper, we propose a new sparsity-constrained deep NMF with total variation (SDNMF-TV) technique for hyperspectral unmixing. First, by adopting the concept of deep learning, the NMF algorithm is extended to deep NMF model. The proposed model consists of pretraining stage and fine-tuning stage , where the former pretrains all factors layer by layer and the latter is used to reduce the total reconstruction error. Second, in order to exploit adequately the spectral and spatial information included in the original hyperspectral image, we enforce two constraints on the abundance matrix. Specifically, the <inline-formula> <tex-math notation="LaTeX">L_{1/2} </tex-math></inline-formula> constraint is adopted, since the distribution of each endmember is sparse in the 2-D space. The TV regularizer is further introduced to promote piecewise smoothness in abundance maps. For the optimization of the proposed model, multiplicative update rules are derived using the gradient descent method. The effectiveness and superiority of the SDNMF-TV algorithm are demonstrated by comparing with other unmixing methods on both synthetic and real data sets.
The spatial characteristics of cracks are significant indicators to assess and evaluate the health of existing buildings and infrastructures. However, the current manual crack description method is ...time consuming and labor consuming. To improve the efficiency of crack inspection, advanced computer vision‐based techniques have been utilized to detect cracks automatically at image level and grid‐cell level. But existing crack detections are of (high specificity) low generality and inefficient, in terms that conventional approaches are unable to identify and measure diverse cracks concurrently at pixel level. Therefore, this research implements a novel deep learning technique named fully convolutional network (FCN) to address this problem. First, FCN is trained by feeding multiple types of cracks to semantically identify and segment pixel‐wise cracks at different scales. Then, the predicted crack segmentations are represented by single‐pixel width skeletons to quantitatively measure the morphological features of cracks, providing valuable crack indicators for assessment in practice, such as crack topology, crack length, max width, and mean width. To validate the prediction, the predicted segmentations are compared with recent advanced method for crack recognition and ground truth. For crack segmentation, the accuracy, precision, recall, and F1 score are 97.96%, 81.73%, 78.97%, and 79.95%, respectively. For crack length, the relative measurement error varies from −48.03% to 177.79%, meanwhile that ranges from −13.27% to 24.01% for crack width. The results show that FCN is feasible and sufficient for crack identification and measurement. Although the accuracy is not as high as CrackNet because of three types of errors, the prediction has been increased to pixel level and the training time has been dramatically decreased to several per cents of previous methods due to the novel end‐to‐end structure of FCN, which combines typical convolutional neural networks and deconvolutional layers.
Genetically encoded fluorescent biosensors are powerful tools used to track chemical processes in intact biological systems. However, the development and optimization of biosensors remains a ...challenging and labor-intensive process, primarily due to technical limitations of methods for screening candidate biosensors. Here we describe a screening modality that combines droplet microfluidics and automated fluorescence imaging to provide an order of magnitude increase in screening throughput. Moreover, unlike current techniques that are limited to screening for a single biosensor feature at a time (e.g. brightness), our method enables evaluation of multiple features (e.g. contrast, affinity, specificity) in parallel. Because biosensor features can covary, this capability is essential for rapid optimization. We use this system to generate a high-performance biosensor for lactate that can be used to quantify intracellular lactate concentrations. This biosensor, named LiLac, constitutes a significant advance in metabolite sensing and demonstrates the power of our screening approach.
Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost ...fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼ 16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization.
Plastic pollution represents a major and growing global problem. It is well-known that plastics are a source of chemical contaminants to the aquatic environment and provide novel habitats for marine ...organisms. The present study quantified the impacts of plastic leachates from the seven categories of recyclable plastics on larval survival and settlement of barnacle Amphibalanus (=Balanus) amphitrite. Leachates from plastics significantly increased barnacle nauplii mortality at the highest tested concentrations (0.10 and 0.50 m2/L). Hydrophobicity (measured as surface energy) was positively correlated with mortality indicating that plastic surface chemistry may be an important factor in the effects of plastics on sessile organisms. Plastic leachates significantly inhibited barnacle cyprids settlement on glass at all tested concentrations. Settlement on plastic surfaces was significantly inhibited after 24 and 48 h, but settlement was not significantly inhibited compared to the controls for some plastics after 72–96 h. In 24 h exposure to seawater, we found larval toxicity and inhibition of settlement with all seven categories of recyclable commercial plastics. Chemical analysis revealed a complex mixture of substances released in plastic leachates. Leaching of toxic compounds from all plastics should be considered when assessing the risks of plastic pollution.
The aim of this study was to determine the validity of acute myocardial infarction (AMI) diagnosis coding in the National Health Insurance Research Database (NHIRD) by cross-comparisons of discharge ...diagnoses listed in the NHIRD with those in the medical records obtained from a medical center in Taiwan.
This was a cross-sectional study comparing records in the NHIRD and discharge notes in one medical center (DNMC) in the year 2008. Positive predictive values (PPVs) for AMI diagnoses were evaluated by reviewing the relevant clinical and laboratory data recorded in the discharge notes of the medical center. Agreement in comorbidities, cardiac procedures, and antiplatelet agent (aspirin or clopidogrel) prescriptions between the two databases was evaluated.
We matched 341 cases of AMI hospitalizations from the two databases, and 338 cases underwent complete chart review. Of these 338 AMI cases, 297 were confirmed with clinical and lab data, which yielded a PPV of 0.88. The consistency rate for coronary intervention, stenting, and antiplatelet prescription at admission was high, yielding a PPV over 0.90. The percentage of consistency in comorbidity diagnoses was 95.9% (324/338) among matched AMI cases.
The NHIRD appears to be a valid resource for population research in cardiovascular diseases.
In the metagenomic assembly of a microbial community, abundant species are often thought to assemble well given their deeper sequencing coverage. This conjuncture is rarely tested or evaluated in ...practice. We often do not know how many abundant species are missing and do not have an approach to recover them.
Here, we propose k-mer based and 16S RNA based methods to measure the completeness of metagenome assembly. We show that even with PacBio high-fidelity (HiFi) reads, abundant species are often not assembled, as high strain diversity may lead to fragmented contigs. We develop a novel reference-free algorithm to recover abundant metagenome-assembled genomes (MAGs) by identifying circular assembly subgraphs. Complemented with a reference-free genome binning heuristics based on dimension reduction, the proposed method rescues many abundant species that would be missing with existing methods and produces competitive results compared to those state-of-the-art binners in terms of total number of near-complete genome bins.
Our work emphasizes the importance of metagenome completeness, which has often been overlooked. Our algorithm generates more circular MAGs and moves a step closer to the complete representation of microbial communities.
Enantioenriched chiral amines are of exceptional importance in the pharmaceutical industry. Recently, several new methods for the installation of these functional groups directly from non-acidic C(sp
...3
)-H bonds by catalytic intermolecular enantioselective amination have been reported. These methods represent significant advances of the field and most of them display high levels of enantioselectivity, utilize the C(sp
3
)-H substrate as the limiting reagent, feature good functional group tolerance, and show compatibility with late-stage C(sp
3
)-H amination of advanced substrates. This perspective provides an overview of the recent developments in this rapidly advancing field and outlines possibilities and limitations, which will help identify unsolved challenges and guide future research efforts.
Recently, the field of intermolecular enantioselective amination of non-acidic C(sp
3
)-H bonds has witnessed rapid advances, which are discussed in this perspective