Synergistic use of photocatalysis and convergent paired electrolysis for nickel-catalyzed arylation of cyclic alcohols.

The merging of transition metal catalysis with electrochemistry has become a powerful tool for organic synthesis because catalysts can govern the reactivity and selectivity. However, coupling catalysts with alkyl radical species generated by anodic oxidation remains challenging because of electrode passivation, dimerization, and overoxidation. In this study, we developed convergent paired electrolysis for the coupling of nickel catalysts with alkyl radicals derived from photoinduced ligand-to-metal charge-transfer of cyclic alcohols and iron catalysts, providing a practical method for site-specific and remote arylation of ketones. The synergistic use of photocatalysis with convergent paired electrolysis can provide alternative avenues for metal-catalyzed radical coupling reactions.

A novel transformer-based method for predicting air absorbed dose rates in nuclear radiation environmental monitoring.

Many studies have used various methods to estimate future nuclear radiation levels to control radiation contamination, provide early warnings, and protect public health and the environment. However, due to the high uncertainty and complexity of nuclear radiation data, existing prediction methods face the challenges of low prediction accuracy and short warning time. Therefore, accurate prediction of nuclear radiation levels is essential to safeguard human health and safety. This study proposes a novel Mixformer model to predict future hourly nuclear radiation data. The seasonality and trend of nuclear radiation data are extracted by data decomposition. To address the slow speed problem common in traditional methods for long-time series prediction tasks, Mixformer simplifies the decoder with convolutional layers to speed up the convergence of the model. The experiments consider the air-absorbed dose rate of nuclear radiation data, spectral data, six climatic conditions, and two other conditions. We use MSE and MAE metrics to verify the effectiveness of Mixformer prediction. The results show that the Mixformer proposed in this paper has better prediction performance compared to the currently popular models. Therefore, the proposed model is a feasible method for industrial nuclear radiation data processing and prediction.

Bone age assessment from articular surface and epiphysis using deep neural networks.

Bone age assessment is of great significance to genetic diagnosis and endocrine diseases. Traditional bone age diagnosis mainly relies on experienced radiologists to examine the regions of interest in hand radiography, but it is time-consuming and may even lead to a vast error between the diagnosis result and the reference. The existing computer-aided methods predict bone age based on general regions of interest but do not explore specific regions of interest in hand radiography. This paper aims to solve such problems by performing bone age prediction on the articular surface and epiphysis from hand radiography using deep convolutional neural networks. The articular surface and epiphysis datasets are established from the Radiological Society of North America (RSNA) pediatric bone age challenge, where the specific feature regions of the articular surface and epiphysis are manually segmented from hand radiography. Five convolutional neural networks, i.e., ResNet50, SENet, DenseNet-121, EfficientNet-b4, and CSPNet, are employed to improve the accuracy and efficiency of bone age diagnosis in clinical applications. Experiments show that the best-performing model can yield a mean absolute error (MAE) of 7.34 months on the proposed articular surface and epiphysis datasets, which is more accurate and fast than the radiologists. The project is available at https://github.com/YameiDeng/BAANet/, and the annotated dataset is also published at https://doi.org/10.5281/zenodo.7947923.

Paired electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling between α-chloroesters and aryl bromides.

Electrochemical asymmetric catalysis has emerged as a sustainable and promising approach to the production of chiral compounds and the utilization of both the anode and cathode as working electrodes would provide a unique approach for organic synthesis. However, precise matching of the rate and electric potential of anodic oxidation and cathodic reduction make such idealized electrolysis difficult to achieve. Herein, asymmetric cross-coupling between α-chloroesters and aryl bromides is probed as a model reaction, wherein alkyl radicals are generated from the α-chloroesters through a sequential oxidative electron transfer process at the anode, while the nickel catalyst is reduced to a lower oxidation state at the cathode. Radical clock studies, cyclic voltammetry analysis, and electron paramagnetic resonance experiments support the synergistic involvement of anodic and cathodic redox events. This electrolytic method provides an alternative avenue for asymmetric catalysis that could find significant utility in organic synthesis.

MRI characteristics of brain edema in preeclampsia/eclampsia patients with posterior reversible encephalopathy syndrome.

BACKGROUND: The neuroimaging manifestations of eclampsia and preeclampsia often overlap, mainly presenting as posterior reversible encephalopathy syndrome (PRES). The purpose of this retrospective study was to compare the extent and nature of brain edema in eclampsia and preeclampsia patients with PRES based on MRI characteristics. METHODS: One hundred fifty women diagnosed with preeclampsia-eclampsia and undergoing cranial MRI were enrolled; 24 of these were diagnosed as having eclampsia. According to clinicoradiologic diagnosis of PRES, eligible patients were classified as having eclampsia with PRES (group E-PRES) and preeclampsia with PRES (group P-PRES). A scale on T2W FLAIR-SPIR images was established to evaluate the extent of brain edema, and the score of brain edema (SBE) of both groups was compared. In patients of the two groups who also underwent DWI sequence, the presence or absence of hyperintensity on DWI and hypointensity on ADC maps were determined to compare the nature of brain edema. Furthermore, clinical and biochemical data of the two groups were compared. RESULTS: The incidence of PRES in eclampsia patients was significantly higher than that in preeclampsia patients (87.50% vs. 46.03%, P<0.001). The SBE of all regions and typical regions in group E-PRES patients were significantly higher than those in group P-PRES patients (15.88±8.72 vs. 10.90±10.21, P=0.021; 8.52±3.87 vs. 5.01±4.19, P=0.002; respectively). The presence of hyperintensity on DWI was determined more frequently in group E-PRES patients than group P-PRES patients (71.43% vs. 32.00%, P=0.024). Age, systolic blood pressure, white blood cell count, neutrophil count and percentage of neutrophils were significantly different between the two groups (P<0.05). CONCLUSIONS: Certain MRI characteristics that reflect the extent and nature of brain edema were different between eclampsia and preeclampsia patients with PRES. Additional prospective studies are still required to explore whether these MRI characteristics of brain edema may further become a potential predictor for eclamptic seizures in preeclampsia patients with PRES.

Nonlinear Photonics Using Low-Dimensional Metal-Halide Perovskites: Recent Advances and Future Challenges.

Low-dimensional metal-halide perovskites have exhibited significantly superior nonlinear optical properties compared to traditional semiconductor counterparts, thanks to their peculiar physical and electronic structures. Their exceptional nonlinear optical characteristics make them excellent candidates for revolutionizing widespread applications. However, the research of nonlinear photonics based on low-dimensional metal-halide perovskites is in its infancy. There is a lack of comprehensive and in-depth summary of this research realm. Here, the state-of-the-art research progress related to third-and higher-order nonlinear optical properties of low-dimensional metal-halide perovskites with diverse crystal structures from 3D down to 0D, together with their practical applications, is summarized comprehensively. Critical discussions are offered on the fundamental mechanisms beneath their exceptional nonlinear optical performance from the physics viewpoint, attempting to disclose the role of intrinsic attributes (e.g., composition, bandgap, size, shape, and structure) and external modulation strategies (e.g., developing core-shell structures, transition metal ion doping, and hybridization with dielectric microspheres) in tuning the response. Additionally, their potential applications in nonlinear photonics, nonlinear optoelectronics, and biophotonics are systematically and thoroughly summed up and categorized. Lastly, insights into the current technical challenges and future research opportunities of nonlinear photonics based on low-dimensional metal-halide perovskites are provided.

Nickel-Catalyzed N-Arylation of NH-Sulfoximines with Aryl Halides via Paired Electrolysis.

A novel strategy for the N-arylation of NH-sulfoximines has been developed by merging nickel catalysis and electrochemistry (in an undivided cell), thereby providing a practical method for the construction of sulfoximine derivatives. Paired electrolysis is employed in this protocol, so a sacrificial anode is not required. Owing to the mild reaction conditions, excellent functional group tolerance and yield are achieved. A preliminary mechanistic study indicates that the anodic oxidation of a NiII species is crucial to promote the reductive elimination of a C-N bond from the resulting NiIII species at room temperature.

Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts.

Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones (such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C-H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.

Electrochemically Enabled C3-Formylation and -Acylation of Indoles with Aldehydes.

Reported herein is an effective strategy for oxidative cross-coupling of indoles with various aldehydes. The strategy is based on a two-step transformation via a well-known Mannich-type reaction and a C-N bond cleavage for carbonyl introduction. The key step-the C-N bond cleavage of the Mannich product-was enabled by electrochemistry. This strategy (with over 40 examples) ensures excellent functional-group tolerance as well as late-stage functionalization of pharmaceutical molecules.