Streamlined Synthesis of Varied Heteroarene-Condensed Benzofuran Derivatives via [4 + 2] Annulation of Benzofuran-Derived Azadienes and N-Alkyl Quinolinium Salts.

Herein we have pioneered an innovative synthetic strategy for the efficient assembly of various heteroarene-condensed benzofuran derivatives, utilizing benzofuran-derived azadienes (BDAs) and quinolines as the starting materials. This method functions with transition-metal catalysis and uses cost-effective formic acid as the reducing agent. Mechanistic investigations indicate that this transformation would involve a [4 + 2] annulation cascade process. This approach demonstrates a high tolerance to various functional groups and yields excellent results.

Endovascular thrombectomy in wake-up stroke guided by arterial spin-labeling and fluid-attenuated inversion recovery versus diffusion-weighted imaging mismatch on MRI.

OBJECTIVE: This purpose of this study is to investigate the effectiveness and safety of utilizing the arterial spin-labeling (ASL) combined with diffusion-weighted imaging (DWI) and fluid-attenuated inversion recovery (FLAIR) combined with DWI double mismatch in the endovascular treatment of patients diagnosed with wake-up stroke (WUS). METHODS: In this single-center trial, patients diagnosed with WUS underwent thrombectomy if acute ischemic lesions were observed on DWI indicating large precerebral circulation occlusion. Patients with no significant parenchymal hypersignal on FLAIR and ASL imaging showing a hypoperfusion tissue to infarct core volume ratio of at least 1.2 were included. The participants were divided into groups receiving endovascular thrombectomy plus medical therapy or medical therapy alone, based on their subjective preference. Functional outcomes were assessed using the ordinal score on the modified Rankin scale (mRs) at 90 days, along with the rate of functional independence. RESULTS: In this study, a total of 77 patients were included, comprising 38 patients in the endovascular therapy group and 39 patients in the medical therapy group. The endovascular therapy group exhibited more favorable changes in the distribution of functional prognosis measured by mRs at 90 days, compared to the medical therapy group (adjusted common odds ratio, 3.25; 95% CI, 1.03 to 10.26; P < 0.01). Additionally, the endovascular therapy group had a higher proportion of patients achieving functional independence (odds ratio, 4.0; 95% CI, 1.36 to 11.81; P < 0.01). Importantly, there were no significant differences observed in the incidence of intracranial hemorrhage or mortality rates between the two groups. CONCLUSION: Guided by the ASL-DWI and FLAIR-DWI double mismatch, endovascular thrombectomy combined with standard medical treatment appears to yield superior functional outcomes in patients with WUS and large vessel occlusion compared to standard medical treatment alone.

Half-spectrum OFDM to quadruple the spectral efficiency of underwater wireless optical communication with digital power division multiplexing.

Improving the spectrum efficiency (SE) is an effective method to further enhance the data rate of bandwidth-limited underwater wireless optical communication (UWOC) systems. Non-orthogonal frequency-division multiplexing (NOFDM) with a compression factor of 0.5 can save half of the bandwidth without introducing any inter-carrier-interference (ICI) only if the total number of subcarriers is large enough, and we termed it as half-spectrum OFDM (HS-OFDM). To the best of our knowledge, this is the first reported work on a closed-form HS-OFDM signal in the discrete domain from the perspective of a correlation matrix. Due to the special mathematical property, no extra complex decoding algorithm is required at the HS-OFDM receiver, making it as simple as the conventional OFDM receiver. Compared with traditional OFDM, HS-OFDM can realize the same data rate, but with a larger signal-to-noise ratio (SNR) margin. To fully use the SNR resource of the communication system, we further propose a digital power division multiplexed HS-OFDM (DPDM-HS-OFDM) scheme to quadruple the SE of conventional OFDM for the bandwidth-starved UWOCs. The experimental results show that HS-OFDM can improve the receiver sensitivity by around 4 dB as opposed to conventional 4QAM-OFDM with the same data rate and SE. With the help of the DPDM-HS-OFDM scheme, the data rate of multi-user UWOC can reach up to 4.5 Gbps under the hard-decision forward error correction (HD-FEC) limit of a bit error rate (BER) of 3.8×10-3. Although there is some performance degradation in comparison with single-user HS-OFDM, the BER performance of multi-user DPDM-HS-OFDM is still superior to that of conventional single-user 4QAM-OFDM. Both single-user HS-OFDM and multi-user DPDM-HS-OFDM successfully achieve 2 Gbps/75 m data transmission, indicating that the DPDM-HS-OFDM scheme is of great importance in bandwidth-limited UWOC systems and has guiding significance to underwater wireless optical multiple access.

Catalytic Enantioselective 6π Photocyclization of Acrylanilides.

Controlling absolute stereochemistry in catalytic photochemical reactions is generally challenging owing to high rates of background reactivity. Successful strategies broadly rely on selective excitation of the reaction substrate when associated with a chiral catalyst. Recent studies have demonstrated that chiral Lewis acid complexes can enable selective energy transfer from a photosensitizer to facilitate enantioselective triplet state reactions. Here, we apply this approach to the enantioselective catalysis of a 6π photocyclization through the design of an iridium photosensitizer optimized to undergo energy transfer to a reaction substrate only in the presence of a chiral Lewis acid complex. Among a group of iridium(III) sensitizers, enantioselectivity and yield closely correlate with photocatalyst triplet energy within a narrow window enabled by a modest reduction in substrate triplet energy upon binding a scandium/ligand complex. These results demonstrate that photocatalyst tuning offers a means to suppress background reactivity and improve enantioselectivity in photochemical reactions.

Wide-field-of-view auto-coupling optical antenna system for high-speed bidirectional optical wireless communications in C band.

Due to a great many superior features of infrared light communication (ILC), like high capacity and strong privacy, ILC is considered a potential candidate for serving the high demands of beyond fifth-generation/sixth-generation (B5G/6 G) communication systems. However, the terminal's limited field-of-view (FOV) induces great difficulty in establishing line-of-sight (LoS) link between the transceiver and the terminal. In this paper, we propose a wide-FOV auto-coupling optical antenna system that utilizes a wide-FOV telecentric lens to collect incident infrared beams and automatically couple them into a specific single-mode-fiber (SMF) channel of fiber array and optical switch. The performance of this optical antenna system is assessed through simulation and manual alignment operation, and validated by automatic alignment results. A coupling loss of less than 10.6 dB within a FOV of 100° for both downstream and upstream beams in C band is demonstrated by the designed system. Furthermore, we establish a bidirectional optical wireless communications (OWC) system employing this antenna and a fiber-type modulating retro-reflector (MRR) system in the terminal. Both 10-Gbps on-off keying (OOK) downstream and upstream transmissions are successfully realized with the FOV of up to 100° in C band where the measured bit-error-rate (BER) is lower than 3.8 × 10-3. To the best of our knowledge, this is a brand-new auto-coupling optical antenna system with the largest FOV in ILC automatic alignment works in terminals that have ever been reported.

Copper-catalyzed one-pot [3 + 2] cycloadditions of ethynyl indoloxazolidones with 1,3-cyclohexanediones.

Fused furans are commonly found units in natural products and medicinal molecules, and methods for their introduction are of fundamental importance. Here we report one-pot cycloadditions of ethynyl indoloxazolidones with 1,3-cyclohexanediones enabled by copper catalysis, leading to a series of functionalized furan derivatives in good yields. This method features mild reaction conditions, high efficiency, and wide substrate scope.

Experimental demonstration of real-time optical DFT-S DMT signal transmission for a blue-LED-based UWOC system using spatial diversity reception.

Underwater wireless optical communication (UWOC) has broad prospects in underwater real-time applications. We design and experimentally demonstrate a real-time discrete Fourier transform spread discrete multi-tone (DFT-S DMT) signal transmission based on a field programmable gate array for a blue-LED-based UWOC system with a data rate of up to 30 Mbps over a 15-m underwater channel. The architecture and usage of an on-chip resource as well as power consumption are analyzed and discussed. To reduce the impacts of multipath fading and received intensity fluctuation, spatial diversity reception is also introduced. Furthermore, the receiver sensitivity at a specified bit error rate (BER) threshold and the quality of the images are evaluated using three types of Reed-Solomon (RS) codes. At the BER threshold of 10-4, over 2.8-dB receiver sensitivity improvement is obtained by the DFT-S DMT scheme with the RS (64, 56) code as compared to the uncoded one at the data rate of 30 Mbps. The performance of BER, color difference, and structural similarity in the image transmission of DFT-S DMT is superior to that of the conventional hard clipping quadrature amplitude modulation DMT in a high-data-rate region because of the low peak-to-average-power ratio and ability to mitigate high-frequency fading in a band-limited UWOC system. With schemes of the RS code, DFT-S, and diversity reception, error-free transmission of images is achieved over a 15-m water channel. The proposed UWOC system has the advantages of low power consumption and portability, which foresees a bright future in underwater applications over short to moderate distances.

Label-reconstruction-based pseudo-subscore learning for action quality assessment in sporting events.

Most existing action quality assessment (AQA) methods provide only an overall quality score for the input video and lack an evaluation of each substage of the movement process; thus, these methods cannot provide detailed feedback for users. Moreover, the existing datasets do not provide labels for substage quality assessment. To address these problems, in this work, a new label-reconstruction-based pseudo-subscore learning (PSL) method is proposed for AQA in sporting events. In the proposed method, the overall score of an action is not only regarded as a quality label but also used as a feature of the training set. A label-reconstruction-based learning algorithm is built to generate pseudo-subscore labels for the training set. Moreover, based on the pseudo-subscore labels and overall score labels, a multi-substage AQA model is fine-tuned from the PSL model to predict the action quality score of each substage and the overall score for an athlete. Several ablation experiments are performed to verify the effectiveness of each module. The experimental results show that our approach achieves state-of-the-art performance.

An ionic lock and a hydrophobic zipper mediate the coupling between an insect pheromone receptor BmOR3 and downstream effectors.

Pheromone receptors (PRs) recognize specific pheromone compounds to guide the behavioral outputs of insects, which are the most diverse group of animals on earth. The activation of PRs is known to couple to the calcium permeability of their coreceptor (Orco) or putatively with G proteins; however, the underlying mechanisms of this process are not yet fully understood. Moreover, whether this transverse seven transmembrane domain (7TM)-containing receptor is able to couple to arrestin, a common effector for many conventional 7TM receptors, is unknown. Herein, using the PR BmOR3 from the silk moth Bombyx mori and its coreceptor BmOrco as a template, we revealed that an agonist-induced conformational change of BmOR3 was transmitted to BmOrco through transmembrane segment 7 from both receptors, resulting in the activation of BmOrco. Key interactions, including an ionic lock and a hydrophobic zipper, are essential in mediating the functional coupling between BmOR3 and BmOrco. BmOR3 also selectively coupled with Gi proteins, which was dispensable for BmOrco coupling. Moreover, we demonstrated that trans-7TM BmOR3 recruited arrestin in an agonist-dependent manner, which indicates an important role for BmOR3-BmOrco complex formation in ionotropic functions. Collectively, our study identified the coupling of G protein and arrestin to a prototype trans-7TM PR, BmOR3, and provided important mechanistic insights into the coupling of active PRs to their downstream effectors, including coreceptors, G proteins, and arrestin.

Counterion-Mediated Enantioconvergent Synthesis of Axially Chiral Medium Rings.

There are few enantioconvergent reactions in which racemic substrates bearing multiple stereochemical features are converted into products with high levels of diastereo- and enantiocontrol. Here, we disclose a process for the highly enantio- and diastereoselective syntheses of medium ring lactams via an intramolecular counterion-directed C-alkylation reaction. The treatment of racemic biaryl anilides that exist as a complex mixture of enantiomers and diastereoisomeric conformers by virtue of multiple axes of restricted rotation with a quinidine-derived ammonium salt under basic conditions affords medium ring lactams bearing elements of both axial and point chirality via an enolate-driven configurational relaxation process. Thermal equilibration of the syn- and anti-product diasteroisomers has demonstrated that the barriers to bowl inversion are >124 kJ mol-1. We propose that the chiral ammonium salt differentiates between a complex and rapidly equilibrating mixture of enolate and rotational isomers, ultimately leading to highly enantioselective alkylative ring closure. This dynamic and enantioconvergent process offers an operationally simple approach to the synthesis of valuable chiral medium ring lactams for which there are few catalytic and enantioselective approaches.

100-m/3-Gbps underwater wireless optical transmission using a wideband photomultiplier tube (PMT).

In this paper, a wideband photomultiplier tube (PMT)-based underwater wireless optical communication (UWOC) system is proposed and a comprehensive experimental study of the proposed PMT-based UWOC system is conducted, in which the transmission distance, data rate, and attenuation length (AL) is pushed to 100.6 meters, 3 Gbps, and 6.62, respectively. The receiver sensitivity at 100.6-meter underwater transmission is as low as -40 dBm for the 1.5-Gbps on-off keying (OOK) modulation signal. To the best of our knowledge, this is the first Gbps-class UWOC experimental demonstration in >100-meter transmission that has ever been reported. To further minimize the complexity of channel equalization, a sparsity-aware equalizer with orthogonal matching pursuit is adopted to reduce the number of the filter coefficients by more than 50% while keeping slight performance penalty. Furthermore, the performance of the proposed PMT-based UWOC system in different turbidity waters is investigated, which shows the robustness of the proposed scheme. Thanks to the great sensitivity (approaching the quantum limit) and a relatively larger effective area, benefits of misalignment tolerance contributed by the PMT is verified through a proof-of-concept UWOC experiment.

Nonylphenol Promoted Epithelial-Mesenchymal Transition in Colorectal Cancer Cells by Upregulating the Expression of Regulator of Cell Cycle.

Nonylphenol (NP) is a widely used chemical, which has been considered a kind of endocrine-disrupting chemical and is involved in the occurrence and development of many types of cancers. Our recent studies demonstrated that NP exposure is related to colorectal cancer (CRC) progression. In this study, we also found epithelial-mesenchymal transition (EMT) promoted by NP treatment in CRC cells. However, the mechanism of NP on tumor metastasis is still unclear. In this study, we focused on the effect of the regulator of cell cycle (RGCC) induced by NP treatment. The cancer genome atlas (TCGA) analysis suggested that the expression of RGCC increased in CRC tissues, and our clinical samples showed that the expression of RGCC in tumor tissues is positively correlated with the serum level of NP in CRC patients. Further studies revealed that overexpression of RGCC could enhance the NP-induced EMT process in CRC cells and activate ERK signaling pathways. Inhibiting ERK signaling by ERK inhibitors or the knockdown of RGCC could attenuate the NP-induced EMT process. In addition, both RGCC overexpression and NP treatment could activate ERK pathways and attenuate the effect of ERK inhibitors on the EMT process in CRC cells. Altogether, this study demonstrated that NP could induce cell invasion and migration by increasing the expression of RGCC to enhance the EMT process, which might be through the activation of ERK signaling pathways. This finding supported a potential target for studying NP exposure-related colorectal cancers.

Visible-Light-Induced Difunctionalization of Alkenyl Ketones with α-Carbonyl Alkyl Bromide: Concomitant Installation of C-C Bonds.

The visible-light-promoted difunctionalization of alkenyl ketones has been developed for easy access of various tetralones, cyclopropane, or alkenyl migration compounds. With fac-[Ir(ppy)3] as the photocatalyst, alkenyl ketones captured the α-carbonyl alkyl radical and evolved through intramolecular cyclization and the elimination of a proton to give the difunctionalized products. This strategy is characterized by good yields, mild reaction conditions, and outstanding functional group tolerance.

Silver-Rich Hybrid Framework Iodide Based on [Ag8I6]2+ Clusters Displays Low-Temperature Dual Emission and Luminescence Thermochromism.

Cluster-based framework metal iodides have diverse structures and excellent luminescence properties, and show promising applications in sensing and solid-state lighting. However, the design and synthesis of these materials remain great challenges because excess I- ions introduced into the synthesis systems decrease the condensation degree of M-I units. In this work, a new strategy is developed to control the condensation behavior of Ag-I units, and a new silver-rich cluster-based framework iodide [DabcoAg8I6(SPh)2]n (1) (Dabco = 1,4-diazabicyclo [2.2.2] octane) has been synthesized under solvothermal conditions in the presence of silver thiophenolate (AgSPh)n. Compound 1 features a three-dimensional (3-D) cluster-based framework with a pillared layer structure composed of cationic [Ag8I6]2+ clusters bridged by SPh- and Dabco, and displays low-temperature dual emission and luminescence thermochromism.

Underwater wireless optical communication utilizing low-complexity sparse pruned-term-based nonlinear decision-feedback equalization.

The nonlinearity of the light-emitting diode (LED) in underwater wireless optical communication (UWOC) systems is considered the one major limiting factor that degrades the system's performance. Volterra series-based nonlinear equalization is widely employed to mitigate such nonlinearity in communication systems. However, the conventional Volterra series-based model is of high complexity, especially for the nonlinearity of higher-order terms or longer memory lengths. In this paper, by pruning away some negligible beating terms and adaptively picking out some of the dominant terms while discarding the trivial ones, we propose and experimentally demonstrate a sparse pruned-term-based nonlinear decision-feedback equalization (SPT-NDFE) scheme for the LED-based UWOC system with an inappreciable performance degradation as compared to systems without the pruning strategy. Meanwhile, by replacing the self/cross beating terms with the terms formed by the absolute operation of a sum of two input samples instead of the product operation terms, a sparse pruned-term-based absolute operation nonlinear decision-feedback equalization (SPT-ANDFE) scheme is also introduced to further reduce complexity. The experimental results show that the SPT-NDFE scheme exhibits comparable performance as compared to the conventional NDFE (nonlinear decision-feedback equalization) scheme with lower complexity (the nonlinear coefficients are reduced by 63.63% as compared to the conventional NDFE scheme). While the SPT-ANDFE scheme yields suboptimal performance with further reduced complexity at the expense of a slight performance degradation, the robustness of the proposed schemes in different turbidity waters is experimentally verified. The proposed channel equalization schemes with low complexity and high performance are promising for power/energy-sensitive UWOC systems.

Experimental demonstration of 50-m/5-Gbps underwater optical wireless communication with low-complexity chaotic encryption.

In this paper, a low-complexity two-level chaotic encryption scheme is introduced and experimentally demonstrated to improve the physical layer security of a 450-nm laser underwater optical wireless communication (UOWC) system using discrete Fourier transform spread discrete multi-tone (DFT-S DMT) modulation. In the first encryption stage, the original bit stream is encrypted with a chaotic sequence based on a one-dimensional Logistic map. In the second encryption stage, the real and imaginary components of the DFT-S symbols are further encrypted with a pair of separate chaotic sequences, which are generated from a two-dimensional Logistic iterative chaotic map with infinite collapse (2D-LICM). The experimental results indicate that the encryption operation has no negative effect on the performance of the proposed UOWC system. For chaotic encryption, the DFT-S DMT gives a better performance than the DMT scheme under different water turbidities. 55-m/4.5-Gbps and 50-m/5-Gbps underwater transmissions are successfully demonstrated by the chaotic encrypted DFT-S DMT scheme. To the best of our knowledge, this is the first time to verify the feasibility of chaotic encryption in a high-speed UOWC system.

Brønsted Acid-Catalyzed Formal (3+3)-Annulation of Propargylic (Aza)-para-Quinone Methides with 4-Hydroxycoumarins and 1,3-Dicarbonyl Compounds.

Herein, we describe a highly effective 1,8-conjugate-addition-mediated formal (3+3)-annulation of (aza)-para-quinone methides in situ generated from propargylic alcohols with 4-hydroxycoumarins and 1,3-dicarbonyl compounds under the catalysis of a Brønsted acid. This methodology affords efficient and practical access to synthetically important and highly functionalized pyranocoumarins and pyrans in excellent yields under mild conditions. Importantly, these products exhibit impressive inhibitory activity toward α-glucosidase.

Clinical differences in chest CT characteristics between the progression and remission stages of patients with COVID-19 pneumonia.

INTRODUCTION: Computed tomography (CT) can be effective for the early screening and diagnosis of COVID-19. This study aimed to investigate the distinctive CT characteristics of two stages of the disease (progression and remission). METHODS: We included all COVID-19 patients admitted to Wenzhou Central Hospital from January to February, 2020. Patients underwent multiple chest CT scans at intervals of 3-10 days. CT features were recorded, such as the lesion lobe, distribution characteristics (subpleural, scattered or diffused), shape of the lesion, maximum size of the lesion, lesion morphology (ground-glass opacity, GGO) and consolidation features. When consolidation was positive, the boundary was identified to determine its clarity. RESULTS: The ratios of some representative features differed between the remission stage and the progression phase, such as round-shape lesion (8.0% vs 34.4%), GGO (65.0% vs 87.5%), consolidation (62.0% vs 31.3%), large cable sign (59.0% vs 9.4%) and crazy-paving sign (20.0% vs 50.0%). Using these features, we pooled all the CT data (n = 132) and established a logistic regression model to predict the current development stage. The variables consolidation, boundary feature, large cable sign and crazy-paving sign were the most significant factors, based on a variable named "prediction of progression or remission" (PPR) that we constructed. The ROC curve showed that PPR had an AUC of 0.882 (cutoff value = 0.66, sensitivity = 0.75, specificity = 0.875). CONCLUSION: CT characteristics, in particular, round shape, GGO, consolidation, large cable sign, and crazy-paving sign, may increase the recognition of the intrapulmonary development of COVID-19.

Asymmetric Catalytic [4+5] Annulation of ortho-Quinone Methides with Vinylethylene Carbonates and its Extension to Stereoselective Tandem Rearrangement.

Palladium-catalyzed asymmetric [4+5] annulation of ortho-quinone methides (o-QMs) with substituted vinylethylene carbonates (VECs) is described for the first time, giving a novel enantioselective approach to chiral nine-membered benzoheterocycles. Based on this designed [4+5] annulation, an unprecedented silica gel-promoted tandem rearrangement reaction featuring a unique asymmetric aromatic Claisen rearrangement is explored at room temperature, offering a new method for asymmetric construction of all-carbon quaternary stereocenters embedded in chiral functionalized homoallylic alcohols.

Visible-Light-Promoted Cascade Radical Cyclization: Synthesis of Chroman-4-ones and Dihydroquinolin-4-ones.

A novel visible-light photoredox catalysis protocol for the effective and efficient synthesis of 3-substituted chroman-4-ones and 2,3-dihydroquinolin-4(1H)-ones via tandem radical addition/cyclization of alkenyl aldehydes has been described. This reaction features a broad substrate scope, mild reaction conditions, and good functional group tolerance character.