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Recently, algorithm-hardware (HW) co-exploration for neural networks (NNs) has become the key to obtaining high-quality solutions. However, previous efforts for field-programmable gate arrays (FPGAs) focus on neural architecture search (NAS) while lacking HW architecture search (HAS), thus limiting the full potential of co-design. Although expanding the scope of HAS offers performance potential, the exponentially increased joint search space presents a formidable challenge. To address this, we propose a deep and efficient framework NAF, which jointly searches for Networks and Accelerators for FPGAs in a balanced co-search space. First, we adjust the NAS space and then introduce a block-level bitwidth search on the software side. Meanwhile, we design a HW-friendly quantization algorithm to facilitate HW efficiency and accuracy. Second, we design a dataflow-configurable HW unit with computation and memory access optimizations for quantized multiplication. Based on this, we incorporate critical heterogeneous multicore architecture exploration on the HW side. Third, to enable rapid HW feedback in the enlarged HAS space, we perform resource and performance modeling and design a fast HW generation algorithm based on the genetic algorithm. Specifically, we apply optimization techniques, like mapping space pruning, greedy bandwidth allocation, and coarse-grained search, to speed up this process. We validate NAF in edge and cloud scenarios. Experimental results show that NAF efficiently explores a significantly larger joint space and provides high-quality solutions. Compared with previous state-of-the-art co-design works, the searched convolutional neural network-accelerator pairs improve the throughput by $2.07\times \sim 7.10\times $ and energy efficiency by $1.41\times \sim 2.27\times $ under similar accuracy on the ImageNet dataset.

ABSTRACTAs a global infrastructure development strategy launched by the Chinese government in 2013, the “Belt and Road Initiative” has attracted increasing attention. Most studies have interpreted the strategy from the perspectives of macro policy, diplomatic and economic influence, and education communication. However, there is a scarcity of studies focusing on factors influencing BRI students’ decision to study in China. With a sequential explanatory mixed method, the paper compared BRI and non-BRI students and found that the two groups’ students have significantly different motivations to study in China. Their decisions are usually based on whether external factors can meet their personal needs and the possible benefits and cost of meeting such needs. Hence, it is suggested that China take different marketing strategies in response to different students’ needs and improve the quality and visibility of higher education to China’s international education’s sustainable development.

Objective: To analyze the spatial autocorrelation and spatiotemporal clustering characteristics of severe fever with thrombocytopenia syndrome(SFTS) in Anhui Province from 2011 to 2023. Methods: Data of SFTS in Anhui Province from 2011 to 2023 were collected. Spatial autocorrelation analysis was conducted using GeoDa software, while spatiotemporal scanning was performed using SaTScan 10.0.1 software to identify significant spatiotemporal clusters of SFTS. Results: From 2011 to 2023, 5720 SFTS cases were reported in Anhui Province, with an average annual incidence rate of 0.7131/100,000. The incidence of SFTS in Anhui Province reached its peak mainly from April to May, with a small peak in October. The spatial autocorrelation results showed that from 2011 to 2023, there was a spatial positive correlation(P< 0.05) in the incidence of SFTS in all counties and districts of Anhui Province. Local autocorrelation high-high clustering areas are mainly located in the south of the Huaihe River. The spatiotemporal scanning results show three main clusters of SFTS in recent years: the first cluster located in the lower reaches of the Yangtze River, the eastern region of Anhui Province; the second cluster primarily focused on the region of the Dabie Mountain range, while the third cluster primarily focused on the region of the Huang Mountain range. Conclusions: The incidence of SFTS in Anhui Province in 2011–2023 was spatially clustered.

To facilitate depolymerization of cellulose into fermentable sugars, a novel deep eutectic solvent (DES)–mediated Fenton-like system was developed for efficient removal of hemicellulose and lignin components from lignocellulosic biomass. Water hyacinth (WH) was treated with the newly synthesized DES (choline chloride-ethylene glycol-FeCl3; ChCl-EG-FeCl3) at 140 °C for 2 h and then subjected to treatment with 32 mL 30 wt% H2O2(Fe3+: H2O2= 1:50 mol·mol–1) for 1 h in a Fenton-like reaction system (DES/H2O2). Hydrolysate containing 28 g·L–1glucose was obtained, which was 19.6- and 1.6-fold of raw WH and WH pretreated by DES, respectively. The DES/H2O2-WH hydrolysate was further evaluated for butanol fermentation; no significant inhibition was observed on butanol production, giving butanol titer of 8.3 g·L–1, along with a yield of 0.18 g·g–1glucose and a productivity of 0.12 g·L–1·h–1. Remarkably, DES could be recovered and recycled for five consecutive batches.

The growing Chinese universities are implementing open innovation (OI). However, the function of OI in the innovation activities is still unclear. This article elaborates on how outbound OI (OOI) and inbound OI (IOI), which includes four types of partners [i.e., domestic research institutions, domestic higher education, domestic enterprises, and foreign institutions], influence the innovation efficiency of invention patents (IPA) and scientific papers (FPA) in the context of Chinese universities. Based on a panel dataset from 2009 to 2018 in China, we find that OOI significantly facilitates innovation efficiency of universities. IOI with DHE and FI can promote innovation efficiency in IPA and FPA, respectively. Moreover, we also investigate the moderating role of absorptive capacity in the relationship between OI and innovation efficiency. The results show some heterogeneity in the different types of OI. The study enriches the influencing factors of innovation efficiency in relation to OI and expands the research subject of OI topic. Furthermore, this article supplements the knowledge regarding the boundary conditions under which the effect of OI is strengthened or weakened.

Deep clustering, which can elegantly exploit data representation to seek a partition of the samples, has attracted intensive attention. Recently, combining auto-encoder (AE) with graph neural networks (GNNs) has accomplished excellent performance by introducing structural information implied among data in clustering tasks. However, we observe that there are some limitations of most existing works: 1) in practical graph datasets, there exist some noisy or inaccurate connections among nodes, which would confuse network learning and cause biased representations, thus leading to unsatisfied clustering performance; 2) lacking dynamic information fusion module to carefully combine and refine the node attributes and the graph structural information to learn more consistent representations; and 3) failing to exploit the two separated views’ information for generating a more robust target distribution. To solve these problems, we propose a novel method termed deep fusion clustering network with reliable structure preservation (DFCN-RSP). Specifically, the random walk mechanism is introduced to boost the reliability of the original graph structure by measuring localized structure similarities among nodes. It can simultaneously filter out noisy connections and supplement reliable connections in the original graph. Moreover, we provide a transformer-based graph auto-encoder (TGAE) that can use a self-attention mechanism with the localized structure similarity information to fine-tune the fused topology structure among nodes layer by layer. Furthermore, we provide a dynamic cross-modality fusion strategy to combine the representations learned from both TGAE and AE. Also, we design a triplet self-supervision strategy and a target distribution generation measure to explore the cross-modality information. The experimental results on five public benchmark datasets reflect that DFCN-RSP is more competitive than the state-of-the-art deep clustering algorithms. The corresponding code is available at https://github.com/gongleii/DFCN-RSP.

Wind power (WP) represents a Renewable Energy Source (RES) that has noticed substantial development as people continuously search for green energy sources. Utilizing predominantly Predictive Maintenance (PM) of Wind Turbines (WT), this research analyzes the potential benefits that could be generated by Wind Energy (WE) through the use of the Internet of Things (IoT) and Wireless Sensor Networks (WSN). This research recommends an Internet of Things-WSN model for PM comprised of three distinct phases: the primary phase is the collection of data via sensors, the second phase is the transmission of that data through a connection to the Internet, and the final phase is the implementation of data analytics on that data in the context of cloud computing. For PM analytics, this work introduces a Predictive Maintenance Convolutional Long Short-Term Memory (PM-C-LSTM) model that combines the spatial pattern recognition capabilities of a Convolutional Neural Network with the sequential data prowess of LSTM networks. The PM-C-LSTM model combines CNN for recognizing spatial patterns and LSTM networks for analyzing sequential data in a way that doesn't affect the accuracy of WT-PM. A Failure Sample Generator model is also fused into the study to measure soft failure and hard failure factors and improve the predictive accuracy of the Machine Learning (ML) model. Data became available over 16 months while the model was applied to a Wind Farm (WF) positioned on the Qinghai-Tibet Plateau. It has been demonstrated that the PM-C-LSTM model possesses enhanced PM capabilities by comparing its efficiency to other standard models using a selection of performance metrics. The result of the test indicates that there is a probability that the hybrid IoT and ML will improve PM methods in WT, which will subsequently help improve the effectiveness and sustainability of WE generation.

Redox-active organic materials are capturing growing attention as cathode materials for sustainable alkaline metal ion batteries. However, the storage of Na+in most organic materials-based cathodes is plagued by low capacity and unsatisfying rate performance due to their low active site densities and limited exposed active sites. Herein, two polyimide-linked covalent organic frameworks (COFs), namely HATN-PD-COF and HATN-TAB-COF, were fabricated from hydrothermal synthesis with redox-active triphenylene-2,3,6,7,10,11-hexacarboxylic acid and aromatic amines as starting materials. Powder X-ray diffraction and electron microscopy analysis indicate the high crystalline nature of these COFs with AA stacking configuration and orderly mesoporous tunnel. N2sorption measurement discloses the permanent porosity of these two COFs with a Brunauer-Emmett-Teller surface area of 1,065–1,200 m2g−1and a large pore size of 2.0–3.1 nm. Galvanostatic intermittent titration technique and density functional theory calculations reveal the facile Na+ion diffusion along the mesoporous tunnel of these COFs with a small energy barrier of 0.13–0.40 eV. In particular, the as-prepared COFs based-cathodes show ultrafast and stable Na+storage associated with their conjugated electronic structure, highly ordered mesoporous tunnel, robust structure, and redox-active C=N/C=O-rich framework as exemplified by the high reversible capacity of 210 mA h g−1at 200 mA g−1, record-high rate performance (195 mA h g−1at a high current density of 10,000 mA g−1) among organic electrodes and the capacity retention of nearly 91% at 10,000 mA g−1after 7,000 cycles for HATN-PD-COF.

Fish in nature exhibit a variety of swimming modes such as forward swimming, backward swimming, turning, pitching, etc., enabling them to swim in complex scenes such as coral reefs. It is still difficult for a robotic fish to swim autonomously in a confined area as a real fish. Here, we develop an untethered robotic manta as an experimental platform, which consists of two flexible pectoral fins and a tail fin, with three infrared sensors installed on the front, left, and right sides of the head to sense the surrounding obstacles. To generate multiple swimming modes of the robotic manta and online switching of different modes, we design a closed-loop Central Pattern Generator (CPG) controller based on distance information and use a combination of phase difference and amplitude of the CPG model to achieve stable and rapid adjustment of yaw angle. To verify the autonomous swimming ability of the robotic manta in complex scenes, we design an experimental scenario with a concave obstacle. The experimental results show that the robotic manta can achieve forward swimming, backward swimming, in situ turning within the concave obstacle, and finally exit from the area safely while relying on the perception of external obstacles, which can provide insight into the autonomous exploration of complex scenes by the biomimetic robotic fish. Finally, the swimming ability of the robotic manta is verified by field tests.

Graphical abstract:

Due to the low efficiency of a single metal Bi in the CO2reduction reaction (CO2RR) to formates, enhancing the conductivity and yield through surface engineered composites is an alluring approach. In this study, we reconstruct Bi nanoparticles in situgrowth in 3D nanoporous copper structures. Benefiting from the 3D nanoporous conductive network and the strong interaction between Cu and Bi, the Fermi level becomes shifted upward and the resulting Bi@np-Cu displays a surprising CO2RR performance. Bi@np-Cu demonstrates a formate faradaic efficiency of 97.7% at a potential of −0.97 V vs. reversible hydrogen electrode with a remarkable current density of 82 mA cm−2. Importantly, this catalyst also has a faradaic efficiency of more than 90% for a continuous CO2RR of 40 h. Density function theory calculations reveal that np-Cu effectively modulates the electronic states of Bi, optimizing the intermediate adsorption energy and leading to increased intrinsic activity of Bi. This study provides a novel perspective on the applications of nanoporous metals in catalysis.

Graph random walk sampling is becoming increasingly important with the widespread popularity of graph applications. It aims to capture the desirable graph properties by launching multiple walkers to collect feature paths. However, previous research suffers long sampling latency and severe memory access bottlenecks due to intrinsic data dependency and skewed vertex distribution. Thus, in this paper, we propose FastRW, a dedicated accelerator to boost graph random walk operation on FPGAs. Specifically, FastRW first integrates multiple parallel processing engines to achieve data-level parallelism, where each processing engine also leverages dataflow scheduling to resolve data dependency and hide long sampling latency. Secondly, FastRW leverages a combination of multiple storage resources to implement a hybrid memory architecture adapted to skewed vertex distribution. By integrating the above optimizations, FastRW develops a performance model to take advantage of the balance between computation parallelism and bandwidth demand. We evaluate FastRW with two classic sampling algorithms on a wide range of real-world graph datasets. The experimental results show that FastRW achieves a speedup of 37.52$\boldsymbol{\times}$× on average over the system running on two 8-core Intel CPUs. FastRW also achieves an average of 28.04$\boldsymbol{\times}$× speedup over the architecture implemented on V100 GPU.

A highly effective approach based on an organophotocatalytic α-C(sp3)–H functionalization/radical cyclization cascade has been developed. This method enables the synthesis of various tricyclic heterocycles containing S, O, and N atoms with excellent site selectivity and diastereoselectivity. Mechanistic investigations have confirmed that the reaction involves photoredox-triggered C(sp3)–H cleavage followed by a radical cyclization and aromatization process. These findings are expected to pave the way for developing cost-effective tandem radical reactions and synthesizing heterocyclic drugs.

Background: Anastomosis-related complications such as bleeding, leakage, and strictures, continue to be serious complications of gastric cancer surgery. Presently, these complications have yet to be reliably prevented. Here we design a comprehensive leak testing procedure which combines gastroscopy, air, and methylene blue (GAM) leak testing. We aimed to evaluated the efficacy and safety of the GAM procedure in patients with gastric cancer. Methods: Patients aged 18–85 years without an unresectable factor as confirmed via CT were enrolled in a prospective randomized clinical trial at a tertiary referral teaching hospital and were randomly assigned to two groups: intraoperative leak testing group (IOLT) and no intraoperative leak testing group (NIOLT). The primary endpoint was the incidence of postoperative anastomosis-related complications in the two groups. Results: 148 patients were initially randomly assigned to the IOLT group (n= 74) and to the NIOLT group (n= 74) between September 2018 and September 2022. After exclusions, 70 remained in the IOLT group and 68 in the NIOLT group. In the IOLT group, 5 patients (7.1%) were found to have anastomotic defects intraoperatively, which included anastomotic discontinuity, bleeding, and strictures. The NIOLT group had a higher incidence of postoperative anastomotic leakage compared to the IOLT group: 4 patients (5.8%) vs 0 patients (0%), respectively. No GAM-related complications were observed. Conclusion: The GAM procedure is an intraoperative leak test that can be performed safely and efficiently after a laparoscopic total gastrectomy. GAM anastomotic leak testing may effectively prevent technical defect-related anastomotic complications in patients with gastric cancer who undergo a gastrectomy.

Electrocatalytic synthesis of urea from CO2and under ambient conditions provides an appealing alternative to the traditional energy-intensive urea synthetic protocol. Highly active and selective electrocatalysts for efficient urea production are therefore urgently desired owing to the unsatisfactory performance of the thus far reported catalysts. Herein, a phthalocyanine-based (Pc-based) covalent organic framework (COF), namely CoPc-COF, fabricated from the nucleophilic substitution reaction of hexadecafluorophthalocyaninato cobalt with octahydroxylphthalocyanine cobalt, in situgrew on the surface of multilayered TiO2nanotubes (NTs), generating the CoPc-COF@TiO2NTs composite. Powder X-ray diffraction analysis in combination with electron microscopy measurements discloses the uniform coating of crystalline CoPc-COF on the multilayered TiO2NTs in CoPc-COF@TiO2NTs. Remarkably, electrochemical tests reveal the superior electrocatalytic activity of CoPc-COF@TiO2NTs towards urea production from CO2and with a record-high yield of 1,205 µg h−1cm−2and an outstanding Faraday efficiency of 49% at −0.6 V versusreversible hydrogen electrode due to the significant synergistic catalysis effect. {tiIn situ} attenuated total reflection infrared spectroscopic investigation and theoretical calculations unveil the efficient C–N coupling reaction between *CO intermediate derived from CO2on CoPc moieties and *NH2intermediate formed from on TiO2NTs during the urea formation process over CoPc-COF@TiO2NTs. This work should be helpful towards designing and fabricating high-performance electrocatalysts for sustainable synthesis of urea through efficient synergistic effect of multiactive centers

Self-torque has recently been observed as a novel property of light that features time-varying orbital angular momentum (OAM) along a light pulse. This property offers an additional degree of freedom for manipulating light fields and light-matter interactions on ultrafast time scales. In this work, we theoretically study the self-torque's role in modulating tightly focused fields and reveal spin-orbit interactions (SOIs) in the focused fields using time-dependent vectorial diffraction theory. It is found that time-varying SOIs occur between the spin angular momentum (SAM), intrinsic OAM and extrinsic OAM. Specifically, the spin-to-orbit conversion, orbit-to-local-spin conversion, and optical spin-Hall effect are observed in the focused self-torqued beams. In particular, when the incident beams are circularly polarized, the time-dependent transverse SAM distributions will appear in the focal plane. Moreover, the self-torque of the focused light fields can be controlled via spin-to-orbit conversion. These observations could benefit potential applications in ultrafast light field modulation, microscopy, and optical manipulation.

Growing pattern matching applications are employing finite automata as their basic processing model. These applications match tens to thousands of patterns on a large amount of data, which brings a great challenge to conventional processors. Therefore hardware-based solutions have emerged frequently and achieved high throuphput automata processing. However, existing methods are generally difficult to achieve both processing speed and storage efficiency, and are often too heavy to be integrated into a small chip and have to rely on off-chip DRAMs or other high capacity memories even on some simple data sets, leading to the potential area and power consumption issues. In this paper, we focus on building a more lightweight automata processing engine, hoping to store the whole automata model into on-chip memory and run effectively and independently. We propose LAP, a lightweight automata processing engine. Powered with a novel automata model (A-DFA) and efficient packing algorithms, extremely high storage efficiency compared with traditional DFA is achieved in LAP. Meanwhile, we identify the key parallelization factors in the A-DFA model and then propose a specialized microarchitecture with novel instructions to further accelerate the state transition process. As a result, LAP can obtain more effective trade-off between processing speed and storage efficiency. Evaluation results show that LAP achieves extremely high storage efficiency on simple data sets, exceeding IBM's RegX by 8×, and achieves significant improvements in processing speed ranging from 1.32× to 1.91× compared with previous lightweight hardware implementations. Moreover, LAP has good scalability in hardware architecture. It is easy to build an acceleration system with higher throughput by increasing the number of cores. We prototype a 16-core system into Xilinx ZC702 FPGA and a 64-core system into Xilinx ZCU102 FPGA respectively. The prototype system on ZC702 on average achieves 3.5 GB/s throughput on simple data sets, and the prototype system on ZCU102 can obtain higher throughput and compute density values on part of large datasets in ANMLZoo compared with modern in-memory NFA-based solutions.

There is a pressing demand for efficient electromagnetic interference (EMI) shielding materials with strong electromagnetic wave absorption and low reflection for the protection of next-generation communication technologies and wearable electronic devices. In this work, silicone rubber/MXene/Fe3O4(SRMF) composites with a sandwich-like structure were fabricated using vacuum-assisted dipping and curing. The top and bottom layers of the SRMF composites are magnetic layers containing Fe3O4particles and silicone rubber (SR), while the middle layer is a 3D conductive network of MXene aerogel film and SR. This sandwich-like structure enables the composites to effectively shield incident electromagnetic waves and improve the absorption of electromagnetic waves through a mechanism of “absorption–reflection–reabsorption”. The electromagnetic shielding performance of a sandwich-structured SR composite containing 1.2 wt % MXene and 20 wt % Fe3O4reached 55.5 dB, which was higher than that of a blended SRM1.2F20bcomposite containing the same proportion of MXene and Fe3O4(23.1 dB), while the power coefficient of reflectivity was 0.65. The SRMF composites also retained their EMI shielding performance after 1000 bending cycles and displayed good tensile strength. These flexible SRMF composites have broad application prospects in the field of electromagnetic protection of wearable devices.

Sodium-ion batteries (SIBs) are considered as a promising next-generation energy storage system. To achieve the large-scale application of SIBs, it is crucial to develop cost-effective anode materials with high Na-ion storage capacity. Herein two-dimensional (2D) conjugated covalent organic frameworks (cCOFs) with N-rich phthalocyanine (Pc) units fused viabenzene moieties (named MPc-2D-cCOFs) were explored as the SIBs anode materials. Electrochemical tests reveal their high reversible capacities of 538 and 342 mA h g−1at 50 and 1000 mA g−1, respectively, good rate performance, and excellent stability, comparable to the state-of-the-art anode materials of SIBs, indicating their outstanding Na-ion storage performance. Ex situX-ray photoelectron and Fourier transform infrared spectroscopies together with theoretical calculations disclose the N atoms at the pore channels and conjugated pyrrole moieties of MPc-2D-cCOFs provide abundant Na-ion storage sites. This, in cooperation with the enhanced electrical conductivity owing to the 2D conjugated structure, contributes to the outstanding Na-ion storage capacity of MPc-2D-cCOFs. The present result is surely helpful for developing high-performance and cost-effective COFs as electroactive materials for SIBs.

The effect of small changes in isomers on electrochemical performance have not been focused in batteries and two isomers are reported for Zn-ion batteries here. The isomer tetrathiafulvalene (TTF) could store two monovalent anions reversibly, showing remarkable performance that outperformed most of the reported organic electrode materials for zinc-ion batteries.The isomer tetrathianaphthalene (TTN) could only reversibly store one monovalent anion and upon further oxidation, it would undergo an irreversible solid-state molecular rearrangement to TTF.

Radical chemistry, a rapidly growing field in organic synthesis, offers numerous innovative approaches for the cleavage and construction of challenging chemical bonds. Recent findings have underscored the pivotal contributions of alkali metal ions in radical-driven reactions, where they play a crucial role in lowering the energy barriers required to initiate these processes and in stabilizing vital transient radical species. These properties contribute significantly to the advancement of next-generation synthetic techniques. This article offers a concise yet thorough examination of the roles alkali metal ions assume within radical chemistry, with a specific focus on their diverse modes of activation and the associated mechanistic contexts. Our objective is to encourage and expand their strategic use across various facets of organic synthesis, catalysis, and environmentally conscious green chemistry applications.Graphical AbstractWithin this highlight review, we underscore the critical role that alkali metal ions play in the domain of radical chemistry, with a special focus on their intricate engagements with organic compounds. The insights presented herein are expected to provide invaluable guidance for future scholars seeking to grasp and capitalize on this emergent activation paradigm.

The coexistence of multiple substances in the flue gas, such as alkali metal and SO2, results in the NH3-SCR catalysts suffering from serious deactivation. Therefore, we systematically studied the effects of coexisting SO2and Na on the FeW oxides for NOxelimination. This study elucidates that the joint influence mechanism of these substances on SCR activity was regulated by reaction temperatures. When the temperature was below 300 °C, the catalyst suffered a double whammy. The addition of SO2in process of NH3-SCR resulted in a decrease in the activity of Na-poisoned FeW catalyst. It was largely due to the formation of inorganic SO42-, which not only consumed the NH3but also blocked active sites. With the increase of reaction temperatures above 300 °C, the SO2could interact with Na2O to construct a ternary electron interaction of SO42--Na+-FeW, contributing to the improvement of alkali metal resistance. This sulfate adjusted the D-band center energy of the catalyst closer to the Fermi level, thereby boosting the adsorption energies of NH3and NO, increasing their adsorption abilities. Furthermore, sulfate binding broke the Na-O-Fe and Na-O-W bonds, resulting in the restoration of Fe-O-W and Fe-O-Fe active sites and accumulation of Na+species. Precise characterizations and theoretical calculations shed light on the joint mechanism of SO2and alkali metals which provide guidance to the design SCR catalyst with excellent resistance to SO2and alkali metal poisoning.

Supplemental Digital Content is available in the text.Transcriptome expression profiles of laryngeal squamous cell carcinoma (LSCC) are altered, and we aimed to investigate expression and role of hsa_circ_0005033 (circ_0005033), microRNA (miR)-107 and insulin-like growth factor 1 receptor (IGF1R) in LSCC. Real-time PCR, western blotting and immunohistochemistry detected RNA and protein expression levels. Functional assays were performed using MTT assay, EdU assay, apoptosis assay, flow cytometry, Transwell assay, and xenograft tumor model. Direct interaction was predicted by Starbase algorithm and validated by dual-luciferase reporter assay and RNA immunoprecipitation. Expression of circ_0005033 was substantially upregulated in LSCC tissues and cells, and allied with miR-107 downregulation and IGF1R upregulation. Circ_0005033 showed a closed-loop structure and long half-life. Essentially, circ_0005033 and IGF1R were competing endogenous RNAs for miR-107 via target binding. Silencing circ_0005033 facilitated apoptosis rate and lowered cell viability, proliferation, migration and invasion of LSCC cells, as well as delayed xenograft tumor growth. Allied with that, cleaved-caspase 3/8/9 expression was elevated via death receptor-mediated and mitochondrial pathways, and expression of matrix metalloproteinase-2 (MMP2), MMP9, cyclin D1 and proliferating cell nuclear antigen was decreased. Moreover, Cisplatin-induced inhibition of cell viability was exacerbated by inhibiting circ_0005033. These functional effects of circ_0005033 depression were consistent with those of miR-107 overexpression. Furthermore, depleting miR-107 and restoring IGF1R abated the effects of circ_0005033 knockdown and miR-107 overexpression, respectively. Circ_0005033 was oncogenic in LSCC by regulating cell progression and Cisplatin sensitivity at least via miR-107/IGF1R axis.

To investigate the safety and clinical efficacy of microparticle transcatheter arterial chemoembolization (mTACE) combined with surgical resection for the treatment of huge hepatocellular carcinoma (hHCC; ≥ 10 ​cm).

The development of practical methods for the direct and selective C(sp3)-H functionalization of hydrocarbons is an attractive topic in synthetic chemistry. Although the radical-mediated hydrogen atom transfer (HAT) process has shown considerable potential in such reactions, it still faces fundamental problems associated with reactivity and selectivity. Herein, we report a convenient and economic approach to site-selective C(sp3)-H sulfonylation viaphoto-induced HAT catalysis. Employing a conjugated polycyclic quinone as a direct HAT photocatalyst, commercially available inorganic sulfinates as the sulfonylation source, copper triflate as an inexpensive oxidant, a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions. The mechanistic studies reveal that the reaction sequence involves direct HAT-induced radical formation and a subsequent copper-mediated organometallic process for the C-S bond formation. This method offers an appealing opportunity to furnish high value-added products from abundant hydrocarbon starting materials and inexpensive reagents.

In this work, novel metal–organic framework/polyimide (MOF/PI) composite films possessing dielectric properties were synthesized via a solution blending method. UiO-66 and UiO-66–NH2nanoparticles were first prepared by a hydrothermal method and added into PI to obtain the composite films. Compared with pure PI, the dielectric properties of the MOF/PI composites were substantially enhanced. The amine functionalization gave UiO-66–NH2/PI composite films better dielectric properties in comparison with UiO-66/PI composite films because of improved interaction between PI and UiO-66–NH2. It showed that the dielectric constant of the PI composite film containing 20 wt% UiO-66–NH2is 8.8 at 102Hz, which was approximately 2.5 times that of the pure PI (3.5 at 102Hz). The dielectric loss of the composite film was less than 0.034. Moreover, the breakdown strength of 20 wt% UiO-66–NH2/PI composite films was found to be 208 kV/mm. We describe this new perspective for the preparation of high-performance polymer-based dielectric materials and their application as electrical materials.

Electrochemical conversion of carbon dioxide into high value-added fuels or chemicals is a promising and sustainable way to alleviate the negative effects of excessive CO2emissions. Covalent organic frameworks (COFs) are a kind of promising electrocatalyst due to their ordered porous structure and large number of accessible active sites. However, the low current density of COFs limits their further applications. Therefore, we developed a couple of new COFs (TPE-CoPor-COF and TPTPE-CoPor-COF) based on tetraphenylethene and cobalt porphyrin derivatives with enhanced intramolecular electron transfer, in which the tetraphenylethene moiety acted as an electron donor (D) and the cobalt porphyrin moiety as an electron acceptor (A). Fortunately, TPE-CoPor-COF and TPTPE-CoPor-COF exhibit excellent CO faradaic efficiencies (FECO) (i.e., 91–95% from −0.6 to −1.0 V vs.RHE for TPE-CoPor-COF; 89–96% from −0.7 to −1.0 V vs.RHE for TPTPE-CoPor-COF). In particular, the maximum CO partial current density (jCO) of TPE-CoPor-COF reaches up to −30.4 mA cm−2at −1.0 V vs.RHE in a H-cell, exceeding most of reported COF electrocatalysts. Our work should be conducive to the development of new COF-based electrocatalysts for efficient CO2reduction.

In this study, CuO quantum dots were encapsulated in a MIL-125(Ti) MOF viaa simple oxidation method. Upon loading of LiFePO4the composite material LiFePO4/CuO@MIL-125(Ti) was formed. Due to the protection of the MIL-125(Ti) MOF, the composite photocatalyst exhibited stability in water. LiFePO4provided transferable electrons to the CuO QDs which significantly improved the efficiency and selectivity of the photocatalytic CO2reduction. Experiments showed that, at an optimal ratio of 2.5% LiFePO4/1.0% CuO@MIL-125(Ti), the photocatalyst had its highest photocatalytic reduction activity for CO2conversion in the presence of water. The optimized photocatalyst gave yields of methanol, ethanol, and acetic acid of up to 445.38, 966.36, and 844.63 μmol g−1, respectively. This work delivered a robust route for embedding CuO QDs and lithium battery materials into the surface matrix of photocatalysts for the effective reduction of CO2.

Background: NEDD8 (neural precursor cell expressed developmentally downregulatedprotein 8) is one of the ubiquitin-like proteins which is activated by the NEDD8 activating enzyme(NAE). The overexpressed NAE can cause a variety of diseases such as numerous cancer types andinflammatory diseases. The selective inhibition of NAE could mediate the rate of ubiquitination andthe subsequent degradation of proteins associated with cancer so as to achieve the purpose of treatment. Objective: In this article, we decided to study the synthesis and screening of coumarin scaffold derivativesagainst cancer cell lines, specifically the human pancreatic cancer cell line BxPC-3. Methods: Twenty-four targeted compounds were synthesized, and their anti-proliferative activityagainst three cancer cell lines, cytotoxicity against three normal cell lines through CCK-8 and MTTassay were evaluated to screen out the candidate compound. Then the target was further confirmedby both enzyme and cell-based experiments, as well as cell apoptosis research. Results: Several new 4-position substituted coumarin derivatives (12a

Objective: This study investigated the advantages of robot-assisted McKeown esophagectomy (RAME) for extensive superior mediastinal lymph node dissection (LND) versus video-assisted McKeown esophagectomy (VAME). Methods: The cases of 184 consecutive esophageal squamous cell carcinoma (ESCC) patients who underwent minimally invasive McKeown esophagectomy (109 with RAME, 75 with VAME) performed by a single surgical group between June 2017 and December 2019 were retrospectively reviewed. Results: Overall, 59.8% (110/181) patients (70 treated with RAME, 40 treated with VAME; 64.2% vs. 53.3%, respectively, p= 0.139) underwent complete LND around the left recurrent laryngeal nerve (RLN) by pathological assessment. Cumulative sum plots showed increased numbers of LND around the left RLN (3.6 ± 2.0 vs. 5.4 ± 2.7, p= 0.008) and a decreased incidence of recurrent nerve injury (27.9% vs. 7.4%, p= 0.037) after RAME learning curve. Despite similar overall LND results (30.6 ± 10.2 vs. 28.1 ± 10.2, p> 0.05), RAME yielded more LND (5.4 ± 2.7 vs. 4.4 ± 2.2, p= 0.016) and a greater proportion of lymph node metastases (37.0% vs. 7.5%) around the left RLN but induced a lower proportion of recurrent nerve injuries (7.4% vs. 22.5%, p= 0.178) compared with VAME. Further analysis revealed that the complete LND around the left RLN was associated with recurrent nerve injury in the RAME (20.0% vs. 5.1%, p= 0.035) and VAME (22.5% vs. 5.7%, p= 0.041) groups but did not affect other clinical outcomes including surgical duration, intraoperative blood loss, postoperative intensive care unit stay, hospital stay, and other complications. Conclusions: For patients with ESCC, RAME has great advantages in LND around the left RLN and recurrent nerve protection after learning curve of robotic esophagectomy.

Covalent organic frameworks (COFs) are promising crystalline materials for photocatalytic solar- to hydrogen-energy conversion due to the tunable chemical structures and energy band gaps. Herein, we report a chemical modification strategy for improving the photocatalytic activity of COFs. A benzene-1,3,5-tricarbaldehyde (BT)- and benzothiadiazole derivative-based two-dimensional donor–acceptor (D-A) COF, denoted as BT-COF, were fabricated and further modified by using an alternative electron-donating unit, 2-hydroxybenzene-1,3,5-tricarbaldehyde (HBT), to the polycondensation reaction, yielding HBT-COF with an enhanced internal D-A effect and hydrophilicity. Interestingly, the photocatalytic H2production rate of HBT-COF reaches 19.00 μmol h–1, which is 5 times higher than that of BT-COF (3.40 μmol h–1) under visible light irradiation. The increase in photocatalytic activity of HBT-COF is rationally attributed to finely tuned energy levels and improved wettability, which in turn leads to broadened visible light absorption, efficient photoinduced charge separation and transfer, and enhanced interactions between the COF catalyst and reaction substrates. The present results demonstrate that a subtle structural modification can significantly modulate the band structure and interfacial property, thus providing a feasible strategy for the optimization of COF-based photocatalytic systems.

IMPORTANCE: Safety and efficacy of neoadjuvant chemoradiotherapy (nCRT) vs neoadjuvant chemotherapy (nCT) for treatment of locally advanced esophageal squamous cell carcinoma (ESCC) remain uncertain given lack of high-level clinical evidence. OBJECTIVE: To compare safety and long-term survival of nCRT followed by minimally invasive esophagectomy (MIE) with that of nCT followed by MIE for patients with locally advanced ESCC. DESIGN, SETTING, AND PARTICIPANTS: A prospective, multicenter, open-label, randomized clinical trial that compared safety and efficacy of nCRT vs nCT followed by MIE for patients with locally advanced ESCC. From January 1, 2017, to December 31, 2018, 264 patients with ESCC of clinical stages from cT3 to T4aN0 to 1M0 were enrolled. Analysis was performed on an intention-to-treat basis from January 1, 2017, to August 30, 2020. INTERVENTIONS: Eligible patients were randomized to the nCRT group (n = 132) or the nCT group (n = 132) by a computer-generated random system. The chemotherapy, based on paclitaxel and cisplatin, was administered to both groups, while 40 Gy of concurrent radiotherapy was added for the nCRT group. At about 6 weeks after neoadjuvant therapy, MIE via thoracoscopy and laparoscopy was performed for the patients in both groups. MAIN OUTCOMES AND MEASURES: The primary outcome was 3-year overall survival. Secondary outcomes included postoperative complications, mortality, postoperative pathologic outcome, recurrence-free survival time, and quality of life. RESULTS: Among 264 patients (226 men [85.6%]; mean [SD] age, 61.4 [6.8] years), postoperative morbidity was 47.4% in the nCRT group (54 of 114) and 42.6% in the nCT group (46 of 108), with no significant difference between groups (difference, 4.8%; 95% CI, −8.2% to 17.5%; P = .48). Distribution of the severity of complications was similar between the 2 groups based on Clavien-Dindo classification. The 90-day perioperative mortality rate was 3.5% for the nCRT group (4 of 114) and 2.8% for the nCT group (3 of 108) (P = .94). The R0 resection rates were similar between groups (109 of 112 [97.3%] vs 100 of 104 [96.2%]; P = .92). However, patients in the nCRT group had a higher pathologic complete response (residual tumor, 0%) rate (40 of 112 [35.7%] vs 4 of 104 [3.8%]; P < .001) and a higher rate of negative lymph nodes (ypN0, 74 of 112 [66.1%] vs 48 of 104 [46.2%]; P = .03) than those in the nCT group. One-year overall survival using intention-to-treat analysis was 87.1% in the nCRT group (115 of 132) and 82.6% in the nCT group (109 of 132) (P = .30). Furthermore, deaths caused by tumor progression or recurrence were significantly less in the nCRT group than in the nCT group (9 of 132 [6.8%] vs 19 of 132 [14.4%]; P = .046); however, deaths from nontumor causes were similar (8 of 132 [6.1%] vs 4 of 132 [3.0%]; P = .24). CONCLUSIONS AND RELEVANCE: Initial results of the trial showed that nCRT followed by MIE has similar safety to and better histopathologic outcome than nCT followed by MIE for treatment of locally advanced ESCC. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT03001596

Radical-mediated organic synthesis has arisen as a potent technique for forming carbon-carbon and carbon-heteroatom bonds, displaying remarkable compatibility with diverse functional groups and superior chemoselectivity. Integrating radical transformations with asymmetric organocatalysis offers a valuable approach to accessing enantio-enriched molecules through unique pathways that differ from those facilitated by transition metal catalysis. Nevertheless, this combination continues to pose challenges due to the involvement of highly reactive intermediates, which may result in undesired background reactions and struggles in controlling stereochemistry. Recent advances in this field have led to the emergence of sophisticated strategies encompassing chemical, photochemical, and electrochemical methods. This review aims to provide a thorough overview of the mechanistic insights underlying these innovative reactions, including both catalytic activation patterns and bond formation processes. Furthermore, this review will delve into their synthetic applications, limitations, and the progress achieved between 2018 and 2023.

For impelling practical applications of flexible sensors or electronic skins, it is challenging and urgent to fabricate multifunctional flexible mechanical sensors with good linearity over a wide working range in an economical and scalable manner. Currently, it is immensely difficult to simultaneously detect tension, pressure and bending with high linearity over a wide strain range by using one film without sensor integration. Herein, we present a porous flexible mechanical sensor with a spatial electron transport network consisting of ethylene-α-octene random copolymer (ORC) elastic skeleton with surface embedded carbon black (CB) and carbon fiber (CF) bridges. Such an interesting spatial hetero-structure can shunt the electron transport effectively to regulate the resistance change of the sensor during strain loading, resulting in linear electrical signal response to mechanical deformation for a tensile strain up to 320% and a pressure up to 1.3 MPa, as well as a bending angle ranging from− 90 oto 90 o, respectively. Besides, it shows the detection capability of ambient pressure ranging from −0.09 MPa to 0.4 MPa continuously. Such a multifunctional film sensor with ultrawide linear working range demonstrates potential applications for monitoring body motions of athletics and underwater soft robots.

Metal–organic frameworks (MOFs) are important photocatalytic materials for H2production. To clarify the structure–function relationship and improve the photocatalytic activity, herein we explored a series of porphyrin-based zirconium MOFs (PCN-H2/Ptx:y, where x:y= 4:1, 3:2, 2:3, and 0:1) containing different ratios of H2TCPP and PtIITCPP [TCPP = tetrakis(4-carboxyphenyl)porphyrinate] as isostructural ligands and Zr6clusters as nodes. Under visible-light irradiation, PCN-H2/Pt0:1shows the highest average H2evolution reaction rate (351.08 μmol h–1g–1), which decreases along with lowering of the ratio of PtIITCPP in the PCN-H2/Ptx:yseries. The differences in photocatalytic activity are attributed to more uniformly dispersed Pt2+ions in PCN-H2/Pt0:1, which promotes charge transfer from porphyrins (photosensitizers) to PtIIions (catalytic centers), leading to efficient charge separation in the MOF materials. The bifunctional MOFs with photosensitizers and catalytic centers provide new insight for the design and application of porphyrin-based photocatalytic systems for visible-light-driven H2production.

Photocatalytic water splitting is a promising strategy for hydrogen energy production. However, it is still challenging to develop efficient and stable photocatalytic systems. Herein, a donor–acceptor type covalent organic framework (COF) was used to construct TBTA/g-C3N4hybrids by the in situcondensation procedure of 2,4,6-triformylphloroglucinol (TP) and 4,4′-(benzo-1,2,5-thiadiazole-4,7-diyl)dianiline (BTDA) on g-C3N4. The obtained hybrids displayed higher photocatalytic activity than the individual components. The H2evolution rate of the hybrids achieves 11.73 mmol g−1h−1without a noble metal, which is competitive with cutting-edge g-C3N4hybrid materials, and can be further increased to 26.04 mmol g−1h−1with Pt as a co-catalyst. A series of experimental methods combined with theoretical calculations have demonstrated that TBTA/g-C3N4hybrids exhibit broad visible light absorptions and appropriate energy levels, resulting in an efficient charge separation upon irradiation and in turn excellent photocatalytic activity.

In this work, compared with the corresponding pure CsPbCl3nanocrystals (NCs) and Mn2+-doped CsPbCl3NCs, Mn2+/Cu2+-codoped CsPbCl3NCs exhibited improved photoluminescence (PL) and photoluminescence quantum yields (PL QYs) (57.6%), prolonged PL lifetimes (1.78 ms), and enhanced thermal endurance (523 K) as a result of efficient Mn2+doping (3.66%) induced by the addition of CuCl2. Furthermore, we applied pressure on Mn2+/Cu2+-codoped CsPbCl3NCs to reveal that a red shift of photoluminescence followed by a blue shift was caused by band gap evolution and related to the structural phase transition from cubic to orthorhombic. Moreover, we also found that under the preheating condition of 523 K, such phase transition exhibited obvious morphological invariance, accompanied by significantly enhanced conductivity. The pressure applied to the products treated with high temperature enlarged the electrical difference and easily intensified the interface by closer packaging. Interestingly, defect-triggered mixed ionic and electronic conducting (MIEC) was observed in annealed NCs when the applied pressure was 2.9 GPa. The pressure-dependent ionic conduction was closely related to local nanocrystal amorphization and increased deviatoric stress, as clearly described by in situimpedance spectra. Finally, retrieved products exhibited better conductivity (improved by 5–6 times) and enhanced photoelectric response than those when pressure was not applied. Our findings not only reveal the pressure-tuned optical and electrical properties viastructural progression but also open up the promising exploration of more amorphous all-inorganic CsPbX3-based photoelectric applications.

In the present work, dihydric alcohols (including 1,4-butanediol, 2,3-butanediol, and 1,3-propanediol) were paired with choline chloride (ChCl) to form deep eutectic solvents (DESs) with the molar ratio of ChCl to dihydric alcohol fixed at 1:3 and 1:4. The solubility of NH3in these DESs was systematically determined at 303.15, 313.15, 323.15, and 333.15 K under pressures up to 420.0 kPa using the isochoric saturation method and was correlated using the Krichevsky–Kasarnovsky (K–K) equation. The dissolution Gibbs free energy, enthalpy, and entropy changes of NH3solvation were further calculated according to the temperature dependence of Henry’s constants. Based on the reported CO2solubility data, the selectivities of NH3/CO2in DESs used herein were calculated. The density and viscosity data of the DESs were also measured and fitted at a temperature range of 303.15–343.15 K. Overall, the dihydric alcohol-based DESs present quite promising NH3absorption and separation performance, with a value of 3.0 mol NH3per kg DES and an NH3/CO2selectivity of 98 at 303.15 K and 100.0 kPa.

C60H106N12O32Zn3, monoclinic, P21/c(no. 14), a= 18.9877(14) Å, b= 19.7813(15) Å, c= 21.0699(14) Å, β= 103.345(2)°, V= 7700.2(10) Å3, Z= 4, Rgt(F) = 0.0626, wRref(F2) = 0.1752, T= 193 K.

A series of CuO catalysts were fabricated through hydrothermal process, thermal decomposition of the precursors of CuC2O4synthesized by soft reactive grinding route and oxalate-gel co-precipitation method, respectively. The discoloration of methylene blue in the presence of H2O2was selected as the activity test model reaction. The as-prepared catalysts were characterized by powder X-ray diffraction, scanning electron microscopy, infrared diffuse reflectance spectrum, and N2-adsorption analysis. The CuO obtained from calcination of dry-grinding-derived oxalate precursor has better catalytic performance than those prepared by conventional wet-chemical method. Examination of the structural characterization shows that the small particle size and relatively high surface area are the main reasons for its excellent activity. Moreover, the pseudo-first-order kinetics model was also employed to understand the discoloration behavior of grinding-derived CuO and the activation energy was calculated to be 56.5 kJ mol−1. The current preparation mechanism of solid-state synthetic technique was also proposed by tracking the precursor structure.

The removal of SO2from flue gas for the improvement of atmospheric quality and human health has attracted sustainable attention. In this work, 1-ethyl-3-methylimidazolium chloride (EmimCl) was paired with N-formylmorpholine (NFM) to form deep eutectic solvents (DESs) as the media for SO2absorption. The absorption performance of SO2in EmimCl-NFM DESs with various molar ratios was experimentally measured. Results showed that all the DESs exhibited efficient and reversible absorption behavior for low concentration SO2, with SO2absorption capacity as high as 0.220 g SO2/g of DES of EmimCl-NFM (1:1) at 293.15 K and SO2partial pressure of 1.0 kPa, surpassing that of most absorbents/adsorbents previously reported. The DES could retain satisfactory absorption performance and thermal stability after five consecutive cycles. The viscosity, density, thermogravimetric analysis, Fourier transform infrared spectroscopy, and NMR spectroscopy were utilized to characterize systematically the changes between fresh and SO2-loaded DESs. The present DESs showed potential application in the purification of gas containing SO2due to their easy preparation, high absorption capacity, and good reversibility.

Background: NEDD8 activating enzyme (NAE) plays a critical role in various cellularfunctions in carcinomas. The selective inhibition of NAE could mediate the rate of ubiquitinationand the subsequent degradation of proteins associated with cancer so as to achieve the purpose oftreatment.Objective: In this article, we decided to study the synthesis and screening of 4-amino substituted2H-chromen-2-one derivatives against cancer cell lines, specifically the human pancreatic cancercell line BxPC-3.Methods: After synthesis of twenty targeted compounds, we evaluated their anti-proliferative activityagainst six cancer cell lines, cytotoxicity against three normal cell lines through MTT assay,and hemolysis to screen out the candidate compound, which was further conducted drug-likephysical property measurement, target confirmation by enzyme-based experiment, cell apoptosis,and synergistic effect research.Results: Starting from intermediates 4 and 5, several new 4-amino substituted 2H-chromen-2-onederivatives (9-28) were synthesized and evaluated for their cell activities using six cancer celllines. We performed tests of cytotoxicity, hemolysis, ATP-dependent NAE inhibition in the enzyme-based system, apoptosis, and synergistic effect in BxPC-3 cells against the best candidatecompound 21.Conclusion: Based on these results, we found that compound 21 inhibited NAE activity in anATP-dependent manner in the enzyme-based system, induced apoptosis in BxPC-3 cells, and synergizedwith bortezomib on BxPC-3 cell growth inhibition. Additionally, it had low toxicity withreasonable Log P-value and water solubility.