Mechanochemical Synthesis of Silylcyclopentenes via Ball Milling.

The development of innovative methods for synthesizing silylcyclopentene compounds is particularly important for enriching and improving the synthetical toolbox of organosilicon compounds. Herein, a facile approach has been developed for the synthesis of silylcyclopentenes promoted by mechanochemically generated organolithium species as silicon nucleophiles under ball milling conditions, avoiding the requirement of large amounts of bulk solvent. This operationally simple method demonstrates good functional group compatibility, which provides a great opportunity for further exploration of the synthetic applications of silylcyclopentenes. Density functional theory calculations indicated that the transient lithiosilole intermediates undergo a stepwise nucleophilic addition process, which governs this mechanic-force-promoted [4+1] cycloaddition reaction.

Radiomics model based on contrast-enhanced computed tomography imaging for early recurrence monitoring after radical resection of AFP-negative hepatocellular carcinoma.

BACKGROUND: Although radical surgical resection is the most effective treatment for hepatocellular carcinoma (HCC), the high rate of postoperative recurrence remains a major challenge, especially in patients with alpha-fetoprotein (AFP)-negative HCC who lack effective biomarkers for postoperative recurrence surveillance. Emerging radiomics can reveal subtle structural changes in tumors by analyzing preoperative contrast-enhanced computer tomography (CECT) imaging data and may provide new ways to predict early recurrence (recurrence within 2 years) in AFP-negative HCC. In this study, we propose to develop a radiomics model based on preoperative CECT to predict the risk of early recurrence after surgery in AFP-negative HCC. PATIENTS AND METHODS: Patients with AFP-negative HCC who underwent radical resection were included in this study. A computerized tool was used to extract radiomic features from the tumor region of interest (ROI), select the best radiographic features associated with patient's postoperative recurrence, and use them to construct the radiomics score (RadScore), which was then combined with clinical and follow-up information to comprehensively evaluate the reliability of the model. RESULTS: A total of 148 patients with AFP-negative HCC were enrolled in this study, and 1,977 radiographic features were extracted from CECT, 2 of which were the features most associated with recurrence in AFP-negative HCC. They had good predictive ability in both the training and validation cohorts, with an area under the ROC curve (AUC) of 0.709 and 0.764, respectively. Tumor number, microvascular invasion (MVI), AGPR and radiomic features were independent risk factors for early postoperative recurrence in patients with AFP-negative HCC. The AUCs of the integrated model in the training and validation cohorts were 0.793 and 0.791, respectively. The integrated model possessed the clinical value of predicting early postoperative recurrence in patients with AFP-negative HCC according to decision curve analysis, which allowed the classification of patients into subgroups of high-risk and low-risk for early recurrence. CONCLUSION: The nomogram constructed by combining clinical and imaging features has favorable performance in predicting the probability of early postoperative recurrence in AFP-negative HCC patients, which can help optimize the therapeutic decision-making and prognostic assessment of AFP-negative HCC patients.

Altering the CO2 Electroreduction Pathways Towards C1 or C2+ Products via Engineering the Strength of Interfacial Cu-O Bond.

Copper (Cu)-based catalysts have established their unique capability for yielding wide value-added products from CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O-containing organic species (squaric acid (H2C4O4) and cyclohexanehexaone (C6O6)). It is revealed that the strength of Cu-O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO2RR. Specifically, the C6O6-Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7 % at -0.6 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4-Cu with an about perfect crystalline structure results in uniformly dispersed Cu-atoms, showing a notable FE of 65.8 % for C2+ products with enhanced capability of C-C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm-2 at -1.0 VRHE, i.e., is already at the boarder of practical relevance. This study sheds light on the rational design of Cu-based catalysts for directing the CO2RR reaction pathway.

Bifunctional sensing based on an exceptional point with bilayer metasurfaces.

Exceptional points (EPs), the critical phase transition points of non-Hermitian parity-time (PT) systems, exhibit many novel physical properties and associated applications, such as ultra-sensitive detection of perturbations. Here, a bilayer metasurface with two orthogonally oriented split-ring resonators (SRRs) is proposed and a phase transition of the eigenpolarization states is introduced via changing the conductivity of vanadium dioxide (VO2) patch integrated into the gap of one SRR. The metasurface possesses a passive PT symmetry and an EP in polarization space is observed at a certain conductivity of the VO2. Two sensing schemes with the metasurface are proposed to achieve high-sensitivity sensing of temperature and refractive index in the terahertz (THz) range. The metasurface is promising for applications in THz biosensing and polarization manipulation.

Diverse ranking metamaterial inverse design based on contrastive and transfer learning.

Metamaterials, thoughtfully designed, have demonstrated remarkable success in the manipulation of electromagnetic waves. More recently, deep learning can advance the performance in the field of metamaterial inverse design. However, existing inverse design methods based on deep learning often overlook potential trade-offs of optimal design and outcome diversity. To address this issue, in this work we introduce contrastive learning to implement a simple but effective global ranking inverse design framework. Viewing inverse design as spectrum-guided ranking of the candidate structures, our method creates a resemblance relationship of the optical response and metamaterials, enabling the prediction of diverse structures of metamaterials based on the global ranking. Furthermore, we have combined transfer learning to enrich our framework, not limited in prediction of single metamaterial representation. Our work can offer inverse design evaluation and diverse outcomes. The proposed method may shrink the gap between flexibility and accuracy of on-demand design.

Phased Feature Extraction Network for Vehicle Search Tasks Based on Cross-Camera for Vehicle-Road Collaborative Perception.

The objective of vehicle search is to locate and identify vehicles in uncropped, real-world images, which is the combination of two tasks: vehicle detection and re-identification (Re-ID). As an emerging research topic, vehicle search plays a significant role in the perception of cooperative autonomous vehicles and road driving in the distant future and has become a trend in the future development of intelligent driving. However, there is no suitable dataset for this study. The Tsinghua University DAIR-V2X dataset is utilized to create the first cross-camera vehicle search dataset, DAIR-V2XSearch, which combines the cameras at both ends of the vehicle and the road in real-world scenes. The primary purpose of the current search network is to address the pedestrian issue. Due to varying task scenarios, it is necessary to re-establish the network in order to resolve the problem of vast differences in different perspectives caused by vehicle searches. A phased feature extraction network (PFE-Net) is proposed as a solution to the cross-camera vehicle search problem. Initially, the anchor-free YOLOX framework is selected as the backbone network, which not only improves the network's performance but also eliminates the fuzzy situation in which multiple anchor boxes correspond to a single vehicle ID in the Re-ID branch. Second, for the vehicle Re-ID branch, a camera grouping module is proposed to effectively address issues such as sudden changes in perspective and disparities in shooting under different cameras. Finally, a cross-level feature fusion module is designed to enhance the model's ability to extract subtle vehicle features and the Re-ID's precision. Experiments demonstrate that our proposed PFE-Net achieves the highest precision in the DAIR-V2XSearch dataset.

CompleteInst: An Efficient Instance Segmentation Network for Missed Detection Scene of Autonomous Driving.

As a fundamental computer vision task, instance segmentation is widely used in the field of autonomous driving because it can perform both instance-level distinction and pixel-level segmentation. We propose CompleteInst based on QueryInst as a solution to the problems of missed detection with a network structure designed from the feature level and the instance level. At the feature level, we propose Global Pyramid Networks (GPN) to collect global information of missed instances. Then, we introduce the semantic branch to complete the semantic features of the missed instances. At the instance level, we implement the query-based optimal transport assignment (OTA-Query) sample allocation strategy which enhances the quality of positive samples of missed instances. Both the semantic branch and OTA-Query are parallel, meaning that there is no interference between stages, and they are compatible with the parallel supervision mechanism of QueryInst. We also compare their performance to that of non-parallel structures, highlighting the superiority of the proposed parallel structure. Experiments were conducted on the Cityscapes and COCO dataset, and the recall of CompleteInst reached 56.7% and 54.2%, a 3.5% and 3.2% improvement over the baseline, outperforming other methods.

Enhancing Local CO2 Adsorption by L-histidine Incorporation for Selective Formate Production Over the Wide Potential Window.

Electrochemical carbon dioxide reduction reaction (CO2 RR) to produce valuable chemicals is a promising pathway to alleviate the energy crisis and global warming issues. However, simultaneously achieving high Faradaic efficiency (FE) and current densities of CO2 RR in a wide potential range remains as a huge challenge for practical implements. Herein, we demonstrate that incorporating bismuth-based (BH) catalysts with L-histidine, a common amino acid molecule of proteins, is an effective strategy to overcome the inherent trade-off between the activity and selectivity. Benefiting from the significantly enhanced CO2 adsorption capability and promoted electron-rich nature by L-histidine integrity, the BH catalyst exhibits excellent FEformate in the unprecedented wide potential windows (>90 % within -0.1--1.8 V and >95 % within -0.2--1.6 V versus reversible hydrogen electrode, RHE). Excellent CO2 RR performance can still be achieved under the low-concentration CO2 feeding (e.g., 20 vol.%). Besides, an extremely low onset potential of -0.05 VRHE (close to the theoretical thermodynamic potential of -0.02 VRHE ) was detected by in situ ultraviolet-visible (UV-Vis) measurements, together with stable operation over 50 h with preserved FEformate of ≈95 % and high partial current density of 326.2 mA cm-2 at -1.0 VRHE .

Versatile polarization manipulation in vanadium dioxide-integrated terahertz metamaterial.

Broadband and switchable versatile polarization metamaterial is crucial in the applications of imaging, sensing and communication, especially in the terahertz frequency. Here, we investigated versatile polarization manipulation in a hybrid terahertz metamaterial with bilayer rectangular rods and a complementary vanadium dioxide (VO2) layer. The VO2 phase transition enables a flexible switching from dual-band asymmetric transmission to dual-band reflective half-wave plate. The full width half maximum (FWHM) bandwidths of dual-band asymmetric transmission are 0.77 and 0.21 THz, respectively. The polarization conversion ratio (PCR) of the reflective metamaterial is over 0.9 in the frequency ranges of 1.01-1.17 THz and 1.47-1.95 THz. Angular dependences of multiple polarization properties are studied. The proposed switchable polarization metamaterial is important to the development of multifunctional polarization devices and multichannel polarization detection.

Chiral Fluorescence Recognition by Anthracene Fluorescent Dyes ⊂ Water-Soluble Pillar[5] arene containing Phosphonic Acid Group (PWP[5]).

Chirality plays a pivotal role in drugs, agrochemicals and food additives et al. The enantiomers of a chiral molecule often show huge difference in bioactivity, metabolism, and toxicity et al. thereby, the recognition of chiral molecules shows an increasingly important priority. In this paper, a novel method for chiral fluorescence recognition based on anthracene fluorescent dyes (AD) ⊂ water-soluble pillar[5] arene containing phosphonic acid group (PWP[5]) is developed. The AD as guest molecule can complex with PWP [5] to form 1:1 AD ⊂ PWP[5] assembly, and this assembly can be further used as a fluorescent probe to identify D/L-phenylalanine and D/L-phenylalaninol by fluorescent titration. The fluorescence intensity of the assembly was significantly reduced for D-phenylalanine and D-phenylalaninol, while L-phenylalanine or L-phenylalaninol was added to AD ⊂ PWP[5] assembly, the fluorescence intensity of the assembly almost unchanged. Hence, the chiral recognition based on assembly between the achiral fused ring fluorescent dye and achiral PWP[5] was developed.

Highly sensitive gas sensor based on a parity-time-symmetric system.

Achieving extremely high sensitivity is an important indicator in the development of novel and stable gas concentration sensors. In this paper, we present a gas concentration sensor with parity-time symmetry for high sensitivity at low concentrations. The proposed sensor can detect toxic gases, such as benzene, bromine, and acetone, by probing the faint changing of the permittivity. Furthermore, the level of the sensitivity can be adjusted by the resistance segment, which is realized by various metallic formations. Our proposed structure provides a novel idea for the development of future gas concentration sensors, showing an exciting prospect for gas sensing technologies.

Effective Treatment of Single-Stage Revision Using Intra-Articular Antibiotic Infusion for Polymicrobial Periprosthetic Joint Infection.

BACKGROUND: The treatment of polymicrobial periprosthetic joint infection (PJI) confronted distinct challenges. No reports have assessed the efficacy of local antibiotic delivery combined with 1-stage exchange in polymicrobial PJI. METHODS: Between January 2013 and December 2018, we retrospectively analyzed the data of 126 patients, including 19 polymicrobial PJIs and 107 monomicrobial PJIs, who underwent single-stage revision using intra-articular antibiotic infusion. The risk factors, microbiology, infection control rate, and clinical outcomes were compared between the 2 groups. RESULTS: Higher body mass index, presence of a sinus tract, and prior revisions were the risk factors for polymicrobial PJI. Isolation of Staphylococcus epidermidis, Streptococcus, Enterococcus, and Gram-negative pathogens was highly associated with polymicrobial PJI. Of the 19 polymicrobial PJIs, only 2 patients occurred infection recurrence, which is similar with the result of 6 of 107 patients in the monomicrobial PJI (P = .225). The Harris Hip Score of the polymicrobial group showed no difference from that of the monomicrobial group (78 vs 80; P = .181). Nevertheless, the polymicrobial group exhibited inferior Hospital for Special Surgery knee score relative to the monomicrobial group (77 vs 79; P = .017). CONCLUSION: With rational and targeted use of antibiotics, single-stage revision can effectively control polymicrobial infections, and achieve favorable outcomes similar to that in monomicrobial patients. However, this regimen is still needed to be further confirmed, especially in the infections with different microbial species simultaneously. Additionally, obese patients with a sinus tract and those who had prior revisions had a greater risk of polymicrobial PJI.

Biomimetic Total Synthesis of the Spiroindimicin Family of Natural Products.

A unified strategy for the biomimetic total synthesis of the spiroindimicin family of natural products was reported. Key transformations include a one-pot two-enzyme-catalyzed oxidative dimerization of L-tryptophan/5-chloro-L-tryptophan to afford the bis-indole precursors chromopyrrolic acid/5',5''-dichloro-chromopyrrolic acid, and regioselective C3'-C2'' and C3'-C4'' bond formation converting a common bis-indole skeleton to two skeletally different natural products, including (±)-spiroindimicins D and G with a [5,5] spiro-ring skeleton, and (±)-spiroindimicins A and H with a [5,6] spiro-ring skeleton, respectively.

Large asymmetric anomalous reflection in bilayer gradient metasurfaces.

Gradient metasurfaces have attracted much attention due to intriguing wavefront and polarization manipulation. Here, a bilayer gradient metasurface is constructed by use of a rectangular nanorod layer and its complementary nanoaperture. It reveals asymmetric anomalous reflection and symmetric anomalous transmission for two counter-propagating directions. The dependence of the anomalous reflection and transmission phenomena on nanostructure thickness are numerically studied in optical frequencies. The increasing metallic layer thickness of the gradient metasurface greatly enhances anomalous reflection of the left-handed circularly polarized wave (LCP) for the nanorod side and suppresses anomalous reflection for the other side. Both resonant frequencies of anomalous reflection and transmission linearly shift with the refractive index. The bilayer gradient metasurface is important for realizing wavefront modulation and optical sensing.

Inherently Area-Selective Atomic Layer Deposition of Manganese Oxide through Electronegativity-Induced Adsorption.

Manganese oxide (MnOx) shows great potential in the areas of nano-electronics, magnetic devices and so on. Since the characteristics of precise thickness control at the atomic level and self-align lateral patterning, area-selective deposition (ASD) of the MnOx films can be used in some key steps of nanomanufacturing. In this work, MnOx films are deposited on Pt, Cu and SiO2 substrates using Mn(EtCp)2 and H2O over a temperature range of 80-215 °C. Inherently area-selective atomic layer deposition (ALD) of MnOx is successfully achieved on metal/SiO2 patterns. The selectivity improves with increasing deposition temperature within the ALD window. Moreover, it is demonstrated that with the decrease of electronegativity differences between M (M = Si, Cu and Pt) and O, the chemisorption energy barrier decreases, which affects the initial nucleation rate. The inherent ASD aroused by the electronegativity differences shows a possible method for further development and prediction of ASD processes.

Predictive value of gamma-glutamyl transpeptidase to lymphocyte count ratio in hepatocellular carcinoma patients with microvascular invasion.

BACKGROUND: Microvascular invasion (MVI) is an independent risk factor for poor prognosis in hepatocellular carcinoma (HCC). However, there is still a lack of preoperative markers to predict MVI in HCC. This study intends to explore the potential application value of the gamma-glutamyl transpeptidase (GGT) to lymphocyte count ratio (GLR) in predicting MVI in HCC and provide guidance for clinical diagnosis and treatment. METHODS: From March 2010 to December 2015, 230 HCC patients who underwent surgical treatment in the Affiliated Hospital of Guilin Medical University were selected. Clinicopathological parameters between the MVI group (n = 115) and the non-MVI group (n = 115) were comparatively analyzed. The GLR was used as the potential risk factor for HCC with MVI, and its optimal cut-off value was estimated by using the receiver operating characteristic (ROC) curve. The Kaplan-Meier method was used to analyze the survival of HCC patients, and univariate and multivariate Cox regression analyses were used to establish independent predictors affecting postoperative HCC patients. RESULTS: The GLR levels in the MVI group and non-MVI group were 84.83 ± 61.84 and 38.42 ± 33.52 (p <  0.001), respectively. According to ROC curve analysis, the optimal cut-off value of GLR was 56.0, and the area under the ROC curve (AUC) was 0.781 (95% CI, 0.719-0.833) for the risk prediction of MVI in HCC patients. Multivariate analysis showed that tumor size > 5 cm, HCC combined with MVI and GLR >  56.0 were independent risk factors for poor prognosis in HCC patients. In addition, compared with the non-MVI group, patients in the MVI group had shorter progression-free survival (PFS) and overall survival (OS). CONCLUSION: GLR could be a predictive biomarker of HCC after operation and a potential predictor of HCC combined with MVI.

Reciprocal activation between STAT3 and miR-181b regulates the proliferation of esophageal cancer stem-like cells via the CYLD pathway.

BACKGROUND: Recent studies have suggested that cancer cells contain subpopulations that can initiate tumor growth, self-renew, and maintain tumor cell growth. However, for esophageal cancer cells, the relationship between STAT3, microRNAs and cancer stem cells remains unclear. METHODS: Serum-free culture was used to enrich esophageal cancer stem-like cells (ECSLC). Flow cytometry determined the proportion of ECSLC. qPCR were performed to examine expression level of stemness factors, mesenchymal markers, ATP-binding cassette (ABC) transporters, STAT3, miR-181b, CYLD. Western blot were performed to analyze the expression of STAT3, p-STAT3 and CYLD (cylindromatosis). BALB/c mice xenograft studies were conducted to evaluate the tumorigenicity of enriched ECSLC. Sphere formation assay and colony formation assays were employed to analyze the relationship between STAT3 and miR-181b. Luciferase assays were used to evaluate activity which CYLD is a target of miR-181b. RESULTS: Sphere formation cells (SFCs) with properties of ECSLC were enriched. Enriched SFCs in serum-free suspension culture exhibited cancer stem-like cell properties and increased single-positive CD44 + CD24-, stemness factor, mesenchymal marker expression ABC transporters and tumorigenicity in vivo compared with the parental cells. Additionally, we found that reciprocal activation between STAT3 and miR-181b regulated SFCs proliferation. Moreover, STAT3 directly activated miR-181b transcription in SFCs and miR-181b then potentiated p-STAT3 activity. Luciferase assays indicated that CYLD was a direct and functional target of miR-181b. CONCLUSION: The mutual regulation between STAT3 and miR-181b in SFCs was required for proliferation and apoptosis resistance. STAT3 and miR-181b control each other's expression in a positive feedback loop that regulates SFCs via CYLD pathway. These findings maybe is helpful for targeting ECSLC and providing approach for esophageal cancer treatments.

[Effect of Helium on Diamond Films Deposited Using Microwave PCVD].

Optical emission spectroscopy (OES) was used to in situ diagnose the CH4-H2-He plasma in order to know the effect of helium on the diamond growth by microwave plasma chemical vapor deposition (MPCVD). The spatial distribution of radicals in the plasma as a function of helium addition was studied. The diamond films deposited in different helium volume fraction were investigated using scanning electron microscope (SEM) and Raman spectroscopy. The results show that the spectra intensity of radicals of H(α), H(ß), H(γ), CH and C2 increases with the increasing of helium volume fraction, especially, that of radical H(α) has the most improvement. The spectrum space diagnosis results show that the uniformity of C2, CH radicals in the plasma tends to poor due to the helium addition and resulted in a different thickness along the radial direction The measurement of deposition rate shows that the addition of helium is useful for the improvement of the growth rate of diamond films, due to relative concentration of carbon radicals was increased. The deposition rate increases by 24% when the volume fraction of He was increased from 0 vol. % to 4.7 vol.%. The micrographs of SEM reveal that with the increasing of helium volume fraction, the diamond films' crystallite orientation changes from (111) to disorder and a twins growth becomes obvious. The secondary nucleation density during growth increases because the high relatively concentration of C2 radicals under higher helium volume fraction (4.7 vol. %). In addition, the substrate was etched and sputtered by the plasma, which introduced metallic atoms into the plasma during the deposition of diamond films. Eventually, the existing of secondary nucleation and impurity atoms lead to the appearance of twins and results in the compressive dress.

Suppressing the relaxation oscillation noise of injection-locked WRC-FPLD for directly modulated OFDM transmission.

By up-shifting the relaxation oscillation peak and suppressing its relative intensity noise in a weak-resonant-cavity Fabry-Perot laser diode (WRC-FPLD) under intense injection-locking, the directly modulated transmission of optical 16 quadrature amplitude modulation (QAM) orthogonal frequency division multiplexing (OFDM) data-stream is demonstrated. The total bit rate of up to 20 Gbit/s within 5-GHz bandwidth is achieved by using the OFDM subcarrier pre-leveling technique. With increasing the injection-locking power from -12 to -3 dBm, the effective reduction on threshold current of the WRC-FPLD significantly shifts its relaxation oscillation frequency from 5 to 7.5 GHz. This concurrently induces an up-shift of the peak relative intensity noise (RIN) of the WRC-FPLD, and effectively suppresses the background RIN level to -104 dBc/Hz within the OFDM band between 3 and 6 GHz. The enhanced signal-to-noise ratio from 16 to 20 dB leads to a significant reduction of bit-error-rate (BER) of the back-to-back transmitted 16-QAM-OFDM data from 1.3 × 10(-3) to 5 × 10(-5), which slightly degrades to 1.1 × 10(-4) after 25-km single-mode fiber (SMF) transmission. However, the enlarged injection-locking power from -12 to -3 dBm inevitably declines the modulation throughput and increases its negative throughput slope from -0.8 to -1.9 dBm/GHz. After pre-leveling the peak amplitude of the OFDM subcarriers to compensate the throughput degradation of the directly modulated WRC-FPLD, the BER under 25-km SMF transmission can be further improved to 3 × 10(-5) under a receiving power of -3 dBm.

Graphene oxide-based micropatterns via high-throughput multiphoton-induced reduction and ablation.

In this study, a developed temporal focusing-based femtosecond laser system provides high-throughput multiphoton-induced reduction and ablation of graphene oxide (GO) films. Integrated with a digital micromirror device to locally control the laser pulse numbers, GO-based micropatterns can be quickly achieved instantly. Furthermore, the degree of reduction and ablation can be precisely adjusted via controlling the laser wavelength, power, and pulse number. Compared to point-by-point scanning laser direct writing, this approach offers a high-throughput and multiple-function approach to accomplish a large area of micro-scale patterns on GO films. The high-throughput micropatterning of GO via the temporal focusing-based femtosecond laser system fulfills the requirement of mass production for GO-based applications in microelectronic devices.