Exploring the chemical diversity of sesquiterpenes from the rarely studied south China sea soft coral Sinularia tumulosa assisted by molecular networking strategy.

Molecular networking strategy-based prioritization of the isolation of the rarely studied soft coral Sinularia tumulosa yielded 14 sesquiterpenes. These isolated constituents consisted of nine different types of carbon frameworks, namely asteriscane, humulane, capillosane, seco-asteriscane, guaiane, dumortane, cadinane, farnesane, and benzofarnesane. Among them, situmulosaols A-C (1, 3 and 4) were previously undescribed ones, whose structures with absolute configurations were established by the combination of extensive spectral data analyses, quantum mechanical-nuclear magnetic resonance and time-dependent density functional theory electronic circular dichroism calculations, the Snatzke's method, and the modified Mosher's method. Notably, situmulosaol C (4) was the second member of capillosane-type sesquiterpenes. The plausible biogenetic relationships of these skeletally different sesquiterpenes were proposed. All sesquiterpenoids were evaluated for their antibacterial, cytotoxic and anti-inflammatory effects. The bioassay results showed compound 14 exhibited significant antibacterial activities against a variety of fish and human pathogenic bacteria with MIC90 values ranging from 3.6 to 33.8 µg/mL. Moreover, moderate cytotoxic effects against HEL cells for components 13 and 14 and moderate inhibitory effect on lipopolysaccharide-induced inflammatory responses in RAW264.7 cells for substance 13 were also observed.

Anti-inflammatory Steroids from the South China Sea Sponge Spongia officinalis.

One new highly degraded steroid, namely 21-nor-4-ene-chaxine A (1) furnishing a 5/6/5-tricyclic, along with one known related analogue (2), were isolated from the South China Sea sponge Spongia officinalis. Their structures including absolute configurations were established by extensive spectroscopic data analysis, TDDFT-ECD calculation, and comparison with the spectral data previously reported in the literature. Compound 1 represent the new member of incisterols family with a highly degradation in ring B. In vitro bioassays revealed compound 2 exhibited significant anti-microglial inflammatory effect on lipopolysaccharide (LPS)-induced inflammation in BV-2 microglial cells.

High-Frequency Discrete-Interval Binary Sequence in Asynchronous C-VEP-Based BCI for Visual Fatigue Reduction.

In code-modulated visual evoked potential (c-VEP) based BCI systems, flickering visual stimuli may result in visual fatigue. Thus, we introduced a discrete-interval binary sequence (DIBS) as visual stimulus modulation, with its power spectrum optimized to emphasize high-frequency components (40 Hz-60 Hz). 8 and 17 subjects participated, respectively, in offline and online experiments on a 4-target asynchronous c-VEP-based BCI system designed to realize a high positive predictive value (PPV), a low false positive rate (FPR) during idle states, and a high true positive rate (TPR) in control states, while minimizing visual fatigue level. Two visual stimuli modulations were introduced and compared: a maximum length sequence (m-sequence) and the high-frequency discrete-interval binary sequence (DIBS). The decoding algorithm was compared among the canonical correlation analysis (CCA), the task-related component analysis (TRCA), and two approaches of sub-band component weight calculation (the traditional method and the proportional method) for FBCCA and FBTRCA. In the online experiments, the average PPV, FPR and TPR achieved, respectively [Formula: see text], [Formula: see text], [Formula: see text] with m-sequence, while [Formula: see text], [Formula: see text] and [Formula: see text] with DIBS. Estimated by objective eye-related metrics and a subjective questionnaire, the visual fatigue in DIBS cases is significantly smaller than that in m-sequence cases. In this study, the feasibility of a novel modulation approach for visual fatigue reduction was proved in an asynchronous c-VEP system, while maintaining comparable performance to existing methods, which provides further insights towards enhancing this field's long-term viability and user-friendliness.

Carboxymethyl cellulose and metal-organic frameworks immobilized into polyacrylamide hydrogel for ultrahigh efficient and selective adsorption U(VI) from seawater.

Metal-organic frameworks (MOF)-polymer hybrid hydrogel solves the processable forming of MOF powder and energy consumption of uranium extraction. However, the hybrid hydrogel by conventional synthesis methods inevitably lead to MOF agglomeration, poor filler-polymer interfacial compatibility and slowly adsorption. Herein, we designed that ZIF-67 was implanted into the carboxymethyl cellulose/polyacrylamide (CMC/PAM) by network-repairing strategy. The carboxyl and amino groups on the surface of CMC/PAM drive the uniform growth of ZIF-67 inside the CMC/PAM, which form an array of oriented and penetrating microchannels through coordination bonds. Our strategy eliminate the ZIF-67 agglomeration, increase the interfacial compatibility between MOF and polymer. The method also improve the free and fast diffusion of uranium in CMC/PAM/ZIF-67 hydrogel. According to the experimental, these enhancements synergistically enabled the CMC/PAM/ZIF-67 have a maximum adsorption capacity of 952 mg g-1. The adsorption process of CMC/PAM/ZIF-67 fits well with pseudo-second-order model and Langmuir isotherm. Meanwhile, the CMC/PAM/ZIF-67 maintain a high removal rate (87.3 %) and chemical stability even during ten adsorption-desorption cycles. It is worth noting that the adsorption amount of CMC/PAM/ZIF-67 in real seawater is 9.95 mg g-1 after 20 days, which is an ideal candidate adsorbent for uranium extraction from seawater.

Nine New Antibacterial Diterpenes and Steroids from the South China Sea Soft Coral Lobophytum catalai Tixier-Durivault.

Five new cembrane-type diterpenes, lobocalines A-E (1-5), and four new steroids, lobocaloids A-D (9-12), along with six known related compounds (6-8 and 13-15) were isolated from the Yalong Bay soft coral Lobophytum catalai Tixier-Durivault. The structures of the new compounds were elucidated by extensive spectroscopic analysis, NMR calculation with DP4+ analysis, time-dependent density functional theory-electronic circular dichroism (TDDFT-ECD) calculations, X-ray diffraction analyses and comparison with the reported spectroscopic data of known compounds. Further, with the aid of X-ray diffraction analysis, the structure of lobocrasol B (15) was firmly revised as 15a. In in vitro bioassays, compound 2 showed moderate antibacterial activities against fish pathogenic bacteria Streptococcus parauberis KSP28 and Phoyobacterium damselae FP2244 with minimum inhibitory concentration (MIC) values of 8.7 and 17.3 µg/mL, respectively. All the steroids exhibited antibacterial activities against the S. parauberis KSP28 with MIC values ranging from 12.3 to 53.6 µg/mL. Compounds 2, 7 and 14 have remarkable inhibitory effects on the hemolysin production of Staphylococcus aureus, while compounds 8-12 have medium inhibitory effects on the pyocyanin production in Pseudomonas aeruginosa.

Enhancing the electrochemical properties of a lithium-sulfur battery using a modified separator with a phase-inversion layer.

The commercial application of lithium-sulfur (Li-S) batteries is limited by the inherent defects of poor conductivity of sulfur and the shuttling effect of polysulfides. To overcome these limitations, a modified layer comprising a porous network PVDF-PMMA skeleton and Ketjen black (KB) carbon nanoparticles was coated on the polyethylene (PE) separator using the phase inversion method. The PVDF-PMMA-KB (PPK) composite layer with a structure abundant in mesopores can effectively limit the shuttling effect of polysulfides via a physical barrier and adsorption. Moreover, the utilization of active substances substantially increased as the KB carbon nanoparticles could provide additional reaction sites for activating inactive polysulfides and depositing lithium sulfide. The electrochemical properties of the Li-S battery were considerably enhanced using the modified separator with a PPK layer, which was reflected in the higher rate capability and longer cycling life. The cell with a modified separator delivered a specific capacity of 723 mA h g-1 at 1 C, and the capacity retention reached 73.3% after 400 cycles with a low decay rate of 0.223% per cycle. This work provides a novel preparation method for a modified layer on the separator and promotes the large-scale application of Li-S batteries.

Prediction of mortality and overt hepatic encephalopathy undergoing transjugular intrahepatic portosystemic shunt: a retrospective cohort study.

PURPOSE: Data on medium- and long-term efficacy and safety of Transjugular intrahepatic portosystemic shunt (TIPS) using Viatorr stents in Chinese patients are limited. This study aimed to evaluate the 5-year mortality and the incidence of overt hepatic encephalopathy (OHE) after Viatorr stent insertion, and construct a model to predict post-TIPS OHE preoperatively. METHODS: One hundred thirty-two patients undergoing Viatorr stent insertion in our institution between August 2016 and December 2019 were included, and randomly divided into training and validation cohort at a 70/30 ratio. Patients were followed up until death or the end date of follow-up (December 31st, 2021). The primary end point was all-cause mortality, and the secondary end points were OHE, variceal rebleeding, recurrent ascites and shunt dysfunction. RESULTS: The 1-, 2-, 3-, 4- and 5-year cumulative survival rates were 92.4%, 87.9%, 85.3%, 80.2% and 80.2%, respectively. Post-TIPS OHE and Child-Pugh grade were independent prognostic factors. The rates of variceal rebleeding, recurrent ascites, shunt dysfunction and post-TIPS OHE were 9.1%, 14.3%, 5.3% and 28.0%, respectively. The variables of nomogram predicting post-TIPS OHE included age, diabetes and ascites grade. The area under time-dependent receiver operation characteristic (ROC) curve (AUC) in training and validation cohort were 0.806 and 0.751, respectively. The decision curve analysis (DCA) showed good net benefit both in training and validation cohort. CONCLUSION: Post-TIPS OHE and Child-Pugh grade are independent prognostic factors for early mortality in cirrhosis patients, thus we construct a simple and convenient prediction model for post-TIPS OHE to identify high-risk patients preoperatively.

Coriaceumins A-D, the First Nitrogen-Containing Crenulide Diterpenoids from the Brown Alga Dictyota coriacea Collected in the East China Sea.

A phytochemical investigation of an East China Sea collection of the brown alga Dictyota coriacea has led to the isolation of four novel nitrogen-containing crenulide diterpenoids, named coriaceumins A-D (1-4), two rare nitrogenous xenicane diterpenoids, dictyolactams C (5) and D (6), and one known crenulide diterpenoid, hydroxycrenulide (7). The structures of the new compounds were elucidated by detailed spectroscopic data analyses, including HRESIMS and 1D/2D NMR. The absolute configurations were determined by a comparison of the experimental ECD spectra with the spectra computed by DFT-based quantum chemical calculations. Coriaceumins A-D (1-4) represent the first examples of nitrogen-containing crenulide diterpenoids. In a bioassay, compounds 2, 3, 5, and 7 were found to exhibit different levels of inhibitory effects against protein tyrosine phosphatase 1B (PTP1B) with IC50 values ranging from 7.3 to 19 µM. In addition, the primary structure-activity relationships of all the isolates were summarized.

Four uncommon cycloamphilectane-type diterpenoids with antibacterial activity from the South China Sea soft coral Sinularia brassica.

The chemical investigation on the soft coral Sinularia brassica collected off Xuwen Country, Guangdong Province, China, has resulted in the isolation and characterization of three uncommon cycloamphilectane-type diterpenoids, namely sinucycloamtin A-C (1-3), along with two known analogues (5 and 6). In addition, compounds 2 and 3 were hydrolyzed and their hydrolytic derivative sinucycloamtin D (4) was obtained. The structures of these previously undescribed compounds were established on the basis of extensive spectroscopic analysis, X-ray diffraction analysis, chemical conversion, as well as the comparison with the literature reported data. Compounds 1-3 represented the first examples of benzene-containing cycloamphilectane-type diterpenoids isolated from soft coral of genus Sinularia. In the in vitro bioassays, all the isolated and derived diterpenoids exhibited significant antibacterial activities against the fish pathogenic bacteria Phoyobacterium damselae FP2244 and Streptococcus parauberis SPOF3K with MIC90 values ranging from 3.7 to 9.1 µM.

Decoding movement frequencies and limbs based on steady-state movement-related rhythms from noninvasive EEG.

Objective.Decoding different types of movements noninvasively from electroencephalography (EEG) is an essential topic in neural engineering, especially in brain-computer interface. Although the widely used sensorimotor rhythm (SMR) is efficient in limb decoding, it lacks efficacy in decoding movement frequencies. Accumulating evidence supports the notion that the movement frequency is encoded in the steady-state movement-related rhythm (SSMRR). Our study has two primary objectives: firstly, to investigate the spatial-spectral representation of SSMRR in EEG during voluntary movements; secondly, to assess whether movement frequencies and limbs can be effectively decoded based on SSMRR.Approach.To comprehensively examine the representation of SSMRR, we investigated the frequency characteristics and spatial patterns associated with various rhythmic finger movements. Coherence analysis was performed between the sensor or source domain EEG and finger movements recorded by data gloves. A fusion model based on spectral SNR features and filter-bank common spatial pattern features was utilized to decode movement frequencies and limbs.Main results.At the group-level, sensor domain, and source domain coherence maps demonstrated that the accurate movement frequency (f0) and its first harmonic (f1) were encoded in the contralateral motor cortex. For the four-class classification, including two movement frequencies for both hands, the decoding accuracies for externally paced and internally paced movements were 73.14 ± 15.86% and 66.30 ± 17.26% (averaged across ten subjects, chance levels at 31.05% and 30.96%). Notably, the average results of five subjects with the highest decoding accuracies reached 87.21 ± 7.44% and 80.44 ± 7.99%.Significance.Our results verified the EEG representation of SSMRR and proved that the movement frequency and limb could be effectively decoded based on spatial-spectral features extracted from SSMRR. We suggest that SSMRR can serve as a complement to SMR to expand the range of decodable movement types and the approaches of limb decoding.

Four New Diterpenoids from the South China Sea Soft Coral Sinularia nanolobata and DFT-Based Structure Elucidation.

Three new cembranoids (1-3) and a new casbanoid (4), along with three known analogues (5-7), have been isolated from the soft coral Sinularia nanolobata collected off Ximao Island. The structures, including the absolute configurations of new compounds, were established using extensive spectroscopic data analysis, time-dependent density functional theory/electronic circular dichroism (TDDFT-ECD) calculations, and the comparison with spectroscopic data of known compounds. In the in vitro bioassay, compounds 1 and 5 exhibited moderate cytotoxic activities against human erythroleukemia (HEL) cell lines, with IC50 values of 37.1 and 42.4 µM, respectively.

Origin of Deformation Twinning in bcc Tungsten and Molybdenum.

Twinning is profuse in bcc transition metals (TMs) except bulk W and Mo. However, W and Mo nanocrystals surprisingly exhibit twinning during room temperature compression, which is completely unexpected as established nucleation mechanisms are not viable in them. Here, we reveal the physical origin of deformation twinning in W and Mo. We employ density functional theory (DFT) and a reduced-constraint slip method to compute the stress-dependent generalized stacking fault enthalpy (GSFH), the thermodynamic quantity to be minimized under constant loading. The simple slipped structures and GSFH lines show that compressive stresses stabilize a two-layer twin embryo, which can grow rapidly via twinning disconnections with negligible energy barriers. Direct atomistic simulations unveil the explicit twinning path in agreement with the DFT GSFH lines. Twinning is thus the preferred deformation mechanism in W and Mo when shear stresses are coupled with high compressive stresses. Furthermore, twinnability can be related to the elastic constants of a stacking fault phase (SFP). The hcp phase may serve as a candidate SFP for the {112}⟨1[over ¯]1[over ¯]1⟩ twinning system in bcc TMs and alloys, which is coincident with the {111}⟨112[over ¯]⟩ twinning in fcc structures.

Two new compounds from the Hainan Soft Corals Sinularia tumulosa and Sinularia depressa with their anti-inflammatory or cytotoxic activities.

The detailed chemical investigations of the South China Sea soft corals Sinularia tumulosa and Sinularia depressa, yielded two new compounds, namely tumulosterol A (1) and 11'-hydroxy-α-tocopherylquinone (3), along with four related known ones (2, 5-7). Their structures were determined by extensive spectroscopic analysis and comparison with the spectral data previously reported in the literature. In bioassays, compound 1 displayed significant cytotoxic effects against H1975 and MDA-MB-231 cells with IC50 values of 6.0 and 6.3 µM, respectively. In addition, compound 3 exhibited interesting inhibitory effect on lipopolysaccharide (LPS)-induced inflammatory responses in RAW264.7 cells with IC50 value of 9.5 µM.

Ocellatuspyrones A‒G, new antibacterial polypropionates from the Chinese mollusk Placobranchus ocellatus.

Marine invertebrates serve as rich sources of secondary metabolites with intriguing chemical diversities and a wide spectrum of biological activities. Particularly, marine shell-less sacoglossan mollusks have attracted much attentions due to the fact that mollusks apply complex metabolites as chemical defense agents against to their predators. With the purpose of discovering bioactive secondary metabolites to develop marine-derived medicines from the South China Sea, we have conducted a chemical study on the photosynthetic mollusk Placobranchus ocellatus. As a result, seven new γ-pyrone polypropionates, namely ( ±)-ocellatuspyrone A (1), ( ±)-ocellatuspyrone B (2), and ocellatuspyrones C-G (5, 9-12), along with five known polypropionates, have been isolated and characterized from the South China Sea photosynthetic mollusk Placobranchus ocellatus. Extensive spectroscopic analysis, single crystal X-ray diffraction analysis, modified Mosher's method, ECD comparison, CD exciton chirality method, TDDFT-ECD calculation, and chemical conversion were used to determine the structures and absolute configurations of the new compounds and the stereochemistry of undefined known compounds 4, 6 and 7. All these isolated polypropionates were evaluated in bioassays for their biological activities, including antibacterial, neuroprotective effect, anti-inflammatory, PTP1B inhibitory, and antiviral activities. Compounds 7, 8 and 11 were found for the first time to show antibacterial activity against fish pathogenic bacteria Streptococcus parauberis (the main pathogen causing fish streptococcal infections and acute death) with MIC values of 35.8, 34.2, and 37.4 µg/mL, respectively, which might be potential novel antibacterial agents for the treatment of fish infectious diseases. Supplementary Information: The online version contains supplementary material available at 10.1007/s42995-023-00179-w.

The dynamics and removal efficiency of antibiotic resistance genes by UV-LED treatment: An integrated research on single- or dual-wavelength irradiation.

Antimicrobial resistance has gained increasing attention, because of the awareness of its potential health risks. Strategies for the removal of antibiotic resistance genes (ARGs) are urgently required. In the present study, UV-LEDs at wavelength of 265 and 285 nm were integrated at five conditions, including single 265 nm UV-LED, single 285 nm UV-LED, and combined 265 nm and 285 nm UV-LED at different intensities, to remove tet A, cat 1, and amp C. The ARGs removal efficiency, gene behavior, and possible cellular mechanism were analyzed using real-time quantitative PCR, flow cytometry, and transmission electron microscopy (TEM). The 265 nm UV-LED is more effective than the 285 nm UV-LED and their combinations in terms of ARGs control, in which 1.91, 1.71, and 1.45 log were removed for tet A, cat 1, and amp C, respectively, at a UV dosage of 500 mJ/cm2. The intracellular gene leakage was detected in all five UV-LED experiment scenarios even when the cell membrane damage was insignificant with the highest increase of 0.69 log ARGs. ROS was generated during the irradiation, and the ROS was strongly negative correlated with intracellular ARGs, which could promote the degradation and removal of ARGs. This study provides a new insight of intracellular ARGs removal, because direct irradiation, ROS oxidation, and leakage to the extracellular serve as the three main pathways under high-dosage UV-LED irradiation. Further research should be focused on the mechanism and optimization of UV technology with 265 nm UV-LED for ARG control.

Surface Modification of Super Arborized Silica for Flexible and Wearable Ultrafast-Response Strain Sensors with Low Hysteresis.

Conductive hydrogels exhibit high potential in the fields of wearable sensors, healthcare monitoring, and e-skins. However, it remains a huge challenge to integrate high elasticity, low hysteresis, and excellent stretch-ability in physical crosslinking hydrogels. This study reports the synthesis of polyacrylamide (PAM)-3-(trimethoxysilyl) propyl methacrylate-grafted super arborized silica nanoparticle (TSASN)-lithium chloride (LiCl) hydrogel sensors with high elasticity, low hysteresis, and excellent electrical conductivity. The introduction of TSASN enhances the mechanical strength and reversible resilience of the PAM-TSASN-LiCl hydrogels by chain entanglement and interfacial chemical bonding, and provides stress-transfer centers for external-force diffusion. These hydrogels show outstanding mechanical strength (a tensile stress of 80-120 kPa, elongation at break of 900-1400%, and dissipated energy of 0.8-9.6 kJ m-3 ), and can withstand multiple mechanical cycles. LiCl addition enables the PAM-TSASN-LiCl hydrogels to exhibit excellent electrical properties with an outstanding sensing performance (gauge factor = 4.5), with rapid response (210 ms) within a wide strain-sensing range (1-800%). These PAM-TSASN-LiCl hydrogel sensors can detect various human-body movements for prolonged durations of time, and generate stable and reliable output signals. The hydrogels fabricated with high stretch-ability, low hysteresis, and reversible resilience, can be used as flexible wearable sensors.

Anti-Inflammatory Steroids from the South China Sea Soft Coral Lobophytum sarcophytoides.

Three new steroids, along with two known related analogs, were isolated from the Xisha Island soft coral Lobophytum sarcophytoides. The structures and absolute configurations of the new compounds were elucidated by extensive spectroscopic data analyses, time dependent density functional theory electronic circular dichroism calculation, and comparison with the spectral data previously reported in the literature. In in vitro bioassay, four compounds showed interesting suppressive effects on lipopolysaccharide (LPS) induced inflammation in BV-2 microglial cells at 10 µM level.

Boosting membrane carbon capture via multifaceted polyphenol-mediated soldering.

Advances in membrane technologies are significant for mitigating global climate change because of their low cost and easy operation. Although mixed-matrix membranes (MMMs) obtained via the combination of metal-organic frameworks (MOFs) and a polymer matrix are promising for energy-efficient gas separation, the achievement of a desirable match between polymers and MOFs for the development of advanced MMMs is challenging, especially when emerging highly permeable materials such as polymers of intrinsic microporosity (PIMs) are deployed. Here, we report a molecular soldering strategy featuring multifunctional polyphenols in tailored polymer chains, well-designed hollow MOF structures, and defect-free interfaces. The exceptional adhesion nature of polyphenols results in dense packing and visible stiffness of PIM-1 chains with strengthened selectivity. The architecture of the hollow MOFs leads to free mass transfer and substantially improves permeability. These structural advantages act synergistically to break the permeability-selectivity trade-off limit in MMMs and surpass the conventional upper bound. This polyphenol molecular soldering method has been validated for various polymers, providing a universal pathway to prepare advanced MMMs with desirable performance for diverse applications beyond carbon capture.

Cembrane Diterpenes Possessing Nonaromatic Oxacycles from the Hainan Soft Coral Sarcophyton mililatensis.

Documents on the chemical composition of the soft coral Sarcophyton mililatensis are sparse. The present investigation of the Hainan soft coral S. mililatensis resulted in the discovery of six new cembrane diterpenes, sarcoxacyclols A-F (1-6) and four known analogs (7-10). Their structures were elucidated by extensive spectroscopic analysis along with a comparison with the data in current literature. The nonaromatic oxacycles in their structures were the rarely found tetrahydrofuran ether across C-1 and C-12 and tetrahydropyran ether across C-1 and C-11, respectively. Moreover, the absolute configuration of compound 4 was established unambiguously by X-ray diffraction analysis using Ga Kα radiation (λ = 1.34139 Å). Based on the biogenetical consideration, the absolute configurations of other five new compounds were tentatively assumed. Assessment of the bioactivity for these secondary metabolites revealed that compound 1 exhibited significant tumor necrosis factor (TNF)-α inhibitory activity (IC50 = 9.5 µmol/L), similar to the positive control dexamethasone (IC50 = 8.7 µmol/L), but no obvious cytotoxicity towards RAW264.7 cells (CC50 > 50 µmol/L). The preliminary molecular docking suggested the crucial roles of the hydroxyl and acetoxyl groups in the computational prediction of the binding mode between the diterpene and the protein.

Nanolobatone A, An Unprecedented Diterpenoid and Related New Casbanoids from the Hainan Soft Coral Sinularia nanolobata.

Nanolobatone A, featuring an unprecedented tricyclo[10.3.0.01,2 ]pentadecane carbon skeleton, along with four new polyoxygenated and four unusual endoperoxide-bridged casbane-type diterpenoids were isolated from the Hainan soft coral Sinularia nanolobata. The structures of the new compounds were established by extensive spectroscopic analysis, X-ray diffraction analysis, and time-dependent density functional theory/electronic circular dichroism calculations. A plausible biosynthetic pathway of new isolates was proposed. Bioassays revealed that nanolobatone A showed weak antibacterial activity against the Gram-positive bacteria Streptococcus pyogenes.