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High entropy metallic glass nanoparticles (HEMG NPs) are very promising materials for energy conversion due to the wide tuning possibilities of electrochemical potentials offered by their multimetallic character combined with an amorphous structure. Up until now, the generation of these HEMG NPs involved tedious synthesis procedures where the generated particles were only available on highly specialized supports, which limited their widespread use. Hence, more flexible synthetic approaches to obtain colloidal HEMG NPs for applications in energy conversion and storage are highly desirable. We utilized pulsed laser ablation of bulk high entropy alloy targets in acetonitrile to generate colloidal carbon-coated CrCoFeNiMn and CrCoFeNiMnMo HEMG NPs. An in-depth analysis of the structure and elemental distribution of the obtained nanoparticles down to single-particle levels using advanced transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) methods revealed amorphous quinary and senary alloy phases with slight manganese oxide/hydroxide surface segregation, which were stabilized within graphitic shells. Studies on the catalytic activity of the corresponding carbon-HEMG NPs during oxygen evolution and oxygen reduction reactions revealed an elevated activity upon the incorporation of moderate amounts of Mo into the amorphous alloy, probably due to the defect generation by atomic size mismatch. Furthermore, we demonstrate the superiority of these carbon-HEMG NPs over their crystalline analogies and highlight the suitability of these amorphous multi-elemental NPs in electrocatalytic energy conversion.

Computational study on relationship between molecular structure and property of small molecule hole-transporting materials (HTMs) is an efficient pathway to acquire potential HTMs for perovskite solar cells (PSCs). Herein, by conjugating the acceptor groups of electron-deficient diazatriphenylene (DAT), tetraazatriphenylene (TAT) and hexaazatriphenylene (HAT), and p-methoxy-substituted triphenylamine (MeOTPA) electron-donors, six novel donor–acceptor-donor (D-A-D) typed HTMs (SM11 ~ SM16) are designed. Furthermore, three thiophene-substituted acceptors (SM17 ~ SM19) are also investigated. The influences of acceptor moiety on the performance of HTMs are studied by carrying out theoretical chemical calculations. Compared with the reported HTM with triphenylene unit (TPH-T), the new tailored HTMs (SM11 ~ SM19) exhibit more negative highest occupied molecular orbital (HOMO) energy levels and slightly red-shifted light absorption due to the increased electron-deficient property of acceptor group and linked positions with the MeOTPA-donor. Meanwhile, our results show that the small torsion angle between the acceptor and the donor is beneficial to promote the hole transport in HTMs, and the thiophene units on acceptor may also be helpful to enhance the charge mobility of HTMs. In addition, the large charge transfer amounts and small exciton binding energies are found for designed HTMs, which will be favorable to facilitate the electron-hole separation in HTMs. The stability of HTMs may be decreased based on the calculated results of electrostatic surface potential and absolute hardness. We hope this work could highlight the potential of azatriphenylene acceptor-based D-A-D typed HTMs for efficient PSCs.

Summary Objectives This study aimed to evaluate the clinical efficacy and reliability of a novel monocanalicular silicone intubation (nMCI) technique for canalicular laceration repair in a series of patients treated over a 3-year period. Methods The case records of 86 patients (86 eyes) who had undergone nMCI-based surgical repair of canalicular lacerations were retrospectively reviewed. The silicone tube removal was planned for 3 months postoperatively. A minimal follow-up of 6 months was adopted for the final analysis. The primary outcome measures included anatomical patency on irrigation and relief from epiphora, which were assessed subjectively and objectively through a fluorescein dye disappearance test. Results A total of 86 patients (72 males and 14 females; mean age = 34 years) were included. The upper canaliculus was damaged in 13 cases, while the lower canaliculus was damaged in 73 cases. Successful stenting was achieved in all cases. The postoperative eyelid position was satisfactory in the majority of the patients. The mean period of stenting was 3 months, while the mean postoperative follow-up period was 6 months. There were no cases of premature stent extrusion. The functional drainage following stent removal was normal in 95% of the patients, while the syringing revealed full patency with no narrowing or reflux. Conclusion The present results suggest that the nMCI technique presents an effective and atraumatic surgical approach for adult patients with canalicular lacerations. The main advantages of the technique are the simple insertion and the easy removal of the tube, which results in high anatomical and functional success rates and offers an effective alternative in the treatment of monocanalicular lacerations.

Extracellular vesicles (EVs) are nano-sized vesicle structures secreted from a variety of cells, which carry numerous biological macromolecules, participate in cell signal transduction and avoid immune system clearance. EVs have a plethora of specific signal recognition factors, and many studies have shown that they can play an important role in the precise treatment of tumors. This review aims to compile the applications of EVs as nanocarriers for antitumor drugs, gene drugs and other nanomaterials with anticancer capability. Additionally, we systematically summarize the preparation methodology and expound upon how to improve the drug loading and cancer-targeting capacity of EVs. We highlight that EV-based drug delivery has the potential to become the future of precise cancer treatment.

Novel highly stereoselective syntheses of (+)-streptol and (-)-1-epi-streptol starting from naturally abundant (-)-shikimic acid were described in this article. (-)-Shikimic acid was first converted to the common key intermediate by 11 steps in 40% yield. It was then converted to (+)-streptol by three steps in 72% yield, and it was also converted to (-)-1-epi-streptol by one step in 90% yield. In summary, (+)-streptol and (-)-1-epi-streptol were synthesized from (-)-shikimic acid by 14 and 12 steps in 29 and 36% overall yields, respectively.

Autophagy is the process of lysosomal degradation and removal of abnormal or damaged organelles, which plays a pivotal role in a variety of physiological states and involves a variety of pathological processes. Moreover, acidic pH environments of lysosomes can induce and promote autophagy levels. Therefore, it is significant to distinguish between neutral and acidic lysosomes in the process of autophagy. Herein, a dual-channel signal fluorescent probe RD based on two fluorophores was developed for detecting lysosomal pH changes in living cells during the starvation-induced autophagy process. The dual fluorophores of the probe RD made the detection of lysosomal pH changes during autophagy more accurate and visual. More importantly, the probe RD realizes the visualization of distinguishing between natural lysosomes and acidic lysosomes during autophagy in living cells.

Ionic liquids (ILs) play an important role in conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) based electronics and thermoelectrics through regulating morphology and electronic properties. Herein, the hole transport and interface electronic coupling properties of three kinds of IL ([BMIM]:[BF4], [BuPhIM]:[BF4], and [BnPhIM]:[BF4]) mediated PEDOT systems have been researched via multiscale molecular mechanics simulations and quantum mechanics calculations, where the cations of the ILs feature gradually extended π-conjugation. It is indicated that [BnPhIM]:[BF4] induces PEDOT to show more ordered π–π stacking than its counterparts, where the chains are oriented with face-to-face alignment. This is attributed to the larger evenness of the net charge distribution at the [BnPhIM]:[BF4]-PEDOT interface. Consequently, the average mobility in [BnPhIM]:[BF4]-PEDOT is 4.01 cm2 V−1 s−1 and the instantaneous maximum reaches 17 cm2 V−1 s−1, far surpassing its counterparts. Although the predicted PEDOT single crystal presents a well-ordered lamellar structure, the one-dimensional orientation causes hole tunneling along the nanowire-like direction, leading to its mobility lagging behind the [BnPhIM]:[BF4] decorated system by one order of magnitude. On the other hand, the interface electronic coupling and doping efficiency in [BnPhIM]:[BF4]-PEDOT is strengthened, confirming that improving the π-conjugation of the cation of the IL can enhance the mobility of PEDOT and interface electronic coupling synergistically. To improve the mobility further, a novel series of cations containing [BnPhIM-oOMe]+, [BnPhIM-mOMe]+, and [BnPhIM-pOMe]+ has been designed based on the outstanding properties of [BnPhIM]+. Combining the novel designed cations with [BF4]− and [B(CN)4]−, it is observed that [BnPhIM-pOMe]:[B(CN)4] causes PEDOT to assemble with well-ordered π–π stacking. Assessments rationalize that it could serve as a potential candidate for application in PEDOT-based electronics, since it shows similar interface electronic coupling and has a 35–43% improvement in PEDOT mobility compared to the excellent reference [BnPhIM]:[BF4].

A mild, efficient and eco-friendly method for the oxidation of 1-Bn-DHIQs to 1-Bz-DHIQs without concomitant excessive oxidation of 1-Bz-DHIQs to 1-Bz-IQs is very important for the syntheses of 1-Bz-DHIQ alkaloids and analogues. In this article, we developed a novel Cu(II)-catalyzed and acid-promoted highly regioselective oxidation of tautomerizable C(sp3)–H bonds adjacent to the C-1 positions of various 1-Bn-DHIQs. It was observed that when 0.2 equiv. of Cu(OAc)2·2H2O was used as the catalyst, 3.0 equiv. of AcOH was used as the additive and air (O2) was used as a clean oxidant, various 1-Bn-DHIQs could be efficiently oxidized to corresponding 1-Bz-DHIQs at 25 °C in DMSO. Especially, almost no concomitant excessive oxidation of 1-Bz-DHIQs to 1-Bz-IQs was observed during the above reaction. In addition, this method was successfully applied in the first total synthesis of the alkaloid canelillinoxine.

Hypochlorous acid (HClO) is a significant signaling species which plays a decisive role in the immune system as an excellent defense against invasive bacteria. Therefore, it is significant to monitor HClO accurately and quickly in organisms. Herein, a new turn-on fluorescent probe (BM-HA) with a simple structure for rapid sensing of HClO is presented. BM-HA has favorable properties, including high selectivity, a large turn-on fluorescence signal (140-fold), and fast response (about 15 s). Additionally, quantum chemical calculations with DFT and TDDFT proved that reduced fluorescence of the BM-HA probe was possible due to the a-PET effect and the non-coplanarity of the coumarin and the benzothiazole. Furthermore, imaging in living cells and zebrafish indicates that the probe can potentially be used to detect HClO in complex biosystems.

The shuttling of soluble lithium polysulfides (LiPSs) intermediates bottlenecks practical uses of lithium-sulfur (Li-S) batteries. A commercial organometallic salt, nickel chloride dimethoxyethane adduct (NiDME), is introduced as the homogenous catalyst dissolved in the electrolyte to suppress the shuttle effect. A very small amount of catalyst (only 0.5 wt% additive relative to the electrolyte) brings the battery capacity a big rise from 408 to 784 mAh g−1 over 500 cycles at 1 C. More promisingly, the required amount of electrolyte is greatly reduced, and the battery works well with a lean electrolyte (5 μL(electrolyte)/mg(sulfur)). The improved performance is attributed to the catalyst-accelerated LiPS conversion which is characterized by largely decreased activation energy (Ea) of the sulfur redox reaction, especially for Li2S deposition, and much reduced accumulation of LiPSs intermediates. Specially, the NiDME additive captures LiPSs in the electrolyte, accelerates the redox reactions homogeneously and regulates a uniform and fast deposition of Li2S, all these contributing to a perfect catalytic cycle with less LiPS shuttling. This work deepens our understanding on catalysis in accelerating sulfur redox conversion and indicates homogeneous catalysis as a simple yet fundamental solution to shuttle effect of LiPSs intermediates, which boosts practical Li-S batteries with less electrolyte needs and long working life.

Radiation-induced acute intestinal injury is a common and serious occurrence following abdominal and pelvic irradiation. The Nod-like receptor protein 3 (NLRP3)-dependant inflammasome and inflammation activation is crucial in this process. In a pre-experimental design of radiation-induced intestinal injury, we found that rosiglitazone inhibited caspase-1 which is a key marker of inflammasome activation. The purpose of the present study was to clarify the inhibitory effect of rosiglitazone on the NLRP3 inflammasome both in vivo and in vitro. Radiation-induced intestinal injury after rosiglitazone treatment, and the expression of interleukin-1β (IL-1β), tumor necrosis factor-α (TNF-α), caspase-1 and NLRP3 in a radiation-induced intestinal injury model in a rat and macrophages were observed. We found that rosiglitazone ameliorated radiation-induced intestinal injury in rats by suppressing the expression of caspase-1, NLRP3, IL-1β and TNF-α. Treatment with rosiglitazone in vitro reduced the expression of NLRP3, and the NLRP3 activator monosodium urate (MSU) reversed the inhibition of IL-1β and TNF-α by rosiglitazone in macrophages. MSU reversed the protective effect of rosiglitazone on radiation-induced intestinal injury in rats by reversing the rosiglitazone-induced inhibition of IL-1β and TNF-α. Taken together, these findings indicate that the peroxisome proliferator-activated receptor gamma (PPARγ) agonist, rosiglitazone, ameliorates radiation-induced intestine inflammation in rats via inhibiting the induction of the NLRP3-dependent inflammasome in macrophages.

Three new cyclometalated iridium(III) complexes [(cf3piq)2Ir(N∧N)][PF6] (Ir1–Ir3) have been synthesized and characterized. The solid structure of Ir1 has been determined by X-ray crystallography. T...

As an important pilot target for shale gas exploration and development in China, the Longmaxi Formation shale in the Dianqianbei Area is characterized by high content of nitrogen, which severely increases exploration risk. Accordingly, this study explores the genesis of shale gas reservoir and the mechanism of nitrogen enrichment through investigating shale gas compositions, isotope features, and geochemical characteristics of associated gases. The high-nitrogen shale gas reservoir in the Longmaxi Formation is demonstrated to be a typical dry gas reservoir. Specifically, the alkane carbon isotope reversal is ascribed to the secondary cracking of crude oil and the Rayleigh fractionation induced by the basalt mantle plume. Such a thermogenic oil-type gas reservoir is composed of both oil-cracking gas and kerogen-cracking gas. The normally high nitrogen content (18.05%–40.92%) is attributed to organic matter cracking and thermal ammoniation in the high-maturity stage. Specifically, the high heat flow effect of the Emeishan mantle plume exacerbates the thermal cracking of organic matter in the Longmaxi Formation shale, accompanied by nitrogen generation. In comparison, the abnormally high nitrogen content (86.79%–98.54%) is ascribed to the communication between the atmosphere and deep underground fluids by deep faults, which results in hydrocarbon loss and nitrogen intrusion, acting as the key factor for deconstruction of the primary shale gas reservoir. Results of this study not only enrich research on genetic mechanism of high-maturity N2 shale gas reservoirs, but also provide theoretical guidance for subsequent gas reservoir resource evaluation and well-drilling deployment in this area.

Six zinc(II) complexes, [Zn(OCOPh)2LR] (R = 1, 2, 3, 4, 5, 6) were synthesized by the reaction of zinc benzoate and six para-substituted 4-phenyl-terpyridine complexes and their structures were confirmed by elemental analysis, FT-IR, 1H NMR and X-ray single crystal diffraction analysis. Their photoluminescent properties in solid and in solutions of DMSO were studied. Three human cancer cell lines were used for antiproliferative potential: human lung cancer cell line (A549), human esophageal cancer cell line (Eca-109) and human breast cancer cell line (MCF-7). The results have shown that these zinc complexes have good inhibitory effects on cancer cells, which are better than that of the commonly used clinical drug cisplatin. The ability of the complexes to binding to CT-DNA was studied by UV spectroscopy and fluorescence titration, while the interaction between the complexes and CT-DNA, AT6, GC6 short-chain DNA sequences and G-quadruplex were analyzed by circular dichroism (CD). It is found that these complexes can bind to DNA, and the binding mode is mainly intercalator. The docking of the complexes with the DNA fragment was simulated using molecular docking software. All the results clearly display that the substituents at these ligands of the complexes have the substitution effects on the properties of photoluminescence, antiproliferative potential and DNA binding study.

Vanadium pentoxide (V2O5) has been extensively used as the cathode material for lithium-ion batteries (LIBs). But the chemical dissolution of V2O5 in the electrolyte greatly restrains its electroch...

Dense polycrystalline cubic boron nitride (PcBN) composites were fabricated by high-pressure and high-temperature (HPHT) sintering using polysilazane (PSN) and Al as sintering additive. After high-energy ball milling, the cBN fine particles were uniformly coated with PSN by ultrasonic treatment. After thermocuring and pyrolysis, the cBN–SiCN particles were mixed with Al. The PcBN composites were prepared after sintering at 1450 °C for 10 min with a pressure of 5 GPa. The refining effect of high-energy ball milling on the cBN particles was studied by scanning electron microscopy (SEM) and laser particle size analyzer. The oxidation of the cBN particles after milling was investigated by nitrogen–oxygen analyzer. The phase composition and microstructure of the sintered PcBN composites were investigated by X-ray diffractometer (XRD) and SEM. The main phases of the sintered PcBN composites are cBN, AlN, SiC and Si3N4. The conversion of cBN to hBN was inhibited by the formation of AlN. The mechanical properties of the sintered PcBN composites were improved by the appearance of SiC and Si3N4. The density and mechanical properties of the PcBN composites both increased with the content of the cBN particles increasing. The sintered sample with 60 wt% cBN, 30 wt% PSN and 10 wt% Al showed the best results: density of 99.7%, Vickers’ hardness of (25.2 ± 0.8) GPa and flexural strength of (602 ± 15) MPa.

Vanadium pentoxide (V2O5)-based composites show outstanding performances as cathode materials in lithium-ion batteries. However, their inferior thermal conductivity restricts the heat dissipation through the cathode electrode. In this study, we measured the thermal conductivity of V2O5 nanowires using the thermal bridge method and found that their thermal conductivity is 3.84 ± 0.38 W m−1 K−1 at T = 300 K. The contact thermal resistance between two nanowires with the same size was measured to be up to 50%–80% of the total thermal resistance in the measured samples, indicating that their contact is the bottleneck for thermal dissipation.

Efficient and highly stereoselective syntheses of (+)-proto-quercitol and (-)-gala-quercitol starting from the naturally abundant (-)-shikimic acid were described in this article. (-)-Shikimic acid was first converted to the key intermediate by eight steps in 53% yield. It was then converted to (+)-proto-quercitol by three steps in 78% yield and was also converted to (-)-gala-quercitol by five steps in 63% yield. In summary, (+)-proto-quercitol and (-)-gala-quercitol were synthesized from (-)-shikimic acid by 11 and 13 steps in 41 and 33% overall yields, respectively.

In this work, two novel electron-deficient groups phenanthrothiadiazole (PT) and triphenylenobisthiadiazole (TBT) are utilized to construct donor–acceptor–donor (D–A–D) type hole-transporting materials (HTMs). The electronic, optical and charge transport properties are evaluated by performing quantum chemical calculations. Our results show that, in comparison with that of the benzothiadiazole (BT, SM-1) unit, the newly designed SM-2 and SM-3 display more deep highest occupied molecular orbital (HOMO) energy levels. Meanwhile, the blue-shifted light absorption spectra are also obtained, which will be helpful in enhancing the absorption of the perovskite layer. Unfortunately, the hole mobilities of SM-2 and SM-3 are slightly lower than that of SM-1 due to the weak intermolecular electronic coupling. In addition, we also find that better solubility and stable dimeric configuration are obtained for the new HTMs. Overall, this work provides some useful clues for designing new acceptor structures in D–A–D-type HTMs, and a potential HTM SM-3 is proposed.

The design of new molecules with theoretical chemistry methods and further obtaining a fundamental understanding of the structure-property relationship are important for the development of high-efficiency hole-transporting materials (HTMs). Herein, the effect of semi-locked and fully-locked cores was systematically investigated based on two conformation-tunable tetrathienylethene (TTE) and tetraphenylethylene (TPE) units. Our results show that the highest occupied molecular orbital (HOMO) levels of the locked TTE-2 and TTE-3 are clearly down-shifted compared with that of the unlocked TTE-1, which is due to the decreased electronic conjugation between the locked cores and the triphenylamine (TPA) arms, whereas the same situation is not found for TPE-3 due to the twisted core configuration. Compared with the TTE-series, the TPE-series exhibits less optical absorption in the visible light region and enhanced stability. Meanwhile, the hole mobility of the designed HTMs displays an increased trend from the unlocked core to the semi-locked and fully-locked cores due to the gradually increasing hole transfer integral with enhanced molecular planarity. In addition, we also found that the reorganization energy of the locked TTE cores is obviously lowered compared to that of the unlocked one, which plays an important role in increasing the hole mobility. In summary, this work can provide some useful clues for designing high-efficiency two-dimensional HTMs, and two potential promising candidates (TTE-3 and TPE-3) are proposed.

Microwave-assisted synthesis of polyheterocyclic-fused quinoline-2-thiones through the annulation of ortho-heteroaryl anilines and CS2 was realized in water without using any catalysts and additives. The desired products were obtained in high yields through simple filtration. A remarkable E-factor of 0.45 and an EcoScale score of 85.5 were obtained.

BackgroundExcessive autophagic activity in alveolar epithelial cells is one of the main causes of acute lung injury (ALI), but the underlying molecular mechanism has not been fully elucidated. Previous studies have shown that microRNAs (miRs) are involved in regulating autophagy in several diseases. This study aimed to determine the role of miR-223 in excessive autophagic activity in alveolar epithelial cells and the underlying mechanism to identify a novel therapeutic targets for the development of new drugs to treat acute respiratory distress syndrome (ARDS).MethodsA549 cells were treated with lipopolysaccharide (LPS) to establish an ALIin vitromodel. The expression of miR-223 and its role of miR-223 in regulating oxidative stress and autophagy in the LPS-treated A549 cells, were examined using RT-PCR, flow cytometry and ELISA. A luciferase reporter assay was performed to verify the interaction between miR-223 and the high-mobility group box 2 (HMGB2) protein.ResultsThe results showed that the LPS treatment downregulated miR-223 expression in alveolar epithelial cells. We further proved that miR-223 directly targeted the 3-untranslated region of the HMGB2 gene and the downregulation of miR-223 increased HMGB2 protein level, which activated the JNK signalling pathway and thus induced oxidative stress and autophagy in LPS-treated alveolar epithelial cells. Knockdown of HMGB2 protein deactivated the JNK signalling pathway and inhibited autophagy and oxidative stress in alveolar epithelial cells.ConclusionsThe results of this study suggest that miR-223 regulates oxidative stress and autophagy in alveolar epithelial cells by targeting HMGB2 via the JNK signalling pathway.

This study investigated the mechanism of toll-like receptor 4(TLR4) in up-regulating autophagy-related protein and matrix metalloproteinase 9(MMP9), MMP14 expression in THP-1 macrophages which were stimulated by Extracellular Matrix Metalloproteinase Inducer (EMMPRIN).

Herein, we fabricate a composite fluorescence sensor by integrating amine-functionalized carbon quantum dots (amine-CQDs) and a zirconium-based metal-organic framework (UiO-67) using a post-synthetic modification approach, and employ the resulting amine-CQDs@UiO-67 composite as a platform for highly selective and sensitive detection of 2,4-dinitrophenol (DNP). In particular, UiO-67 acts as an adsorbent for the selective capture and enrichment of DNP molecules, whereas amine-CQDs serve as functional monomers for selective and sensitive DNP sensing.

With intrinsically disordered atomic structure, metallic glasses (MGs) have been extensively studied as advanced catalysts. Although the nature of widely tunable atomic composition in MGs facilitates accommodation in different catalytic environments, it may also induce the decline of catalytic activity due to surface effect. The role of surface of MGs is still not fully understood. In this work, an Fe50Ni30P13C7 (FeNiPC) glassy ribbon was found to have a strong-binding surface layer with the superior anticorrosion but low catalytic ability. Nevertheless, an effective elimination of surface layer by chemical dealloying could highly promote the catalytic ability of FeNiPC glassy ribbons from 20 min to only 10 min for brilliant black BN dye degradation. Further investigation revealed that chemical dealloying could effectively dissolve the surface layer of FeNiPC glassy ribbons induced reactivation of surface that was previously buried under the strong oxide layer, instead of generating nano-porous structured surface. The reactivation of ribbon surface effectively optimized active reaction sites and the re-exposure of Fe, Ni and P with zero-valent state formed galvanic cells by atomic clusters leading to the acceleration of catalysis. The insight and revelation of intrinsic surface activity in this work provide an effective way to highly promote the catalytic ability of MGs.

Loofah sponge (LS) was used as carrier for high ammonia wastewater treatment with a sequencing batch biofilm reactor (SBBR), aimed at evaluating its nitrogen removal performance and durability to changeable pH and microbial corrosion. The results indicate that the average removal for COD, NH 4 + -N and total nitrogen (TN) accounted for more than 80%, 90%, and 70%, respectively, in 203 days. After SBBR operation for 108 days, the average weight loss of the loofah sponge was 49.1%. Yet, the main structure of utilized loofah sponge remained unaffected (proved by scanning electron microscopy). Moreover, based on attenuated total reflection-infrared spectroscopy (ATR-IR) and X-ray diffraction (XRD) measurements, cellulose, and hemicelluloses in the loofah sponge were reduced significantly obviously causing the proportion of lignin to increase. During the 108th to 203 days, the removal efficiencies of COD (81.6 ± 7.05%), NH 4 + -N (79.4 ± 8.82%), and TN (79.9 ± 2.85%) remained at a high level. PRACTITIONER POINTS: Loofah sponge had good durability to high ammonia and changeable pH. Lignin was the protective material of loofah sponge for resisting pH fluctuation and microbial corrosion. SBBR maintained a steady nitrogen removal performance with a low COD/N ratio.

In the present work, nitrogen-doped mesoporous carbon nanosheets (NMCNs) are prepared and extensively investigated for the oxygen reduction reaction. Initially, by using dual templates, viz. graphene oxide and a cationic surfactant, silica films (thickness: 1.0 nm) are synthesized and characterized using transmission electron microscope (TEM), nitrogen adsorption-desorption (N2 ad/des) measurements, and small-angle X-ray diffraction (SA-XRD). Morphology and structure of silica evolve along with graphene oxide concentration, while the co-operative assembly and the final structure are determined by the electrostatic interaction between the dual templates. The effect of silica template on the resultant NMCNs is investigated physicochemically by photoelectron spectroscopy (XPS), TEM, N2 ad/des and electrochemically by cyclic voltammetry (CV), and linear sweep voltammetry (LSV). NMCNs are featured of a high content of nitrogen dopant, high specific surface area (SSA) and ultrathin thickness (1.5 nm), favoring catalysis and facilitating the mass transport of the reactive species. From the electrochemical tests, it is confirmed that NMCNs yield a high oxygen reduction reaction (ORR) electrocatalytic activity in acid and alkaline environment; this activity is similar or even better as compared with the one measured over carbon supported platinum commercial catalyst (40 wt % Pt/C).

Ni(II) coordination polymer nanosheets (Ni-CPNS) were prepared via a top-down liquid ultrasonication exfoliation method. For the first time, Ni-CPNS was used as a co-catalyst (Ni-CPNS@CdS) via a mechanical grinding strategy. The optimized Ni-CPNS@CdS catalyst reached a super high visible-light photocatalytic hydrogen production activity of 10 210 μmol h−1 g−1, exceeding that of bare CdS nanoparticles by 1480%. Our work can open new avenues towards the design of stable and cheap CPNS co-catalysts to replace expensive and rare noble metals for photocatalysis processes.

Vanadium pentoxide (V2O5), as one of the most important electrode materials for lithium ions batteries, attracts tremendous attention. Here, carbon supported V2O5 hollow nanotubes are synthesized using carbon fibers as templates through solvothermal reaction with subsequent annealing treatment. Morphological features of the samples are investigated by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). X-ray diffraction (XRD) patterns confirm the formation of phase-pure structure. Elemental mapping and XPS studies are used to confirm the existence of carbon and V4+ in nanotubes. Electrochemical Li insertion behavior of nanotubes are explored as cathode in half cell configuration (vs. Li) using cyclic voltammetry, galvanostatic charge-discharge studies and rate tests. The V2O5 hollow nanotubes display a good cycling performance with a specific capacity of 237 mA h g−1 after 50 cycles at 100 mA g−1 in the voltage range of 2.0-4.0 V. Moreover, the nanotubes cathode delivers specific capacities of 165.8, 140.3 and 109.6 mA h g−1 at 1000, 2000 and 5000 mA g−1, respectively, indicating a desirable rate capability. The good electrochemical performance of carbon supported V2O5 hollow nanotubes can be attributed to the unique hollow nanotubes and the existence of carbon and V4+.

N-Octyl-β-valienamine (NOV) 1 and N-octyl-4-epi-β-valienamine (NOEV) 2 are potent chemical chaperone drug candidates for the therapy of lysosomal storage disorders. Novel stereoselective syntheses of NOV 1 and NOEV 2 starting from naturally abundant (−)-shikimic acid are described in this article. The common key intermediate compound 5 was first synthesized from readily available (−)-shikimic acid via 9 steps in 50% yield. Compound 5 was then converted to NOV 1 via 5 steps in 61% yield, and it was also converted to NOEV 2 via 8 steps in 38% yield. In summary, NOV 1 was synthesized via 14 steps in 31% overall yield; and NOEV 2 was synthesized via 17 steps in 19% overall yield.

Photoacoustic (PA) imaging is an emerging biomedical imaging modality that combines the advantages of optical and ultrasound imaging. Carbon monoxide (CO), which is a vital endogenous cell-signaling molecule in the human body, exerts critical physiological functions such as anti-inflammatory, antiapoptotic, and antiproliferative. The imbalance of CO homeostasis is also associated with numerous diseases. Therefore, it is critically important to noninvasively monitor the steady-state changes of CO in vivo. However, the activatable photoacoustic (PA) probes for detecting CO-associated complicated diseases have not yet developed. In this work, we developed the first turn-on PA probe (MTR-CO) to visualize the CO level in the lipopolysaccharide (LPS)-induced acute inflammation murine model through PA imaging technology. MTR-CO is composed of a near-infrared absorption cyanine-like dye (MTR-OH) and allyl formate, showing a 10.2-fold PA signal enhancement at 690 nm upon activation by CO. Furthermore, the results revealed that MTR-CO has high sensitivity, excellent specificity, and good biocompatibility for CO in vivo. MTR-CO was then applied for PA imaging of CO in cells and for monitoring the development of acute inflammation in the murine model by tracking the changes of the CO level. These findings provide a promising strategy for accurately detecting the steady-state changes of CO in living organisms.

Metallic glasses (MGs) with superior catalytic performance have recently been recognized as attractive candidates for wastewater treatment. However, further improving their performance will require knowledge of how to precisely regulate their electronic structures via compositional control. Here, two Fe-based MGs (Fe

SummaryReorganization of microtubules from the centrosome to non-centrosomal subcellular sites is central to cell differentiation. To identify components of non-centrosomal microtubule organizing centers in differentiated cells of a living organism, we developed the biotin ligase-based proximity labeling approach TurboID for use inC. elegans. We identified proteins proximal to the non-centrosomal microtubule minus end protein PTRN-1/Patronin at the apical membrane of epithelial cells, focusing on two conserved proteins: spectraplakin protein VAB-10B and WDR-62, a protein we identify as homologous to vertebrate primary microcephaly disease gene WDR62. We found that WDR-62 and VAB-10B independently regulate the growth and localization of non-centrosomal microtubules and the apical targeting of microtubule minus end proteins. This regulation occurs downstream of cell polarity and in conjunction with actin. Our data suggest a division of labor where microtubule growth and anchoring are regulated by distinct complexes and uncover novel functions of spectraplakins and WDR62 family proteins.

Six new zinc(II) complexes were prepared by the reaction of ZnBr2 or ZnI2 with 4&prime, (substituted-phenyl)-2,2&prime, 6&prime, 2&prime, &prime, terpyridine compounds, bearing p-methylsulfonyl (L1), p-methoxy (L2) and p-methyl (L3), which were characterized by elemental analysis, FT-IR, NMR and single crystal X-ray diffraction. The antiproliferative properties against Eca-109, A549 and Bel-7402 cell lines and the cytotoxicity test on RAW-264.7 of these compounds were monitored using a CCK-8 assay, and the studies indicate that the complexes show higher antiproliferative activities than cisplatin. The interactions of these complexes with CT-DNA and proteins (BSA) were studied by UV-Vis, circular dichroism (CD) and fluorescent spectroscopy, respectively. The results indicate that the interaction of these zinc(II) complexes with CT-DNA is achieved through intercalative binding, and their strong binding affinity to BSA is fulfilled through a static quenching mechanism. The simulation of the complexes with the CT-DNA fragment and BSA was studied by using molecular docking software. It further validates that the complexes interact with DNA through intercalative binding mode and that they have a strong interaction with BSA.

A polarized arrangement of neuronal microtubule arrays is the foundation of membrane trafficking and subcellular compartmentalization. Conserved among both invertebrates and vertebrates, axons contain exclusively ‘plus-end-out’ microtubules while dendrites contain a high percentage of ‘minus-end-out’ microtubules, the origins of which have been a mystery. Here we show that in Caenorhabditis elegans the dendritic growth cone contains a non-centrosomal microtubule organizing center (MTOC), which generates minus-end-out microtubules along outgrowing dendrites and plus-end-out microtubules in the growth cone. RAB-11-positive endosomes accumulate in this region and co-migrate with the microtubule nucleation complex γ-TuRC. The MTOC tracks the extending growth cone by kinesin-1/UNC-116-mediated endosome movements on distal plus-end-out microtubules and dynein clusters this advancing MTOC. Critically, perturbation of the function or localization of the MTOC causes reversed microtubule polarity in dendrites. These findings unveil the endosome-localized dendritic MTOC as a critical organelle for establishing axon-dendrite polarity.

Poly(3,4-ethylenedioxythiophene) (PEDOT) has aroused great interest in organic electrics because of its high electrical conductivity and mechanical flexibility. To improve the charge transport, it can act as an ionic liquid (IL) additive due to its ion characteristics and high electrical conductivity. Herein, we investigated the hole-transport performance of PEDOT treated by ILs featuring specific ion ratios (4 : 1, 3 : 1, 2 : 1, 1 : 1, 1 : 2, 1 : 3, and 1 : 4) of the cation and anion through classical dynamics simulations and quantum mechanics computations. The hole mobility of the amorphous PEDOT, constituting nine EDOT monomers, could be improved to 16.81, 18.03, and 10.14 cm2 V−1 s−1 when synergistically regulating the ion ratio to 2 : 1, 3 : 1, and 4 : 1. Consequently, these ratios potentially achieved nearly a 100-fold improvement in the electrical conductivity with respect to the pristine system. The improvements mainly stemmed from the fact that decreasing the amount of anions in ILs and prolonging the chain length of PEDOT yielded an ordered face-to-face π–π stacking. The electronic coupling and charge excitation further confirmed that the anions play an active role in tunneling the hole transport in ILs/heterogeneous PEDOT, and the highest occupied molecular orbital (HOMO) energy level of PEDOT was up-shifted significantly after treatment by the ratios of 2 : 1, 3 : 1, and 4 : 1, which favored the electron-donating ability and was in line with the extraordinary enhancement of the hole mobility. Our results imply that regulating the ion ratio in ILs is a novel strategy for modulating the electronic properties and π-stacked morphology of PEDOT.

A series of CdCl2 complexes (1a-1f and 2a-2c) with 4'-(substituted-phenyl)-2,2':6',2″-terpyridine compounds bearing hydrogen (L1a), p-methyl (L1b), p-phenyl (L1c), p-tolyl (L1d), p-carboxyl (L1e), p-fluoro (L1f), p-hydroxyl (L2a), m-hydroxyl (L2b) or o-hydroxyl (L2c), were prepared and characterized by 1H NMR, IR, elemental analysis and single crystal X-ray diffraction. All the compounds display interesting photoluminescent properties and different maximal emission peaks due to the difference of the substituent groups. The in vitro antiproliferative activities against four human carcinoma cell lines, A549, Bel-7402, Eca-109 and MCF-7, were investigated and cell viability studies indicate that the compounds have excellent results with the lowest IC50 values of 0.372 (1c), 1.003 (1c), 1.161 (1b) and 0.231 (1c) μM, respectively. The DNA interaction was studied by fluorescence titration, circular dichroism spectroscopy and molecular modeling methods. Spectrophotometric results reveal that the compounds have strong affinity binding with DNA as intercalators and molecular docking studies indicate that the binding is contributed by the π…π stacking and hydrogen bonds.

Excessive ammonia-nitrogen (N) in aquifers has caused groundwater pollution on the Dongting Plain (DTP), which seriously threatens the safety of drinking water. It is urgent and necessary to determine the sources and enrichment mechanisms of ammonia-N in groundwater. Carrying out water and soil collaborative research on a three-dimensional scale can more comprehensively analyze the sources of N, including natural and anthropogenic sources. In this study, surface and groundwater quality characteristics were examined from a total of 77 sites on the DTP. Two subsequent boreholes were drilled in the high ammonia concentration area and normal groundwater area, respectively, to compare the effects of anthropogenic activities. Indicators from hydrogeochemical and pedogeochemical analyses, as well as various isotopes, including δ15N-NH4+, δ15N-TON, δ15N-NO3−, δ18O-NO3−, δ18O-H2O, δD-H2O, and δ13C-TOC were used to identify ammonium sources and transformation mechanisms in the strata. We found that the sediments were contaminated by manure and sewage in the aquifers, and part of the shallow groundwater was additionally contaminated by nitrogen fertilizers. Excessive ammonium-N was also detected in the deep aquitards and sediments, which were mainly dominated by mineralization. Ammonia oxidation (with weak hydroxylamine oxidation) is an important biogeochemical process in which ammonia and nitrate do not accumulate in oxidizing groundwater environments. However, heterotrophic nitrification (HN) and anaerobic ammonium oxidation (ANAMMOX) are the release mechanisms for excessive ammonium-N under reducing conditions. In addition, organic matter (OM) on the DTP had a wide range of biogeochemical proxies generated by phytoplankton within a lake, and the comparatively resilient terrestrial organic residues washed in from the surrounding terrestrial area. This study breaks through the conventional mechanisms for the release of excessive ammonium from sediments to aquifers, which provides new ideas for research on ammonium in sediments and ammonia in groundwater.

Based on total organic carbon (TOC) testing, X-ray diffraction (XRD) analysis, and low-pressure N2 adsorption experiments, vertical change and controlling factors of pore structure and gas content of Wufeng - Longmaxi over mature shales were investigated. The results show that within the most favorable pay zones of shale gas, surface area and pore volume reveal an upward decreasing trend with maximum value occurred in Wufeng and the bottom of Longmaxi Formations. Vertically constant pore size distribution (PSD) and fractal dimensions indicating the dominant pore type remains the same in the studied samples. Increasing of pore volume with depth is mainly caused by volume change of mesopore, especially that with size >4 nm. Surface area, however shows a good correlation with micropore area and is a function of micropore quantity. Pore structure variation of over mature shales is primarily controlled by TOC content and influence of minerals on pore structure is limited. For shales with similar preservation condition and thermal evolution, gas content is a function of reservoir storage capacity (surface area and pore volume) and gas generation. Organic matter acted both as the source of shale gas and as a storage medium and is the major control of gas content.

The aim of this study was to investigate the in vivo degradation mechanism and the mechanical properties of poly(lactide-co-glycolide)/beta-tricalcium phosphate (PLGA/β-TCP) composite anchors. Anchors composed of PLGA and β-TCP were implanted in the dorsal subcutaneous tissue of beagle dogs for 6, 12, 16, and 26 weeks. The degradation of the materials was evaluated by measuring the changes in thermal behavior, crystallinity, and mechanical properties. Scanning electron microscope (SEM) was used to observe the surface and longitudinal section of the material. The evaluation of mechanical strength retention and degradation properties suggest that the addition of β-TCP particles efficiently enhances their mechanical properties and thermal characteristics and delays their degradation rate. By analyzing the results of SEM, X-ray diffraction, and differential scanning calorimetry, we can infer that after 12 weeks, the connection between β-TCP and PLGA becomes less compact, which accelerates the decline of mechanical strength.

Quality of interfaces is a key factor determining photoexcited charge transfer efficiency, and in turn photocatalytic performance of heterostructure photocatalysts. In this paper, we demonstrated CdS-MoS2/RGO-E (RGO-E: reduced graphene oxide modified by ethylenediamine) nanohybrid synthesized by using a facile one-pot solvethermal method in ethylenediamine, with CdS nanoparticles and MoS2 nanosheets intimately growing on the surface of RGO. This unique high quality heterostructure facilitates charge separation and transportation, and thus effectively suppressing charge recombination. As a result, the CdS-MoS2/RGO-E exhibits a state-of-the-art H2 evolution rate of 36.7 mmol g−1 h−1 and an apparent quantum yield of 30.5% at 420 nm, which is the advanced performance among all the same-type photocatalysts (see Table S1), and far exceeding that of bare CdS by higher than 104 times. This synthesis strategy gives an inspiration for the synthesis of other compound catalysts, and higher performance photocatalyst may be obtained.

With an intrinsically disordered atomic structure and a widely tunable atomic constituent, metallic glasses (MGs) have been extensively studied as promising catalysts in different catalytic fields. Particularly, Fe-based MGs with high catalytic activity, relatively low material cost, and environmental friendly compatibility also emerge as advanced catalysts. This review systematically discusses the recent advances of Fe-based MGs in catalytic applications, including wastewater remediation based on reductive degradation by multicomponent Fe-based MGs, oxidative degradation by introduction of advanced oxidation processes (AOPs) and nanocrystallization applied in Fe-based MGs up to date, and renewable energy conversion, with purposes of revealing Fe-based MG catalysts in the further improvement of catalytic performance and exploiting their promising catalytic abilities in a widely catalytic field.

The impacts of long-term pumping on groundwater chemistry remain unclear in the Manas River Basin, Northwest China. In this study, major ions within five surface water and 105 groundwater samples were analyzed to identify hydrogeochemical processes affecting groundwater composition and evolution along the regional-scale groundwater flow paths using the multivariate techniques of hierarchical cluster analysis (HCA) and principal components analysis (PCA) and traditional graphical methods for analyzing groundwater geochemistry. HCA classified the groundwater samples into four clusters (C1 to C4). PCA reduced the dimensionality of geochemical data into three PCs, which explained 86% of the total variance. The results of HCA and PCA were used to identify three zones: "recharge," "transition," and "discharge." In the recharge zone the groundwater type is Ca-HCO3 -SO4 and is primarily impacted by the dissolution of calcite and silicate weathering. In the transition zone the groundwater type is Ca-HCO3 -SO4 -Cl and is impacted by rock dissolution and reverse ion exchange. In the discharge zone the groundwater type is Na-Cl and is impacted by evaporation and reverse ion exchange. In addition, anthropogenic activities impact the groundwater chemistry in the study area. The groundwater type generally changes from Ca-HCO3 -SO4 in the recharge area to Na-Cl in the discharge area along the regional-scale groundwater flow paths. This study provides a process-based knowledge for understanding the interaction of groundwater flow patterns and geochemical evolution within the Manas River Basin.