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Invasion and metastasis of breast cancer cells is an important cause of death in breast cancer patients. In the tumor microenvironment, M2 polarization of macrophages can promote the invasion and metastasis of tumor cells. OVOL2 is an evolutionarily conserved transcription regulator, but its effect in macrophages has not been described previously. The aim of this study was to investigate the effects of OVOL2 on macrophage polarity and the role of these effects in the tumor metastasis. We found that overexpression of OVOL2 in macrophages significantly inhibited M2 polarization and thus inhibits breast cancer metastasis. We propose a novel mechanism in which OVOL2 inhibits M2 polarization of macrophages and thus reduces their ability to induce invasion and metastasis of breast cancer. By shedding new light on the regulation of metastasis in cancers, our study provides a new strategy for the targeted therapy of cancer.

High efficiency and stability have long been the key issues faced by perovskite solar cells (PSCs). It is found that the CsPbIBr2 all-inorganic perovskite has a suitable band gap and satisfactory stability, so it has attracted much attention. However, the many defects in the CsPbIBr2 film are one of the main problems hindering the improvement of power conversion efficiency (PCE) of the CsPbIBr2 PSCs. The substitution of trace impurities is undoubtedly a simple, cost-effective and efficient strategy. In this work, an appropriate amount of Cd2+ (1.0% mol of Pb2+) is added into the CsPbIBr2 precursor solution to fabricate high quality CsPbIBr2 film with improved crystallinity, reduced trap density, suppressed photo-generated carrier recombination, displayed n-type doping and optimized energy level alignment. The corresponding carbon-based all-inorganic Cd2+-doped CsPbIBr2 PSCs achieve a maximum PCE of 10.63% with a high open circuit voltage (VOC) of 1.324 V, which are much higher than those of the control one with a PCE of 8.48% and an VOC of 1.235 V. The unencapsulated device can still retain more than 92% of the initial PCE when stored at ambient atmosphere (25 °C, relative humidity about 30%) for 40 days.

In this study, the groundwater (GW) in the high-fluorine area of the Southwestern Shandong Plain was divided according to the characteristics of high Na% (> 75%), and its water chemistry characteristics and causes were discussed separately, and the hydrochemical process of the formation of high-fluorine GW was determined. Finally, the GW quality of the study area was evaluated. The results proved that silicate hydrolysis can significantly promote the release of F− in fluorine-containing minerals; high %Na can be used as one of the early-warning conditions for judging high-fluoride areas. To this end, 132 GW samples were collected from 66 wells during the dry and wet seasons. The study area was found to have weakly alkaline GW (pH 7.1–8.9) and could be divided into high %Na areas (HNA) and non-HNA. GW exhibited different hydrochemical characteristics between HNA and non-HNA. In non-HNA, total hardness (TH) exceeded 200 mg/L, and total dissolved solids (TDS) ranged from 514.1 to 5246.1 mg/L; in HNA, TH was less than 200 mg/L, TDS ranged from 552.8 to 1298.3 mg/L, and Na+ increased with TDS, whereas Ca2+ and Mg2+ contents were low. The main water type in HNA was HCO3-Na and in non-HNA was SO4·Cl-Ca·Mg and SO4·Cl-Na. The study area is experiencing serious fluoride pollution. GW in HNA is mostly controlled by carbonate and silicate hydrolysis and evaporation, whereas GW in non-HNA is controlled by dolomite dissolution and cation exchange in the main. Moreover, GW in HNA has significantly been altered by albite hydrolysis, which produces Na+ and HCO3− and triggers various reactions promoting the release of F− from fluorine-containing minerals (FCM). Regarding the water quality for irrigation, GW in HNA was found to be less suitable than that in non-HNA. Nevertheless, in terms of the water quality index (WQI), GW is moderate for drinking and poor for irrigation. Therefore, extensive attention should be paid to the exploitation and management of high-sodium GW in the plain area.

Background. Manual acupuncture (MA) with different stimulus frequencies may give rise to varying acupuncture effects. However, the intensity-effect relationship and the underlying mechanisms of MA remain unclear. Objective. To compare the analgesic effects of different frequencies of twirling-rotating MA on rats with complete Freund’s adjuvant- (CFA-) induced pain and explore the underlying mechanism via peripheral sensory nerves. Methods. First, 36 healthy male Wistar rats were randomly divided into 6 groups: control group, 2 r/s MA group (twirling-rotating MA with the frequency of 2 revolutions per second), 4 r/s MA group (twirling-rotating MA with the frequency of 4 revolutions per second), CFA group, CFA + 2 r/s MA group, and CFA + 4 r/s MA group. Rats in three CFA groups received an intraplantar injection of CFA to establish a pain model, while the rats in other three groups received an intraplantar injection of saline. Rats in the 2 r/s MA group and 4 r/s MA group were treated with the corresponding frequencies of twirling-rotating MA on bilateral Zusanli (ST36) and Kunlun (BL60) for 7 days. The ipsilateral nociceptive thresholds (paw withdrawal latency; PWL) were tested to evaluate the analgesic effects. Second, 9 healthy male Wistar rats were randomly divided into 3 groups: control group, 2 r/s MA group, and 4 r/s MA group. The proportion of C-fiber neurons (calcitonin gene-related peptide- (CGRP-) positive neurons) and A-fiber neurons (neurofilament 200- (NF200-) positive neurons) in the dorsal root ganglia (DRG) activated by MA were quantitatively analyzed with the morphological immunofluorescence staining method. Third, 30 healthy male Wistar rats were randomly divided into 6 groups: control group, CFA group, CFA + 2 r/s MA group, CFA + 2 r/s MA + RTX group, CFA + 4 r/s MA group, and CFA + 4 r/s MA + RTX group. Resiniferatoxin (RTX) was injected into the acupoints before acupuncture. PWL was evaluated to investigate the analgesic effect. Results. Both types of MA treatment increased the PWL of saline-injecting rats and pain model rats. Moreover, 4 r/s MA was superior to 2 r/s MA in increasing PWL. A higher quantity of excited C-fiber neurons was observed following 4 r/s MA than 2 r/s MA, while the reverse was observed in the activation of A-fiber neurons. Following the injection of RTX to inhibit the activation of C-fibers, the analgesic effect of 4 r/s MA reduced significantly but not of 2 r/s MA. Conclusion. Strong MA (4 r/s MA) has superior analgesic effects to gentle MA (2 r/s MA) on CFA model rats, which is associated with C-fiber activation.

A novel arabitol dehydrogenase (ArDH) gene was cloned from a bacterium named Aspergillus nidulans and expressed heterologously in Escherichia coli. The purified ArDH exhibited the maximal activity in pH 9.5 Tris-HCl buffer at 40 °C, showed Km and Vmax of 1.2 mg/mL and 9.1 U/mg, respectively. The ArDH was used to produce the L-xylulose and coupled with the NADH oxidase (Nox) for the regeneration of NAD+. In further optimization, a high conversion of 84.6% in 8 hours was achieved under the optimal conditions: 20 mM of xylitol, 100 µM NAD+ in pH 9.0 Tris-HCl buffer at 30 °C. The results indicated the coupling system with cofactor regeneration provides a promising approach for L-xylulose production from xylitol.

After angiogenesis-activated embryonic and early postnatal vascularization, endothelial cells (ECs) in most tissues enter a quiescent state necessary for proper tissue perfusion and EC functions. Notch signaling is essential for maintaining EC quiescence, but the mechanisms of action remain elusive. Here, we show that microRNA-218 (miR-218) is a downstream effector of Notch in quiescent ECs. Notch activation upregulated, while Notch blockade downregulated, miR-218 and its host gene Slit2, likely via transactivation of the Slit2 promoter. Overexpressing miR-218 in human umbilical vein ECs (HUVECs) significantly repressed cell proliferation and sprouting in vitro. Transcriptomics showed that miR-218 overexpression attenuated the MYC proto-oncogene, bHLH transcription factor (MYC, also known as c-myc) signature. MYC overexpression rescued miR-218-mediated proliferation and sprouting defects in HUVECs. MYC was repressed by miR-218 via multiple mechanisms, including reduction of MYC mRNA, repression of MYC translation by targeting heterogeneous nuclear ribonucleoprotein A1 (hnRNPA1), and promoting MYC degradation by targeting EYA3. Inhibition of miR-218 partially reversed Notch-induced repression of HUVEC proliferation and sprouting. In vivo, intravitreal injection of miR-218 reduced retinal EC proliferation accompanied by MYC repression, attenuated pathological choroidal neovascularization, and rescued retinal EC hyper-sprouting induced by Notch blockade. In summary, miR-218 mediates the effect of Notch activation of EC quiescence via MYC and is a potential treatment for angiogenesis-related diseases., Graphical abstract, Endothelial cell (EC) quiescence is important for vessel homeostasis and function, but the mechanism remains elusive. Han and colleagues report that miR-218 mediates the effect of Notch activation on promoting EC quiescence via repressing MYC, which holds potential in the treatment of angiogenesis-related diseases.

In this work, we demonstrate that the strength of anion specificities of thermosensitive polymers is determined by the affinity of direct anion binding to the polymers. We have prepared a series of thermosensitive statistical copolymers with distinct thermoresponsive behaviors. The anions can specifically interact with the different types of thermosensitive polymers in very different strengths. A similar strength of specific anion effects on thermoresponsive behaviors can be observed at very different salt concentrations for the different types of thermosensitive polymers. A stronger anion binding to the thermosensitive polymers gives rise to a more obvious anion specificity and vice versa. The work presented here opens up opportunities for the application of ion binding affinity to modulate the strength of ion specificities of thermosensitive polymers.

Modifying Pt surfaces by foreign metals with a higher oxophilicity is a promising approach to improve the kinetics of hydrogen evolution and oxidation reactions. The role of foreign metals, however, is not fully understood. Here we study Ru-modified Pt as a model system to understand the underlying mechanisms in activity improvement through combining in situ infrared spectroscopy and theoretical calculations. In an alkaline solution, the hydrogen evolution and oxidation reaction activity of Ru-modified Pt is proportional to the Ru coverage due to the strain and electronic effects of the Pt substrate, which lower the energy barrier of the rate-determining Volmer step; these are the governing reasons for the improved catalytic activities. This work not only deepens our understanding of hydrogen electrocatalysis mechanisms, but also provides guidelines for the rational design of advanced electrocatalysts. Modifying Pt surfaces with highly oxophilic metals can increase the hydrogen evolution and oxidation performance in alkaline media, but the underlying mechanism remains elusive. Now, it is demonstrated that the activity improvement of Ru-modified Pt mainly originates from the strain and electronic effects rather than an alternative bifunctional mechanism.

In this study, the manganese cobalt composite (Mn-Co)-loaded SiO2, MgO, TiO2, γ-Al2O3 and silicalite-1 were prepared by ultrasonic complexation method. The catalysts were characterized by XRD, BET, SEM, TEM, H2-TPR and XPS, and the activity of catalytic oxidation of toluene was evaluated. It was found that Mn-Co loaded γ-Al2O3 (Mn2CoOx/γ-Al2O3) exhibited excellent catalytic activity. When the gas hour space velocity (GHSV) was 45,000 h-1, the removal rate of toluene reached 91.2% within 5.5 h, and the selectivity of CO2 was 71.10% at ambient temperature. The operation of Mn2CoOx/γ-Al2O3 at different temperatures was investigated, and the better toluene removal efficiency more than 80% after reacting 9h was obtained at 50 °C. The characterization results showed that better catalytic activity is related to smaller grain size, higher Mn3+/Mn4+ values and the relative content of active oxygen species (OII + OIII). Increased amounts of low state species easily led to the imbalance of the catalyst surface charge and promoted the formation of more oxygen vacancies.

The 7:3LaCoO3/Bi2WO6 composite synthesized in this experiment had a significant effect on the degradation of TC in the solution under visible light (85.5% at 150min). The experimental results proved that the composite material not only had a high removal rate of TC in the water, but also could be recycled and met the requirements of environmental protection. XRD, SEM, FT-IR, XPS and other analysis showed that in the 7:3LaCoO3/Bi2WO6 composite, the two monomers LaCoO3 and Bi2WO6 were well combined together. The two active groups h+ and •O2- played an important role in the photocatalytic degradation process of the composite material. The electrons of the composite material moved from the conduction band of Bi2WO6 to the valence band of LaCoO3, which further enhanced the photocatalytic activity of the composite material. This research provided a new type of photocatalytic material for treating TC in water, also provided a certain theoretical support for the composite of lanthanide-based photocatalytic materials and bismuth-based photocatalytic materials.

The organochlorine insecticide dichlorodiphenyltrichloroethane (DDT) and heavy metal cadmium (Cd) are widespread environmental pollutants. They are persistent in the environment and can accumulate in organisms. Although the individual toxicity of DDT and Cd has been well documented, their combined toxicity is still not clear. Since liver is their common target, in this study, the individual and combined toxicity of DDT and Cd in human liver carcinoma HepG2 and human normal liver THLE-3 cell lines were investigated. The results showed that DDT and Cd inhibited the viability of HepG2 and THLE-3 cells dose-dependently and altered lysosomal morphology and function. Intracellular reactive oxygen species and lipid peroxidation levels were induced by DDT and Cd treatment. The combined cytotoxicity of DDT and Cd was greater than their individual cytotoxicity, and the interaction between Cd and DDT was additive on the inhibition of cell viability and lysosomal function of HepG2 cells. The interaction was antagonistic on the inhibition of cell viability of THLE-3 cells. These results may facilitate the evaluation of the cumulative risk of pesticides and heavy metal residues in the environment.

Background/aim Peroxiredoxin V (Prx V) plays crucial roles in cellular apoptosis and proliferation in various cancer cells by regulating the cellular reactive oxygen species (ROS) levels. Materials and methods Here, we examined the possible regulatory effects of Prx V on doxorubicin (DOX)-induced cellular apoptosis and its mechanisms in the human gastric adenocarcinoma cell line (AGS cells). Results Our findings suggest that Prx V knockdown may significantly increase the DOX-induced apoptosis by aggravating intracellular ROS accumulation. We also found that DOX-induced mitochondrial ROS levels and membrane permeability were significantly higher in short hairpin Prx V cells than in mock cells, and these phenomena were dramatically reversed by ROS scavenger treatment. Prx V knockdown also significantly upregulated the cleaved caspase 9, 3, and B-cell lymphoma 2 (Bcl2)-associated agonist of cell death/Bcl2 protein expression levels, suggesting that Prx V knockdown activates mitochondria-dependent apoptotic signaling pathways. Conclusion Taken together, this study suggests that Prx V may be a strong molecular target for gastric cancer (GC) chemotherapy, and further elucidates the role of Prx V in oxidative stress-induced cell apoptosis.

The aromatic C–H bond etherification with alcohols is one of the most atom-efficient ways to construct aryl ethers. However, it often requires a large excess of alcohols as etherification reagents,...

The outbreak of coronavirus disease 2019 (COVID-19) caused by SARS CoV-2 is ongoing and a serious threat to global public health. It is essential to detect the disease quickly and immediately to isolate the infected individuals. Nevertheless, the current widely used PCR and immunoassay-based methods suffer from false negative results and delays in diagnosis. Herein, a high-throughput serum peptidome profiling method based on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is developed for efficient detection of COVID-19. We analyzed the serum samples from 146 COVID-19 patients and 152 control cases (including 73 non-COVID-19 patients with similar clinical symptoms, 33 tuberculosis patients, and 46 healthy individuals). After MS data processing and feature selection, eight machine learning methods were used to build classification models. A logistic regression machine learning model with 25 feature peaks achieved the highest accuracy (99%), with sensitivity of 98% and specificity of 100%, for the detection of COVID-19. This result demonstrated a great potential of the method for screening, routine surveillance, and diagnosis of COVID-19 in large populations, which is an important part of the pandemic control.

Removal of trace SO2 from an SO2-containing product is now receiving increasing attention. However, designing a robust porous adsorbent with high SO2 adsorption capacity and good SO2/CO2 selectivity, as well as validity under humid conditions, is still a challenging task. Herein, we report a porous cage-based metal-organic framework, namely ECUT-111, which contains two distinct cages with apertures of 5.4 and 10.2 angstrom, respectively, and shows high a BET of up to 1493 m2/g and a pore volume of 0.629 cm3/g. Impressively, ECUT-111 enables an ultrahigh SO2 uptake of up to 11.56 mmol/g, exceeding most reported top-performing adsorbents for such a use. More importantly, complete separation of trace SO2 from SO2/CO2 and SO2/CO2/N2 mixtures, especially under humid conditions, and excellent recycle use were observed for ECUT-111, suggesting its superior application in desulfurization of SO2-containing products.

Dexmedetomidine (Dex), a highly selective α2-adrenergic receptor (α2AR) agonist, has an anti-inflammatory property and can alleviate pulmonary edema in lipopolysaccharide (LPS)-induced acute lung injury (ALI), but the mechanism is still unclear. In this study, we attempted to investigate the effect of Dex on alveolar epithelial sodium channel (ENaC) in the modulation of alveolar fluid clearance (AFC) and the underlying mechanism. Lipopolysaccharide (LPS) was used to induce acute lung injury (ALI) in rats and alveolar epithelial cell injury in A549 cells. In vivo, Dex markedly reduced pulmonary edema induced by LPS through promoting AFC, prevented LPS-induced downregulation of α-, β-, and γ-ENaC expression, attenuated inflammatory cell infiltration in lung tissue, reduced the concentrations of TNF-α, IL-1β, and IL-6, and increased concentrations of IL-10 in bronchoalveolar lavage fluid (BALF). In A549 cells stimulated with LPS, Dex attenuated LPS-mediated cell injury and the downregulation of α-, β-, and γ-ENaC expression. However, all of these effects were blocked by the PI3K inhibitor LY294002, suggesting that the protective role of Dex is PI3K-dependent. Additionally, Dex increased the expression of phosphorylated Akt and reduced the expression of Nedd4-2, while LY294002 reversed the effect of Dex in vivo and in vitro. Furthermore, insulin-like growth factor (IGF)-1, a PI3K agonists, promoted the expression of phosphorylated Akt and reduced the expression of Nedd4-2 in LPS-stimulated A549 cells, indicating that Dex worked through PI3K, and Akt and Nedd4-2 are downstream of PI3K. In conclusion, Dex alleviates pulmonary edema by suppressing inflammatory response in LPS-induced ALI, and the mechanism is partly related to the upregulation of ENaC expression via the PI3K/Akt/Nedd4-2 signaling pathway.

Carboxylic acids, including amino acids (AAs), have been widely used as reagents for decarboxylative couplings. In contrast to previous decarboxylative couplings that release CO2 as a waste byproduct, herein we report a novel strategy with simultaneous utilization of both the alkyl and carboxyl components from carboxylic acids. Under this unique strategy, carboxylic acids act as bifunctional reagents in the redox-neutral carbocarboxylation of alkenes. Diverse, inexpensive, and readily available α-AAs take part in such difunctionalizations of activated alkenes via visible-light photoredox catalysis, affording a variety of valuable but otherwise difficult to access γ-aminobutyric acid derivatives (GABAs). Additionally, a series of dipeptides and tripeptides also participate in this photocatalytic carbocarboxylation. Although several challenges exist in this system due to the low concentration and quantitative amount of CO2, as well as unproductive side reactions such as hydrodecarboxylation of the carboxylic acids and hydroalkylation of the alkenes, excellent regioselectivity and moderate to high chemoselectivity are achieved. This process features low catalyst loading, mild reaction conditions, high step and atom economy, and good functional group tolerance, and it is readily scalable. The resulting products are subject to efficient derivations, and the overall process is amenable to applications in the late-stage modification of complex compounds. Mechanistic studies indicate that a carbanion is generated catalytically and it acts as the key intermediate to react with CO2, which is also generated catalytically in situ and thus remains in low concentration. The overall transformation represents an efficient and sustainable system for organic synthesis, pharmaceutics, and biochemistry.

A flexible temperature sensor based on poly-(3, 4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) with isopropyl alcohol (IPA) treatment is successfully fabricated by screen printing. The distribution of PEDOT is investigated by the SEM, AFM, and Raman techniques. It can be found that the microstructure is manipulated by the ratio of the PEDOT:PSS to IPA content. Raman spectra demonstrate that the transition between quinoid and benzoid structures of PEDOT are tuned by IPA treatment as well. The temperature dependence of resistance for IPA-treated PEDOT:PSS film is found to be well fitted by non-adiabatic small polaron hopping transport. Moreover, a constant temperature coefficient of resistance (TCR) value can be obtained by the optimized ratio of IPA to PEDOT:PSS. Therefore, this paper suggests that the tuned microstructure of PEDOT:PSS film can be realized by IPA treatment, which plays an important role in the physical properties of the temperature sensor based on PEDOT:PSS.

The oxidase-like activity of high-performance Fe–N–C was enhanced by up to 55% by using a secondary N-containing precursor in pyrolysis. Moreover, the exploration of the O2 activation half-reaction using electrochemical methods was disclosed to be a practically facile approach to quantitatively evaluate the factors associated with the activity.

Constructing of single atom catalysts that can stably exist in various energy conversion and storage devices is still in its infancy. Herein, a geometrically optimized three-dimensional hierarchically architectural single atomic Fe N C catalyst with fast mass transport and electron transfer is rationally developed by post-molecule pyrolysis assisted with silicon template and reconstructs by ammonia treating. The ammonia-assisted secondary pyrolysis not only compensates for the volatilization of nitrogen species contained in organic precursors but also optimizes the surface structure of Fe N C catalyst, thus increasing the content of pyridinic nitrogen and boosting the density of active sites (Fe Nx) in Fe N C samples. In addition, the pyridinic nitrogen adjusts the electronic distribution in Fe 3d active center and promotes the catalytic performances. Therefore, this hollow spherical atomically dispersed Fe N C catalyst delivers outstanding oxygen reduction reaction (ORR) activity in pH-universal electrolyte and surpasses the most reported values.

Here we report a strategy for carbonyl addition with unactivated alkenes using an organic photocatalyst on both aldehyde and ketone substrates. This protocol grants us a good alternative to the traditional Barbier–Grignard allylation that exhibits poor functional group tolerance. With this method the stoichiometric use of metals can be avoided, high atom economy can be achieved and fewer by-products are generated.

The Pd-cataylsed direct ortho-C(sp2)–H fluorination of aromatic ketones has been developed for the first time. The reaction features good regioselectivity and simple operations, constituting an alternative shortcut to access fluorinated ketones. A concise synthesis of anacetrapib has also been achieved by using late-stage C–H fluorination as a key step.

A new and efficient strategy for ring-opening reactions of nitrocyclopropanes is developed for the first time for the divergent synthesis of enynes and enesters via in situ generated highly reactive electron-deficient intermediate allenes. Controllable approaches resulted in enynes and enesters with up to 89% and 90% yields, respectively. The reaction features easy operation, involves green solvents and simple inorganic bases, and is transition-metal free.

An efficient ruthenium-catalyzed method has been developed for the direct N-alkylation of sulfur-containing amines with alcohols, for the first time, by a step-economical and environmentally friendly hydrogen borrowing strategy. The present methodology features base-free conditions and broad substrate scope, with water being the only by-product. Moreover, this protocol has been applied to the synthesis of the pharmaceutical drug Quetiapine.

A mild method to access functionalized 2-iminothiazolines in a facile and efficient manner has been developed. The reaction started from 1,3-disubstituted thioureas and 1-bromo-1-nitroalkenes in the presence of triethylamine in THF and proceeded smoothly in air to afford 2-iminothiazoline derivatives in moderate to good yields.

Bond cleavage bioorthogonal chemistry has been widely employed to restore or activate proteins or prodrugs. Nitric oxide (NO), as a free radical molecule, has joined the clinical arena of cancer therapy, since high levels of NO could produce a cancer cell growth inhibitory effect. However, the spatiotemporal controlled release of NO remains a great challenge, and bioorthogonal chemistry may open a new window. Herein, we described a class of O2-3-isocyanopropyl diazeniumdiolates 3a-f as new bioorthogonal NO precursors, which can be effectively uncaged via tetrazine-mediated bond cleavage reactions to liberate NO and acrolein in living cancer cells, exhibiting potent antiproliferative activity. Furthermore, 3a and tetrazine BTZ were respectively encapsulated into two liposomes. It was found that simultaneous administrations of the two liposomes could specifically release large amounts of NO in the implanted cancer cells in zebrafish, thus generating potent tumor suppression activity in vivo. Our findings indicate that the TZ-labile NO precursors could serve to expand the NO-based smart therapeutics and the scope of bioorthogonal chemistry utility in vivo in the near future.

An efficient Pd-catalysed β-C(sp3)–H arylation of diverse native amides with aryl iodides was developed. This protocol overcomes the necessity of the Thorpe–Ingold effect and features broad substrate scope and good functional group tolerance. The potential application of this protocol is collectively demonstrated by gram-scale synthesis and the synthesis of several bioactive molecules.

Ruminants would suffer from gastric distension (bloat) when feeding on alfalfa (Medicago sativa L.; Alf), while tannins can relieve this problem. Thus, this study aimed to evaluate the effect of Alf mixed with paper mulberry (Broussonetia papyrifera) leaves (PML) or condensed tannins (CT) extracted from PML on in vitro fermentation performance. Seven experimental treatments based on the mass ratios of Alf and PML were set up: Alf, PML, 3A1P (Alf:PML = 3:1), 1A1P (Alf:PML = 1:1), 1A3P (Alf:PML = 1:3), A1P (Alf with 1% CT extracted from PML), A2P (Alf with 2% CT extracted from PML), and a blank. The results after fermentation were as follows. (1) The degradable dry matter (DDM) and degradable organic matter (DOM) contents increased simultaneously with the increase in the proportion of PML (p .05), propionic, and butyric acids compared to Alf alone. Adding CT improved the concentrations of propionic and butyric acids over the Alf treatment (p

Herein, we report a novel strategy to access CH2F-containing ketones through Pd-catalysed β-selective methyl C(sp3)-H fluorination. The reaction features high regioselectivity and a broad substrate scope, constituting a modular method for the late-stage transformation of the native methyl (CH3) into the monofluoromethyl (CH2F) group.

Our previous studies have shown that the δ-opioid receptor (DOR) is an important neuroprotector via the regulation of PTEN-induced kinase 1 (PINK1), a mitochondria-related molecule, under hypoxic and MPP+ insults. Since mitochondrial dysfunctions are observed in both hypoxia and MPP+ insults, this study further investigated whether DOR is cytoprotective against these insults by targeting mitochondria. Through comparing DOR-induced responses to hypoxia versus MPP+-induced parkinsonian insult in PC12 cells, we found that both hypoxia and MPP+ caused a collapse of mitochondrial membrane potential and severe mitochondrial dysfunction. In sharp contrast to its inappreciable effect on mitochondria in hypoxic conditions, DOR activation with UFP-512, a specific agonist, significantly attenuated the MPP+-induced mitochondrial injury. Mechanistically, DOR activation effectively upregulated PINK1 expression and promoted Parkin’s mitochondrial translocation and modification, thus enhancing the PINK1-Parkin mediated mitophagy. Either PINK1 knockdown or DOR knockdown largely interfered with the DOR-mediated mitoprotection in MPP+ conditions. Moreover, there was a major difference between hypoxia versus MPP+ in terms of the regulation of mitophagy with hypoxia-induced mitophagy being independent from DOR-PINK1 signaling. Taken together, our novel data suggest that DOR activation is neuroprotective against parkinsonian injury by specifically promoting mitophagy in a PINK1-dependent pathway and thus attenuating mitochondrial damage.

Biochar has strong potential to improve nitrogen (N) use efficiency in both agricultural and horticultural systems. Biochar is usually co-applied with full rates of fertiliser. However, the extent to which N cycling can be affected after biochar application to meet plant N requirement remains uncertain. This study aimed to explore N cycling up to 2 years after biochar application. We applied pine woodchip biochar at 0, 10 and 30 t ha−1 (B0, B10, B30, respectively) in a macadamia orchard and evaluated the N isotope composition (δ15N) of soil, microbial biomass and macadamia leaves. Soil total N (TN) and inorganic N pools were also measured up to 2 years after biochar application. Biochar did not alter soil TN but soil NO3−-N increased at months 12 and 24 after biochar application. Soil NO3−-N concentrations were always over ideal levels of 15 μg g−1 in B30 throughout the study. Stepwise regression indicated that foliar δ15N decreases after biochar application were explained by increased NO3−-N concentrations in B30. Foliar TN and photosynthesis were not affected by biochar application. The soil in the high rate biochar plots had excess NO3−-N concentrations (over 30 μg g−1) from month 20 onwards. Therefore, N fertiliser applications could be adjusted to prevent excessive N inputs and increase farm profitability.

Remote difunctionalization of unactivated alkenes is challenging but a highly attractive tactic to install two functional groups across long distances. Reported herein is the first remote difunctionalization of alkenes with CO2 . This visible-light photoredox catalysis strategy provides a facile method to synthesize a series of carboxylic acids bearing valuable fluorine- or phosphorus-containing functional groups. Moreover, this versatile protocol shows mild reaction conditions, broad substrate scope, and good functional-group tolerance. Based on DFT calculations, a radical adds to an unactivated alkene to smoothly form a new carbon radical, followed by a 1,5-hydrogen atom-transfer process, the rate-limiting step, generating a more stable benzylic radical. The reduction of the benzylic radicals by an IrII species generates the corresponding benzylic carbanions as the key intermediates, which further undergo nucleophilic attack with CO2 to generate carboxylates.

In order to imitate wood truly in structure and content, a viscose solution was used to prepare a cellulose membrane with the hierarchically porous structure of wood by two-step process of ice-templating and low-temperature phase inversion for a solar steam device. The prepared cellulose membrane with microchannels observed by microscopy, which resembled those of wood, showed excellent wicking and water flux characteristics. The physical properties of cellulose membranes, including mechanical and thermal stability, allow their application in many fields. In evaluating of solar steam performance, the water evaporation rate of 1.56 kg m−2 h−1 from a graphene-coated cellulose membrane at the light density of 1 kW m−2 exceeded that of a cellulose membrane with pure water. The water evaporation rate of the cellulose membrane was higher than that of a wood-derived solar steam device. The conversion efficiency was increased from 40.72 to 95.57% with modification of the prepared cellulose membrane using graphene. The collected data showed that the cellulose membrane with a hierarchically porous structure was a promising alternative to wood-based solar steam devices, which have the limitations in the reproducibility of structure and composition.

The functionalization of indoles in the carbocyclic ring has been achieved via organocatalytic enantioselective Friedel–Crafts benzhydrylation of hydroxyindoles with in situ generated ortho-quinome...

High-order assembly plays a significant role in the formation of living organisms containing a large number of biomacromolecules and, thus, enlightens the construction of nanomaterials that can load macromolecular payloads at a high efficiency. Herein, by choosing anionic hyaluronic acid (HA) as a model payload, we demonstrated how the electrostatic-interaction-induced high-order assembly can be used to load efficiently biomacromolecules into complex coacervate nanodroplets. The resultant assemblies were primarily composed of HA and cationic chitosan oligosaccharide/dextran (COS/Dex) nanogels and had a controllable structure while also exhibiting biological functionality. HA in the assemblies is capable of targeting CD44-overexpressed tumor cells through CD44-mediated endocytic pathways, which are elucidated herein. Therefore, this study provides a reliable approach for the efficient loading of macromolecular payloads into complex coacervate nanodroplets via electrostatic-attraction-induced high-order assembly.

Here we demonstrate a general method of mediating the deposition of metal nanostructures on carbon substrates via reductive adsorbates. The adsorbates, quinone molecules, can achieve a well-defined...

Currently, a variety of elastomers with a self-healing capacity and reprocessability have been developed by dynamic chemistry to extend the service life, increase the reliability of polymeric mater...

Carbon micro/nanostructures have advantages in science, technology and application. This work introduced a simple process for producing carbon microfibers, CMF. Experimentally, the alkali lignin wa...

Renal cell carcinoma has the highest incidence rate of cancer types in the urinary system. Moreover, microRNAs (miRNA) have been closely associated with numerous types of tumor. The present study aimed to investigate the effects of miRNA (miR)-133b on the proliferation, invasion and chemosensitivity of renal cell carcinoma cells, and to determine whether its mechanism was regulated by the ERK signaling pathway. Both renal cell carcinoma and adjacent healthy tissues from 60 patients, in addition to renal cell carcinoma lines, ACHN, Caki-1, A-498 and 786-O, and 293 cells, were used in this study. miR-133b expression was measured from renal cell carcinoma, adjacent healthy tissues and renal cell carcinoma cell lines by reverse transcription-quantitative PCR. Cells were transfected with miR-133b mimic to achieve miR-133b overexpression. The proliferative, migratory and invasive ability of the cells were evaluated using MTT, wound healing and Matrigel assays, respectively, and flow cytometry was used to detect the apoptotic rate. Following treatment with an ERK inhibitor, U0126, and activator, LM22B-10, western blotting was used to detect the expression of related proteins and the activity of the ERK signaling pathway. The overexpression of miR-133b significantly inhibited cell proliferation, migration and invasion, whilst inducing apoptosis and increasing the drug sensitivity of renal cell carcinoma cells to cisplatin, docetaxel and doxorubicin. The miR-133b mimic also increased the protein expression levels of Bax and decreased the expression levels of matrix metalloproteinase (MMP)-2, MMP-9, ATP-binding cassette subfamily G2, P-glycoprotein, Bcl-2 and proliferating cell nuclear antigen, as well as the phosphorylation of ERK (P0.05). However, the overexpression of miR-133b combined with LM22B-10 treatment weakened the anticancer effects of miR-133b mimic transfection (P

Fe(OH)3 and Fe2O3 were first prepared by a precipitation method and then sulfated to obtain the SO2−4 -functionalized SO2−4/Fe(OH)3 and SO2−4/Fe2O3 catalysts for the selective catalytic reduction of NOx with NH3 (NH3-SCR); the promoting effect of SO2−4 functionalization on the performance of Fe2O3 catalyst in NH3-SCR was then investigated. The results indicate that the SCR activity of the SO2−4 -functionalized Fe2O3 catalysts is significantly improved in comparison with that of unmodified Fe2O3. In particular, the SO2−4/Fe(OH)3 catalyst exhibits excellent performance in NH3-SCR, with the NOx conversion of over 80% at 250–450°C; besides, it also display high catalytic stability and resistance towards H2O + SO2. A series of characterization results including XRD, Raman spectroscopy, TG analysis, FTIR spectroscopy, H2-TPR, NH3-TPD and in situ DRIFTS reveal that the functionalization with sulfuric acid can inhibit the growth of Fe2O3 grains; moreover, SO2−4 combines with Fe3+ to form the sulfate complex, leading to an increase in the number of surface acid sites and the acid strength, which can inhibit the ammonia over-oxidation on Fe2O3 and enhance the deNOx performance of Fe2O3.

Respiratory syncytial virus (RSV), a member of Paramyxoviridae family is responsible for bronchiolitis and pneumonia. The present study investigated anti-viral and anti-inflammatory activities of jatrophone against RSV-infection in pulmonary epithelial cells in vitro and in mice model in vivo. The changes in viabilities of RSV infected cells by jatrophone treatment were determined by MTT assay. The fluorescence associated with production of ROS was evaluated by fluorescence microscopy using H2DCFDA dye. The IFN-γ secreting cells were detected in mice BALF by stimulation with phorbol myristate acetate and ionomycin. The reduction of BEAS-2B cell viability by RSV was alleviated on treatment with jatrophone in dose based manner. The cytopathogenic changes by RSV infection were prevented and viral growth inhibited by jatrophone in BEAS-2B cells. Jatrophone treatment significantly alleviated RSV mediated overproduction of IL-6/-8 and suppressed ROS generation in the cells. The pulmonary viral titers were found to be markedly lower in mice treated with jatrophone relative to untreated group. The jatrophone treated mice also showed reduced IL-4/-5/-13 levels and elevated IFN-γ level in BALF relative to untreated RSV infected mice. Flow cytometry revealed elevated count of IFN-γ generating cells in RSV infected mice on treatment with jatrophone. Thus jatrophone inhibits viral growth and oxidative damage by RSV in pulmonary epithelial cells. In RSV infected mice jatrophone increased immunity for viral infection by modulating cell phenotype for promotion of anti-viral IFN-γ. Thus jatrophone acts as potential anti-viral compound and may be developed for treatment of respiratory treat infection.

In some cases, we hope to remove the electrospun nanofibrous mesh from the collector easily. But in some cases such as wound dressing, we observe that the in situ electrospun nanofibers can stick to the collector (e.g., skin). Therefore, the adhesion between the in situ electrospun web and the substrate becomes important in the performance and practical application of the electrospun material. In this paper, we reported a direct pulling method to measure the adhesion and understand the adhesion mechanism. In this method, we used gravity to pull the fiber directly from the substrate and then measured the gravity to calculate the adhesion. This new test method is more convenient and practical than the previously reported methods. In addition, the adhesion of the in situ electrospun web on different substrates (e.g., aluminium foil, wood pulp paper, and silicon paper) was also studied by this method. The adhesion was influenced by spinning voltage, electrical conductivity, and surface roughness of the substrates.

We aimed to evaluate the functions of long non-coding RNA taurine upregulated gene 1 (lncRNA TUG1) in renal ischemia-reperfusion (I/R) injury and identify the potential mechanisms. Pathological changes of renal tissues were examined using H&E staining after mimic renal I/R injury in vivo. The contents of serum renal functional parameters and inflammatory factors were measured. The expression of TUG1 and miR-449b-5p in renal tissues and HK-2 cells stimulated by I/R were detected. Then, the effects of TUG1 silencing on inflammation and apoptosis of cells were evaluated. Dual luciferase reporter assays were executed for determining the correlation between miR-449b-5p and TUG1, high mobility group box 1 (HMGB1), or matrix metalloproteinase 2 (MMP2). Subsequently, cells were co-transfected with miR-449b-5p mimic and pcDNA3.1 TUG1. The levels of inflammation, apoptosis, and the expression of HMGB1 and MMP2 were detected. The results revealed that renal tissues were obviously damaged after I/R accompanied by changes in renal functional markers and inflammatory factors. TUG1 was highly expressed whereas miR-449b-5p was lowly expressed. TUG1 silencing reduced the inflammation and apoptosis. Dual luciferase reporter assays confirmed that miR-449b-5p was a target of TUG1 as well as HMGB1 and MMP2 were direct targets of miR-449b-5p. Meanwhile, miR-449b-5p mimic presented the same results with TUG1 silencing, which were reversed after TUG1 overexpression. Moreover, MMP2 and HMGB1 expression was decreased after miR-449b-5p overexpression while that of was increased after TUG1 overexpression. These findings demonstrated that TUG1 silencing attenuates I/R-induced inflammation and apoptosis via targeting miR-449b-5p and regulating HMGB1 and MMP2 expression.

Selective C(sp3)–C(sp2) bond construction is of central interest in chemical synthesis. Despite the success of classic cross-coupling reactions, the cross-dehydrogenative coupling between inert C(s...

Chlorpyrifos (CPF) and cadmium (Cd) are widespread environmental pollutants, which are often present in drinking water and foods. However, the combined effects of CPF and Cd were not entirely clear at present. There was also no biomarker available to diagnose the poisoning of the two chemicals at low dose for long-term exposures. In this study, we investigated the change of serum metabolites of rats with subchronic exposure to CPF, Cd, and CPF plus Cd using gas chromatography-mass spectrometer-based metabolomics approach. We performed a stepwise optimization algorithm based on receiver operating characteristic to identify serum metabolite biomarkers for toxic diagnosis of the chemicals at different doses after 90-day exposure. We found that aminomalonic acid was the biomarker for the toxicity of Cd alone administration, and serine and propanoic acid were unique biomarkers for the toxicities of CPF plus Cd administrations. Our results suggest that subchronic exposure to CPF and Cd alone, or in combination at their low doses, could cause disturbance of energy and amino acid metabolism. Overall, we have shown that analysis of serum metabolomics can make exceptional contributions to the understanding of the toxic effects following long-term low-dose exposure of the organophosphorus pesticide and heavy metal.

Ba(ZrxTi1−x)O3 ceramics (x = 0.15, 0.2, 0.25, 0.3) were prepared with solid-state reaction method. The ratio of Zr/Ti influences the crystal structure, micromorphology, ferroelectric and dielectric properties of BZT ceramics, which were characterized, respectively, by X-ray diffraction, scanning electron microscope, ferroelectric test system and dielectric test system. The X-ray diffraction patterns show that the zirconium titanate ceramic samples adopt cubic phase structure and no secondary phase. As the Zr4+ content increases, the lattice constant increases and the grain size decreases. BZT ceramic sample with 15% zirconium content has the highest dielectric constant. As the Zr4+ content increases, the dielectric constant is gradually decreased, and Curie temperature dropped from 334 to 226 K. The sample has the largest remanent polarization, when the zirconium ion content is 15%. Subsequently, the remanent polarization is reduced as the zirconium ion content increases.

Three series of sulfonate derivatives of paeonol were synthesized and screened in vitro for their anti-oomycete activity against P. capsici, respectively. Among all the compounds, 4m displayed the ...

A new 3-hydroxyphthalimide-based turn-on fluorescent probe is designed and synthesized. This probe can be used to determine the presence of Hg2+ ions by fluorescence spectroscope with high selectivity over other metal ions in aqueous solution. The analytical detection limit for Hg2+ is as low as 6.5 × 10−7 M. The recognition mechanism is attributed to Hg2+-promoted carbonothioate group cleavage and a subsequent excited-state intramolecular proton transfer mechanisms.

Separators are key materials to ensure the safety of lithium-ion batteries and improve their performance. Currently, commercial lithium-ion battery separators are mainly polyolefin organic diaphragms, but their temperature instability leads to battery short circuit and fire risk. A flexible SiO2 nanofiber membrane combined with a poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) nanofiber membrane is prepared by an electrospinning method. The mechanical strength of the SiO2/PVDF-HFP composite nanofiber membrane (SPF) is twice as high as the pure SiO2 nanofiber membrane and at 200°C, there are almost no dimensional changes of the SPF separators. Compared to commercial polyethylene (PE) separators, SPF shows excellent thermal stability and large-area closed cells at 180°C when used in lithium-ion battery separators. The porosity of SPF is 89.7%, which is more than twice than that of an ordinary PE separator. The liquid absorption rate of SPF is much higher than an ordinary PE separator and has reached 483%. Furthermore, the cycle and rate performance of lithium-ion batteries prepared by SPF has been improved significantly. These excellent properties, as well as the potential for large-scale production of electrospinning technology, make SPF an ideal choice for high-power battery separators.