Search

One novel spirolactone, aquilarisinolide (1), three new sesquiterpenoids, (2R,4S,5R,7R)-2-hydroxyeremophila-9,11-dien-8-one (2), (1R,4S,5S,7R,11R)-13-hydroxyepidaphnauran-9-en-8-one (3), and (4R,5S,7R,8S,10S,13R)-8,13-dihydroxyrotunda-1,11-dien-3-one (4), together with 13 known compounds (5–17) were isolated from the resinous heartwood of Aquilaria sinensis (Thymelaeaceae). The structures of the new compounds were elucidated based on the analysis of NMR and MS data and theoretical calculations their ECD spectra. The isolated compounds were evaluated for their protective activities against PC12 cell injury induced by corticosterone (CORT) and 1-methyl-4-phenylpyridine ion (MPP+), as well as inhibitory activities against BACE1. Compound 4, 5,6-dihydroxy-2-(2-phenylethyl)chromone (5), daphnauranol B (7), 6-methoxy-2-[2-(3-methyoxyphenyl)ethyl]chromone (10), isoagarotetrol (14), and 1-hydroxy-1,5-diphenylpentan-3-one (16) showed significant protective effects on CORT-induced injury in PC12 cells at a concentration of 20 μM (P 14) showed a significant protective effect on MPP+-induced injury in PC12 cells at a concentration of 20 μM (P 4 showed a moderate activity (P Graphic Abstract

High-pressure direct-injection (HPDI) of natural gas is one of the most promising solutions for future ship engines, in which the combustion process is mainly controlled by the chemical kinetics. However, the employment of detailed chemical models for the multi-dimensional combustion simulation is significantly expensive due to the large scale of the marine engine. In the present paper, a reduced n-heptane/methane model consisting of 35-step reactions was constructed using multiple reduction approaches. Then this model was further reduced to include only 27 reactions by utilizing the HyChem (Hybrid Chemistry) method. An overall good agreement with the experimentally measured ignition delay data of both n-heptane and methane for these two reduced models was achieved and reasonable predictions for the measured laminar flame speeds were obtained for the 35-step model. But the 27-step model cannot predict the laminar flame speed very well. In addition, these two reduced models were both able to reproduce the experimentally measured in-cylinder pressure and heat release rate profiles for a HPDI natural gas marine engine, the highest error of predicted combustion phase being 6.5%. However, the engine-out CO emission was over-predicted and the highest error of predicted NOx emission was less than 12.9%. The predicted distributions of temperature and equivalence ratio by the 35-step and 27-step models are similar to those of the 334-step model. However, the predicted distributions of OH and CH2O are significantly different from those of the 334-step model. In short, the reduced chemical kinetic models developed provide a high-efficient and dependable method to simulate the characteristics of combustion and emissions in HPDI natural gas marine engines.

Octane sensitivity (OS), as one of the fuel anti-knock quality indexes, is critical with respect to the effective design of next-generation spark ignition (SI) engines. This simulation study focuses on the effects of OS on knock behavior as a function of spark timing (ST) and compression ratio (CR) under boosted high load condition. Eight fuels with identical Research Octane Number (RON) and varying OS were selected to specify the relationship between OS and fuel-specific properties, including a primary reference fuel (PRF), Ethanol Reference Fuels (ERFs), Toluene Reference Fuels (TRFs). It was found that increasing OS to decrease end-gas reactivity is conditional. The end-gas reactivity becomes less sensitive to OS with advancing ST. Analysis for the relationship between OS and fuel-specific properties illustrate that fuel-specific variations beyond OS play an important role in knock tendency when increasing CR, where OS value is insufficient to describe the fuel anti-knock performance. ERF yields better knock resistance than the corresponding OS TRF at high CR conditions. The cause for this behavior is that the decrease in the autoignition temperature moves the end-gas of high OS fuel into a long-ignition-delay region. Comparable chemical and charge cooling effects are effective to retard auto-ignition more dramatically for ERFs.

A comprehensive analytic strategy was performed to study the acaricidal activity ingredients of Bacillus velezensis W1, a strain for biological control of Tetranychus urticae. Through genome mining, 14 biosynthetic gene clusters were identified, which encode secondary metabolites, and these were further confirmed by MALDI-TOF-MS or LC-ESI-MS/MS, including bacillomycin D C13–C17, macrolactin A, 7-O-malonyl-macrolactin A, surfactin C14, and surfactin C15. Moreover, 27 volatile compounds were identified by GC-MS, mainly including cyclodipeptides, alkanes, organic acids, and esters. Finally, 43 compounds identified from W1 were used in the virtual screening of acaricidal activity. The results showed that 16 compounds, including cyclodipeptides, bacillomycins, macrolactins, and surfactins, have acaricidal potential. This work provides a base for studying the mechanism of acaricidal action of B. velezensis W1 and a comprehensive strategy for the study of active ingredients from biocontrol strains.

Developing highly effective photocatalytic hydrogen production in graphitic carbon nitride (g-C3N4) is still a challenging issue. Herein, for the first time, the structural engineering of g-C3N4 nanosheets with Co atoms bonded with compositional N (Co–Nx) is demonstrated to address this challenge. The structure of Co–Nx is formed through the substitution of C atoms in g-C3N4 with Co atoms, which is evidenced by X-ray absorption fine structure spectroscopy (XAFS). Therefore, by adjusting the band structure and electronic structure of g-C3N4, the separation and transfer efficiencies of photo-generated charges are significantly improved. Consequently, the catalysts exhibit a superior visible light photocatalytic hydrogen production rate (5394.35 μmol g−1 h−1) and the apparent quantum efficiency (AQE) of 1.92% at 427 nm.

Our previous study demonstrated that the total saponins from Paris forristii (PCT3) had obvious inhibitory effect on the proliferation of adriamycin-resistant human breast adenocarcinoma cells (MCF-7/ADM), and this effect was significantly stronger than that in parental cells (MCF-7). This study was designed to test the reversal effect of PCT3 on MCF-7/ADM cells and to understand its mechanism of action. Results demonstrated that low cytotoxic concentrations of PCT3 (0.3, 1 and 3 µg/mL) reversed resistance of MCF-7/ADM cells to ADM, cisplatin (DDP) and 5-fluorouracil (5-FU), with reversal fold of 16.4, 19.5 and 31.7 for ADM, 1.6, 1.4 and 1.4 for DDP, 1.7, 1.8 and 5.6 for 5-FU, respectively. Moreover, PCT3 significantly increased the accumulation of ADM and Rhodamine 123 (Rh123) in MCF-7/ADM cells, suggesting that PCT3 may act by affecting the function of drug efflux pump P-glycoprotein (P-gp), which is encoded by MDR1 gene. Both MDR1 gene and P-gp protein expression was downregulated by PCT3 treatment. Further results demonstrated that p38 mitogen-activated protein kinase (MAPK) and extracellular signal-regulated kinase (ERK) pathway was remarkably activated in MCF-7/ADM cells, inhibition of p38 or ERK attenuated P-gp expression. While, only the phosphorylation level of ERK was downregulated by PCT3, indicating that PCT3 sensitized P-gp overexpressed MCF-7/ADM cells to ADM via inhibition of ERK signaling pathway.

High-pressure direct-injection (HPDI) natural gas engines continue to draw much attention for the highly efficient and clean combustion process compared to traditional diesel engines. However, the ...

Two new 2H-pyran-2-one glucosides, cuscutarosides A (1) and B (2), and one new steroidal glucoside, 7β-methoxy-β-sitosterol 3-O-β-glucopyranoside (3), together with 12 known compounds (4–15) were isolated from the whole plant ofCuscuta reflexa(Convolvulaceae) collected from Myanmar. The chemical structures of these new compounds were elucidated based on extensive spectroscopic analysis. The antiobesity activity of these isolates was evaluated using porcine pancreatic lipase (PPL), and the antiplatelet aggregation activity was screened using rabbit platelets induced by thrombin, platelet-activating factor (PAF), arachidonate (AA), or collagen. 7β-Methoxy-β-sitosterol 3-O-β-glucopyranoside (3) showed weak PPL inhibitory activity. Cuscutaroside A (1), its acetylated derivative (1a), and scrophenoside B (8) showed weak inhibitory activity against rabbit platelet aggregation induced by collagen. Compound1aalso showed inhibitory activity against rabbit platelet aggregation induced by AA.Graphic Abstract

The micro-arc oxidization (MAO) ceramic layer on an LA103Z Mg-Li alloy substrate was treated with a hydrothermal treatment at 90 °C for various times. The effect of the hydrothermal treatment time on the microstructure and corrosion behavior of MAO/LDH composite coatings in 3.5 wt.% NaCl solution was investigated, and the mechanism of hydrothermal film formation and corrosion was discussed. The results show that MgO on the surface of the MAO ceramic coating was partially dissolved during the hydrothermal treatment, and the released Mg2+ ions combined with OH− ions in the hydrothermal solution to form Mg(OH)2 nanosheets, which were deposited on the surface of the ceramic coating and its pores. The hydrogen evolution rates of the MAO/LDH composite coatings rank as MAO/LDH-24 h

A luminescent coordination polymer based on Tb(III) has been synthesized with the tripodal carboxylic acid ligand containing N,O codonors (H2PBA = 5-[4-pyridin-3-yl-benzoylamino]-isophthalic acid) as ligand under solvothermal conditions. The chemical formula of this polymer is {[Tb2(PBA)3(H2O)3]·DMF·3H2O}n (1). Complex 1 has good sensitivity and selectivity to picric acid (PA). At 0–30 μmol/L, 1’s quenching constant is 4.5 × 104 L/mol. In the biological function study, the motor function of spinal cord-injured animals after different treatments was evaluated using the blood–brain barrier (BBB) method. The trka expression level on the neural stem cells after treatment was measured to reveal the underlying mechanism.

To improve the corrosion resistance of the ceramic layer prepared by micro-arc oxidation (MAO) on magnesium alloy, a hydrophobic Mg-Al-Co layered double hydroxide (LDH) coating was fabricated on MA...

Calix[4]pyrrole (C4P)-based systems have been extensively explored as binding agents for anions and ion pairs. However, their capacity to act as molecular containers for neutral species remains underexplored. We report here the molecular recognition of pyrazine N,N′-dioxide (PZDO) using a series of aryl extended C4Ps including three α,α-diaryl substituted C4Ps (receptors 1–3), an α,β-diaryl substituted C4P (receptor 4) and an α,α,α,α-tetraaryl substituted C4P (receptor 5). Single crystal structural analyses of the 2 : 1 host–guest complexes between receptors 1–3 and PZDO revealed that the C4P subunits exist in an unusual partial cone conformation and that the PZDO guest is held within electron-rich cavities formed by the lower rims of the individual C4P macrocycle. In contrast, receptor 5 was seen to adopt the cone conformation in the solid state, allowing one PZDO molecule to be accommodated inside the upper-rim cavity. Evidence for guest-directed self-assembly is also seen in the solid state. Evidence for C4P–PZDO interactions in CD3CN/CD3OD solution came from 1H NMR spectroscopic titrations. Electrostatic potential maps created by means of density functional theory calculations were constructed. Density functional theory calculations were also performed to analyse the energetics of various limiting binding modes. On the basis of these studies, it is inferred that interactions between the ‘two-wall’ C4P derivatives (i.e. receptors 1–4) and PZDO involve a complex binding mode that differs from what has been seen in previous host–guest complexes formed between C4Ps and N-oxides. The present study thus paves the way for the further design of C4P-based receptors with novel recognition features., The molecular recognition of pyrazine N,N′-dioxide by aryl extended 'two-walled' calix[4]pyrrole-based receptors is seen to stabilise two different binding modes in the solid state.

It has been a fascinating and significant topic that how the chemical composition and surface structure of nanomaterials govern the catalytic performance. In this paper, we deliberately design molybdenum phosphosulfide nanoparticles anchored on the carbon nanotubes (CNTs) and systematically study the correlation between structure/surface composition and the electrochemical hydrogen evolution reaction (HER) activity and stability. We discover that the HER activities show significant enhancement with the incorporation of P in the molybdenum disulfide structure (MoS2|P/CNT) or S in the molybdenum phosphide structure (MoP|S/CNT). The stability of the MoS2|P/CNT catalyst exhibits high stability which is consistent with the pristine MoS2/CNT, while the stability of the MoP/CNT sample is enhanced after the introduction of the S element. The density function theory (DFT) results indicate that the doped P atoms in the MoS2 structure provide more enhanced active sites, leading to promoted HER activity. For the MoP|S/CNT samples, the doped S site is calculated to be less active for HER yet can greatly enhance P site to present better activity. The anion doping effect unveiled here provides insights into molybdenum phosphosulfides for HER and may also be expanded to broad catalyst design for energy related applications.

A highly efficient, metal-free, chemical oxidation of hydrazines has been implemented using environmentally friendly TCCA as oxidant. This benign protocol provides straightforward access to a wide range of azo compounds in THF in excellent yield. Altogether, 35 azo compounds were obtained in this way and scale-up preparations were performed. Additionally, a plausible mechanism was also proposed. Step-economical process, mild reaction conditions, operational simplicity, high reaction efficiency, and easy scale-up highlight the practicality of this methodology.

The microstructure of the catalyst material is one of the most important factors affecting the photocatalytic performance. In this study, inverse opal structure strontium titanate (SrTiO3, STO) materials with different pore sizes (from 75 to 123 nm) were prepared, and employed as photocatalysts in the degradation of rhodamine B (RhB) dye. The results suggest that the highest photodegradation rate of the inverse opal structure photocatalyst reaches to 88.03%, which is greater than that of the non-inverse opal structure (50.42%) due to its complex three-dimensional porous microstructure. The effect of the pore size of the inverse opal structure STO on the photocatalytic properties was investigated. As the pore size of the inverse opal microstructure decreases, the photocatalytic degradation rate increases regularly, attributing to effective capture of light with decreasing of pore size. The photocatalytic degradation mechanism of inverse opal structure with different pore sizes is discussed in this work.

A visible-light-promoted decarboxylative acyl radical acylation/cyclization cascade reaction of N-methacryloylbenzamides for accessing acylated isoquinoline-1,3(2H,4H)-dione derivatives was described. In this report, α-keto acids were used for generating acyl radicals and inducing radical acylations. This protocol features mild reaction conditions, operational practicality and a broad substrate scope.

A simple, in situ, and one-pot hydrothermal strategy was applied for the successful manufacturing of heterostructured 2D/2D BiOCl/g-C3N4 photocatalysts, and outstanding photodegradation of Rhodamine B in the condition of visible-light irradiation over the composites emerged. The investigation of various BiOCl/g-C3N4 ratios influencing the activity implied that the optimized B2C1 (mole ratio of BiOCl/g-C3N4 with 2:1) exhibited the higher degradation efficiency than that of the rest of the composites, even higher than that of pure BiOCl and pure g-C3N4, which yielded over 90% in the initial 30 min and reached almost 100% during the whole 70 min irradiation process. Kinds of characterizations demonstrated that the enhancement of photodegradation performance was caused by the intimate contact between BiOCl and g-C3N4 to form the heterostructure, which could benefit the generation of abundant visible-light photoinduced carriers and help enhance their separation and then promote their transportation to the surface.

A novel and efficient method for synthesis of polysubstituted trifluoromethylpyridine derivatives by the Bohlmann-Rahtz heteroannulation reaction is described, which use trifluoromethyl-α,β-ynones as trifluoromethyl building blocks to react with β-enamino esters or β-enamino ketones in the presence of ZnBr

The design and fabrication of efficient inexpensive electrocatalysts are critical for electrochemical energy conversion technologies. Control and understanding of electronic configuration at the ac...

α-Amino azines are widely found in pharmaceuticals and ligands. Herein, we report a practical method for accessing this class of compounds via photocatalyzed hydroarylation of azine-substituted enamides with the in situ-generated aryl thianthrenium salts as the radical precursor. This reaction features a broad substrate scope, good functional group tolerance, and mild conditions and is suitable for the late-stage installation of α-amino azines in complex structures.

In conventional electrospinning (e-spinning) process, the curing mechanism can be attributed to the volatilization of solvent or the melt cooling of the jets, which were merely physical processes. To develop novel e-spinning curing mechanism, we propose a conjugate e-spinning one, in which the e-spinning precursors, solution A containing some active monomers, oxidant and solution B containing reductant, are loaded into two different syringes connected with opposite high voltage supplier, respectively. The opposite charged jets attract each other and then meet when flying from spinneret tip to collector. The redox reaction occurs when two jets meet and radicals are produced in situ which can initiate polymerization of active monomers. Then the conjugate jets solidify into fibers under reaction curing mechanism. The new method may give a new approach to produce composite functional fibers.

A new p-terphenyl, 2',3'-diacetoxy-4,5,5',6',4'',5''-hexahydroxy-p-terphenyl (1), along with 12 known compounds were isolated from the fruiting bodies of Sarcodon imbricatus (Bankeraceae). Their st...

Highly active, earth-abundant, and stable electrocatalysts are indispensable for overall water splitting. In this work, hierarchical dendrite-like Co0.75Ni0.25 alloy prepared by a simple hydrothermal reduction route can serve as a high-performance catalyst for hydrogen evolution reaction. The synergistic effect from Co and Ni atoms optimizes the catalytic behavior of their alloy, and the hierarchical dendrite structure enlarges the contact area with the electrolyte, exposing more active sites. Based on the dendrite-like Co0.75Ni0.25 alloy, we further fabricate a core-shell architecture with the conductive N-doped carbon shell coated dendrite-like CoNi/CoNiO2 nanocomposites via a calcination process at 600 ℃ (CoNi/CoNiO2@NC-600). The dendrite-like CoNi/CoNiO2@NC-600 displays significantly improved activity of oxygen evolution reaction due to large active surface area, high conductivity, and the continuous electron transfer among metal, metal oxide, and N-doped carbon. Furthermore, the dendrite-like Co0.75Ni0.25 alloy and CoNi/CoNiO2@NC-600 are assembled into a water splitting electrolyzer with a low voltage of 1.51 V to drive a current density of 10 mA cm−2.

Two cobalt complexes [Co2(L)(phen)(Ac)(PLC)] (1), [Co3(HL)4(CH3O)2(H2O)2] (2) and one zinc complex [Zn2(L)(phen)(Ac)(PLC)] (3), (L = (2-carboxylato-5-(trifluoromethyl)phenyl) (3-hydroxy-4-methoxyphenoxy)amide, phen = 1,10-phenanthroline, Ac = acetate, PLC = 2-amino-4-trifluoromethylbenzoate) have been synthesized and characterized by physicochemical and spectroscopic methods. In addition, X-ray crystallography shows that the Co and Zn atoms in each complex are penta- or six-coordinated, adopting a twisted square pyramid or triangular bi-conical geometry. The antitumor activity of complex against A549 (human lung cancer cells) and Hela (human cervical cancer cells) was screened. Results show that 3 exhibits the most effective antitumor activity (IC50 = 1.369–2.129 μM). Antimicrobial studies also show that 3 exhibits the highest activity.

Objective To clarify the active constituents of the heartwoods of Caesalpinia sappan, a traditional Chinese medicine with the functions of promoting blood circulation (Huoxue in Chinese) and removing blood stasis (Quyu in Chinese). Methods The chemical constituents were isolated and purified by combination of silica gel and Sephadex LH-20 column chromatography, along with semipreparative HPLC. Their chemical structures were established by multiple spectroscopic methods and comparison with literature data. The in vitro antiplatelet aggregation activities were evaluated using mouse platelet induced by AYPGKF-NH2, a gold agonist of protease-activated receptor 4 (PAR4). Results Two new phenols, methyl 2-(4,4′,5′-trihydroxy-2′-(methoxymethyl) biphenyl-2-yloxy) acetate (1) and 1′-methylcaesalpin J (2), together with 24 known compounds (3-26), were isolated from the heartwoods of C. sappan. Among them, sappanchalcone (16) and brazilin (20) showed inhibitory activities against mouse platelet aggregation with IC50 values of 114.8 μmol/L and 100.8 μmol/L, respectively. Conclusion Antiplatelet compounds from C. sappan targeting at PAR4 are reported for the first time.

Deregulation of receptor tyrosine kinase c-Met has been reported in human cancers and is considered as an attractive target for small molecule drug discovery. In this study, a series of 4-phenoxyquinoline derivatives bearing sulfonylurea moiety were designed, synthesized and evaluated for their c-Met kinase inhibition and cytotoxicity against tested four cell lines in vitro. The pharmacological data indicated that most of the tested compounds showed moderate to significant potency as compared with foretinib, with the most promising compound 13x (c-Met kinase IC50 = 1.98 nM) demonstrated relatively good selectivity versus 10 other tyrosine kinases and remarkable cytotoxicities against HT460, MKN-45, HT-29 and MDA-MB-231 with IC50 values of 0.055 µM, 0.064 µM, 0.16 µM and 0.49 µM, respectively. The preliminary structure activity relationships indicated that a sulfonylurea moiety as linker as well as mono-EGWs (such as R1 = 4-F) on the terminal phenyl rings contributed to the antitumor activity.

Ochrocephalamines B-D (1-3), composed of fused quinolizidine and octahydroquinoline rings, were isolated from Oxytropis ochrocephala Bunge. Ochrocephalamine B (1) has a unique bridged tetracyclic ring skeleton fused with a lactam ring. The structures of 1-3 were elucidated using spectroscopic and computational approaches. Ochrocephalamine C (2) and D (3) demonstrated potent anti-HBV activities and are more potent against the secretion of HBeAg than that of HBsAg.

Developing the cost-effective catalyst based on earth-abundant materials is a crucial demand for water oxidation. Doping heteroatom into catalysts is regarded as an effective strategy to regulate electronic configuration and improve the catalytic performance of water oxidation. In this work, N-doped CoS2 on carbon cloth is fabricated by one-step synthesis, in which thiourea acts as both sulfur and nitrogen sources. The N-doped cobalt disulfide shows superior catalytic activity for oxygen evolution, with a low overpotential of 240 mV for 10 mA cm−2, small Tafel slope (56 mV dec−1) and high turnover frequency due to the modification with electronic structure after incorporation of N atom. Moreover, the incorporation of N atom provides a distinctive perspective of doping other heteroatom into the material for modifying the electrochemical properties.

As one of critical base excision repair enzymes, uracil-DNA glycosylase (UDG) can specifically repair uracil-induced DNA damage to maintain the genome integrity of organisms. Moreover, abnormal expression of UDG is related to various cancers and other serious diseases. Therefore, it is essential to accurately and sensitively monitor UDG activity. In this work, a ratiometric fluorescence method using poly-(thymine) DNA template copper nanoclusters (Cu NCs) and 4′,6-diamidino-2-phenylindole (DAPI) as the output signals is developed for simple, selective, and sensitive detection of UDG. A double-stranded DNA (dsDNA) consisting of a uracil-containing single chain and a trigger sequence is designed as a substrate dsDNA. Meanwhile, another dsDNA comprising 30 pairs of A-T bases ((AT)30 dsDNA) is designed to be partially complementary to the trigger chain. The (AT)30 dsDNA itself has no blunt or recessed 3′ end and cannot be cut by exonuclease III (Exo III). With the Exo III-assisted amplification, adding UDG results in the success synthesis of red-emissive Cu NCs, while the dsDNAs in the system are hydrolyzed and the fluorescence signal of DAPI is weak. In contrast, without addition of UDG, the fluorescence intensity of Cu NCs is low, while the DAPI emits significantly enhanced fluorescence signal. The proposed method presents a detection limit of 5.0 × 10−5 U mL−1 and can be applied to the HeLa cell lysate sample with satisfactory results. Additionally, the kinetic parameter is studied and the UDG inhibition effect is evaluated. In summary, this work provides a potential platform for DNA repair enzyme-related analysis and clinical diagnosis.

The dissolution of marine shales and its influence on reservoir physical properties was revealed based on shale samples from the Ordovician-Silurian Wufeng and Longmaxi Formations in the southeast of the Sichuan Basin, China. Three kinds of gas storage spaces were formed by dissolution, including intergranular dissolution (InterD) pores, intragranular dissolution (IntraD) pores and dissolution microfractures (DmF). The diameters of the InterD and IntraD are 10.2–72.4 μm and 0.13–1.52 μm, respectively. The apertures of the DmF are between 0.5 and 11.2 μm. The dissolution effect resulted in a diagenetic environment for quartz cementation and a material basis for calcite veins. The main controlling factors of the dissolution effect are the mineral constituent content in the matrix, the amount of organic matter and the strata burial rate. Dissolution pores and fractures play important roles in shale gas enrichment and migration. The porosity of shale reservoirs with DmF is twice the porosity of reservoirs without DmF, and the spaces formed by dissolution pores and fractures are well connected. A new model for shale gas flow in shale reservoirs was proposed, which provides a new understanding for the connection between organic material pores, and the results can be used for shale reservoirs worldwide.

A metal- and additive-free strategy for the synthesis of oxindoles has been achieved through a chlorine radical-induced cascade chlorination/carbocyclization of N-aryl acrylamides. Trichloroiso­cyanuric acid (TCCA) is used as both radical initiator and chlorine source. A wide range of substrates can be applied in this process to directly afford chlorinated oxindoles via C–Cl and C–C bond formation.

Purpose To investigate the effects of methylene blue (MB) on the viability and secretory phenotype of rat nucleus pulposus (NP) cells in vitro. Methods Rat NP cells were isolated, cultured, and treated with different MB concentrations (0–6.25 ng/mL) for different lengths of time. We evaluated the changes in cell morphology and cell viability. We also examined the cells for expression of collagen II, aggrecan, matrix metalloproteinase (MMP)-3, MMP-9, and inducible nitric oxide synthase (iNOS). Results After 2.5 to 6.25 ng/mL MB induced for 6 hours, numerous NP cells were dyed blue and rounded up. The adherent cell number was reduced by MB treatment. The viability of rat NP cells was significantly inhibited by MB in a dose- and time-dependent manner. Treatment with a very low dose of MB (1.5625 ng/mL) resulted in lower expression of collagen II and aggrecan and higher expression of MMP-3, MMP-9, and iNOS in rat NP cells. Conclusions Rat NP cells exposed in vitro to MB significantly reduced their viability. Moreover, MB upregulated catabolism gene expression and downregulated anabolism gene expression in rat NP cells. These results suggest MB may be harmful to NP cells. The dose of intradiskal injected MB should be as low as possible to prevent or limit the damage to intervertebral disks.

In this paper, surface analysis methods, including ζ-potential (Zp) and cyclic voltammetry (CV), were utilized to obtain the photodegradation mechanism of dye mixture solutions. Firstly, nanostructured SrTiO3 (STO) was prepared as photocatalyst, which is composed of 35–142 nm particles and with specific surface area of 56.90 m2/g. The highest dye degradation efficiency was obtained in the first 30 min of degradation, and enhanced degradation efficiency of methyl orange (MO) was observed in mixture solutions. CV results exhibit different oxidation potential values that demonstrate degraded accessibility under different pH conditions (original pH, 4.30, 2.40, 1.63). ζ-potential (Zp) is measured at different pH values of unitary and binary solutions. Moreover, the influence factors in faintly acidic, neutral and strong acidic conditions are discussed. Kinetic and correlation between H+ and shift of ζ-potential are also studied.

Exploitation of advanced cost-effective electrocatalysts (ECs) is highly desirable for devices engaged in the production of clean energies, such as fuel cells and water electrolyzers. Herein, a series of nickel-based bimetallic selenide, Ni1−xMxSe2 (M = Fe, Co, Cu), nanowires (NWs) grown on carbon fiber paper (CFP) were first synthesized by a general approach, selenizing the corresponding bimetallic oxide NW precursor on CFP, and utilized as anodes for the ammonia-borane (AB) electrooxidation reaction (AOR) in 0.1 M KOH. These nominal Ni1−xMxSe2 anodes exhibit dramatically M-dependent catalytic activities towards the AOR and the electrocatalytic activity follows the order Ni1−xCuxSe2 > Ni1−xFexSe2 > Ni1−xCoxSe2. In particular, the catalytic activity of the Ni1−xCuxSe2 is exceptionally high, surpassing most of the previously reported ECs for the AOR. The follow-up investigations unveil that the Ni1−xMxSe2 NWs on CFP have been converted into ultrathin, porous Ni1−xMxSe2−y–OOH nanosheets (NSs) after the AOR, which presents a unique electrochemical strategy for the synthesis of novel ultrathin bimetallic selenide–oxyhydroxide NSs. Moreover, it is demonstrated that the Ni1−xMxSe2−y–OOH NS anodes exhibit much higher catalytic activities toward the oxygen evolution reaction (OER) than the pristine Ni1−xMxSe2 NW anodes because of the advanced architectures rendering larger electrochemical accessible surface areas (ECSAs) and a modified electronic structure. This work provides a new perspective for design and exploration of highly efficient and durable nonprecious-metal-based ECs for clean energy conversion devices.

Five novel Cd(II) metal–organic frameworks (Cd-MOFs), namely [Cd6(L)4(1,3-bit)2(H2O)4]n (1), [Cd(HL)(4,4′-bbibp)]n (2), [Cd3(L)2(1,4-bimb)2(H2O)2]n (3), [Cd(HL)(4,4′-bidpe)]n (4) and [Cd3(L)2(1,1′-bbi)(H2O)4]n (5) (flexible H3L = 5-(2-carboxylphenoxy)isophthalic acid, rigid 1,3-bit = 1,3-bis(l-imidazoly)toluene, rigid 4,4′-bbibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl, semi-flexible 1,4-bimb = 1,4-bis(imidazol-l-ylmethyl)benzene, semi-flexible 4,4′-bidpe = 4,4′-bis(imidazolyl)diphenyl ether, and flexible 1,1′-bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) were synthesized employing a rational design approach under solvothermal conditions and further characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Diversity architectural topologies have been generated by adjusting the N-donor ligands. They exhibit varied structures: 1 displays an unprecedented 6-nodal (3,3,4,4,8,8)-c 3D topology framework with the point Schlafli symbol of (3·4·5)2(32·42·52·66·78·87·9)(32·63·7)(4·64·8)(410·611·87)(43)2; 2 shows a 2-fold interpenetrating 4-connected cds topology with the point Schlafli symbol of (65·8); 3 exhibits an unprecedented 2-nodal (3,8)-c 3D topology network with the point Schlafli symbol of (42·5)2(44·56·610·75·82·9); 4 shows a 4-connected sql topology with the point Schlafli symbol of (44·62); 5 displays a tfz-d topology 2-nodal (3,8)-c 3D network with the point Schlafli symbol of (43)2(46·618·84). The luminescence studies reveal that MOFs 1–5 display highly sensitive and selective fluorescence sensing towards Fe3+ cations, CrO42− anions and molecular acetone. Meanwhile, the targeted dye adsorption properties of MOFs 1–5 are investigated.

Dye sensitization achieving photoelectrochemical (PEC) signal amplification for ultrasensitive bioanalysis has undergone a major breakthrough. In this proposal, an innovative PEC sensing platform is developed by combining Z-scheme WO3@SnS2 photoactive materials and a G-wire superstructure as well as a dye sensitization enhancement strategy. The newly synthesized WO3@SnS2 heterojunction with outstanding PEC performance is employed as a photoelectrode matrix. Due to the formation of the Z-scheme heterojunction between WO3 and SnS2, the migration dynamics of the photogenerated carrier is evidently augmented. To improve sensitivity, the target excision-driven dual-cycle signal amplification strategy is introduced to output exponential c-myc fragments. Crystal violet is then conjugated into the G-quadruplex to amplify the PEC signal, where crystal violet generates excited electrons by capturing visible light and rapidly injects electrons into the conduction band of SnS2, suppressing the recombination of the photo-induced carrier. Moreover, the G-wire superstructure acts as a universal amplification pathway, ensuring adequate crystal violet loads. Specifically, the biosensor for uracil-DNA glycosylase quantification displays a wide detection range (0.0005-1.0 U/mL) and a lower detection limit (0.00025 U/mL). Furthermore, the Z-scheme electron migration mechanism and the crystal violet sensitization effect are discussed in detail. The construction of the PEC sensor provides a new consideration for signal amplification and material design.

Morphing hydrogels have versatile applications in soft robotics, flexible electronics, and biomedical devices. Controlling component distribution and internal stress within a hydrogel is crucial for shape-changing. However, existing gradient structures of hydrogels are usually non-reconstructable, once encoded by chemical reactions and covalent bonds. Fabricating hydrogels with distinct gradient structures is inevitable for every new configuration, resulting in poor reusability, adaptability, and sustainability that are disadvantageous for diverse applications. Herein, a hydrogel containing reversible photo-crosslinks that enable reprogramming of the gradient structures and 3D deformations into various configurations is reported. The hydrogel is prepared by micellar polymerization of hydrophobic coumarin monomer and hydrophilic acrylic acid. The presence of hexadecyltrimethylammonium chloride micelles increases the local concentration of coumarin units and also improves the mechanical properties of the hydrogel by forming robust polyelectrolyte/surfactant complexes that serve as the physical crosslinks. High-efficiency photodimerization and photocleavage reactions of coumarins are realized under 365 and 254 nm light irradiation, respectively, affording reversible tuning of the network structure of the hydrogel. Through photolithography, different gradient structures are sequentially patterned in one hydrogel that direct the deformations into distinct configurations. Such a strategy should be applicable for other photolabile hydrogels toward reprogrammable control of network structures and versatile functions.

To explore the fuel isomeric effect on ether combustion characteristics, pyrolysis, and laminar flame propagation of di-n-propyl ether (DPE) and diisopropyl ether (DIPE) were investigated. A new kinetic model of DIPE was developed based on our recent DPE model [Fuel 298 (2021) 120797]. The pyrolysis experiments were carried out in two jet-stirred reactors at near-atmospheric pressure with good agreement on the measurements using synchrotron vacuum ultraviolet photoionization mass spectrometry and gas chromatography/mass spectrometry. The decomposition profile of DIPE showed a faster trend than that of DPE, which can be attributed to the faster alcohol elimination reaction of DIPE. The dominant roles of alcohol elimination reaction and H-abstraction reactions in fuel consumption explain the production of fuel-specific oxygenated species, i.e. n-propanol and propanal in DPE and i-propanol, acetaldehyde and acetone in DIPE. The laminar burning velocities of DPE and DIPE were also measured in a high-pressure constant-volume cylindrical combustion vessel at the initial temperature of 373 K and pressures of 1–10 atm. It was found that the linear DPE propagated faster than DIPE with the branched structure under all investigated conditions. Rate of production analysis and sensitivity analysis were also performed to elucidate the key radicals and reactions responsible for the remarkable reactivity of isomeric fuels. Fuel structures have a great influence on the distribution of radical pools, resulting in the easy formation of active radicals in DPE flames such as vinyl and ethyl and stable radicals in DIPE flames like methyl and allyl. The successive decomposition reactions of these dominant radicals promote the DPE flame and inhibit the DIPE flame propagation respectively, which explains the higher laminar burning velocities and reactivity of DPE than that of DIPE. Furthermore, the present model was also examined against the literature data, including pyrolysis and oxidation in the jet-stirred reactor and flow reactor.

Based on the experimental ignition delay results of n-butane/hydrogen mixtures in a rapid compression machine, a Genetic Algorithm (GA) optimized Back Propagation (BP) neural network model is originally developed for ignition delay prediction. In the BP model, the activation function, learning rate and the neurons number in the hidden layer are optimized, respectively. The prediction ability of the BP model is validated in wide operating ranges, i.e., compression pressures from 20 to 25 bar, compression temperatures from 722 to 987 K, equivalence ratios from 0.5 to 1.5 and molar ratios of hydrogen ( X H 2 ) from 0 to 75%. Compared with the BP model, the GA optimized BP model could increase the average correlation coefficient from 0.9745 to 0.9890, in the opposite, the average Mean Square Error (MSE) decreased from 2.21 to 1.06. On the other hand, to assess the BP-GA model prediction ability in the never-seen-before cases, a limited BP-GA model is fostered in the X H 2 range from 0 to 50% to predict the ignition delays at the cases of X H 2 =75%. It is found that the predicted ignition delays are underestimated due to the training dataset lacking of “acceleration feature” that happened at X H 2 =75%. However, three possible options are reported to improve the prediction accuracy in such never-seen-before cases.

The design of Earth-abundant and cost-effective electrocatalysts for highly active and stable electrochemical water splitting in practical production is the primary demand. Herein, bimetallic oxides anchored to three-dimensional (3D) porous conductive nickel foam (NF) are constructed using a simple in situ hydrothermal method for efficient overall water splitting. The vertically aligned Mn3O4/Fe2O3 heterojunction nanosheets have synergy between hierarchical metal oxides and heterogeneous interface, and show excellent performance toward the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in an alkaline environment. By adjusting the molar ratio of Fe : Mn, the morphology, composition and electronic structure of MnFeO-NF-x composites (x represents the ratio of Fe : Mn) can be adjusted to exhibit diverse catalytic activities. In particular, MnFeO-NF-0.4 (0.4 indicates the Fe : Mn ratio of 0.4 : 1) and MnFeO-NF-0.8 display outstanding performance with ultralow overpotentials of 157 mV for the OER and 64 mV for the HER to achieve a current density of 10 mA cm−2, respectively. Furthermore, MnFeO-NF-0.4 and MnFeO-NF-0.8 are assembled into a water splitting electrolyzer, which can reach a current density of 10 mA cm−2 with a low voltage of 1.59 V. Interestingly, Mn–M (M = Co, Ni, and Mo) products can be obtained easily by using different metal salts, indicating the universality of the current one-pot hydrothermal method.

The synergistic corrosion inhibition effect between calcium lignosulfonate (CLS) and three kinds of inorganic inhibitors (Na2MoO4, Na2SnO3, and NaWO4) with various molar ratios on Q235 carbon steel in alkaline solution (pH 11.5) with 0.02 mol/L NaCl was investigated by cyclic potentiodynamic polarization, electrochemical impedance spectroscopy, linear polarization, scanning electron microscopy, and X-ray photoelectron spectroscopy. Molybdate and stannate in hybrid inhibitor could promote the passivation of steel and form a complex film, which could suppress the corrosion effectively. Moreover, the insoluble metal oxides in the complex film formed by three kinds of inorganic inhibitor could help the adsorption of CLS onto the steel surface. The CLS molecules could adsorb onto the steel surface and metal oxides to form an adsorption film to protect the steel from corrosion. A three-layer protection film formed by a hybrid inhibitor, including passivation film, deposition film, and adsorption film, would effectively inhibit the corrosion reactions on the steel surface. The CLS compound with molybdate with the ratio of 2:3 shows the best inhibition effect on both general corrosion and localized corrosion.

An efficient sulfide-catalyzed [2 + 1] annulation of para-quinone methides (p-QMs) with diverse bromides has been achieved. This catalytic strategy provides an efficient and straightforward protocol for accessing a variety of spiro-cyclopropanyl-cyclohexadienone compounds in good to excellent yields (64% to 96% yields) with outstanding diastereoselectivities (>20 : 1 dr), displaying good functional group tolerance as well as gram-scale capacity.

A new green synthetic route to tris[4-(3,4-ethylenedioxythiophene)phenyl]amine (TEPA) monomer has been developed and the molecular structure of TEPA has been determined by using single-crystal XRD. Solution-processable nanoporous poly{tris[4-(3,4-ethylenedioxythiophene)phenyl]amine} (PTEPA) is prepared by a chemical oxidative polymerization in a microemulsion. Based on the distorted structure of TEPA in the solid state, it is proposed that dendritic PTEPA has a distorted 3 D conformation with multiple twisted channels and pores that are narrowed and blocked by bifurcation and distortion of PTEPA, which is consistent with the observed hierarchical pore structure. As a cathode material, PTEPA exhibits a discharge capacity of 89.5 mAh g-1 in the initial cycle with a highly sloping two-stage discharge curve and relatively stable cycling performance. Beyond its excellent energy storage properties, PTEPA also shows relatively good electrochromic performance. Furthermore, an efficient all-solid-state electrochromic supercapacitor (ECSC) with good electrochromic performance and high energy storage capacity (13.3 mF cm-2 ) is assembled from PTEPA and nanoporous graphene films. During charge-discharge processes, the color of the ECSC changes between yellow-green and steel blue. Thus, the energy storage level of the ECSC can be monitored by the corresponding color changes. The fabricated ECSC may have practical applications, for example, in self-powered electrochromic smart windows.